Prosiding Simposium Nasional Polimer V ISSN 1410-8720

PLASTICIZER FROM VEGETABLE OIL DERIVATIVESA REVIEW

Agus l:Iaryono, Riyanto H. Nugroho, Evi T. Wulandari and Wuryaningsih SRResearch Center for Chemistry, Indonesian Institute of Sciences

Kawasan Puspiptek, Serpong 15314, Tangerang

ABSTRACT

PLASTICIZER FROM VEGETABLE OIL DERIVATIVES :A REVIEW. Plasticizer is an additive to enhance

plastic workability and flexibility which added in plastic fonnulation. Most of plasticizers are used for vinyl polymer.Plasticizers used in plastic industries are generally produced from petroleum derivatives, such as phthalatecompounds. Recently, however these plasticizers have much attention in the case of their usage in the field ofmedical equipments and food-grade plastics. These plasticizers are able to migrate in solid and also liquid mediumwhich contact directly with plastic PVe. Many research have been mentioned that if dioctyl phthalate (DOP) hadentered in to human body, the metabolism ofDOP will occurs and DOP derivatives resulted from its metabolism willcause several disruptions in glands perfonnance and male human testis. Although they are still in the area ofdiscussable. Plasticizers from vegetable oil derivatives have major advantages in the case security in food andmedical devices. Epoxidized vegetable oil have advantages in improving light (UY) and heat stability ofPYC plastic.These plasticizers have an equivalent efficiency with DOP from plasticizing mechanism point of view. Estercompounds from vegetable oil derivatives can be used as plasticizers, considering that these molecules own similarstructure with phthalate plasticizers.

Key words: Plasticizers, vegetable oil, epoxies, vegetable oil esters

ABSTRAK

KAJIAN (TINJAUAN) TENTANG PLASTICIZER DARI TURUNAN MINY AK NABATI. Plasticizer

merupakan suatu aditifyang ditambahkan pada pembuatan plasticizer untuk menambah daya kerja dan fleksibilitasplastik. Plasticizer yang sedang dipakai sekarang umumnya berasal dari turunan minyak bumi, seperti senyawaptalat. Tetapi plasticizer turunan minyak bumi ini memiliki kekurangan dalam hal penggunaannya sebagai kemasanmakanan dan peralatan medis mengingat plasticizer bisa bermigrasi pada medium yang cair maupun padat yangberkontak langsung dengan plastik. Banyak riset yang menyebutkan bahwa apabila Dioctyl Phthalate (DOP) telahmemasuki tubuh, DOP akan tennetabolisme akan mengganggu kinerja dari kelenjar honnon dan testis pada manusia.

Meskipun hal ini masih diperdebatkan. Plasticizer dari turunan minyak nabati memiliki keuntungan dari segi keamanandi bidang makanan dan kesehatan. Senyawa epoksi minyak nabati memiliki kelebihan dalam meningkatkan kestabilanplastik PYC terhadap panas dan cahaya (ultra violet). Plasticizer senyawa epoksi juga memberikan efisiensiplastisasi yang setara dengan DOP. Senyawa ester turunan minyak nabati capat dipergunakan sebag<1iplasticizer,mengingat kemiripan struktur molekul yang dimilikinya dengan senyawa ptalat.

Kata kunci : Plasticizer, minyak nabati, senyawa epoksi, s.;:nyawa ester, minyak nabati

INTRODUCTION

Definition of plasticizer aGcording tothe Council of the International Union of Pure

and applied Chemistry (IUPAC) is :a substanceor material incorporated in a material (usuallya plastic or elastomer) to increase its flexibility,workability, or distensibility, also reduce the meltviscosity, lower the temperature of secondorder transition, or lower the elastic modulus ofthe product.

240

High purity, absence of color, neutralreaction, freedom from taste or odor andconsistent quality are required in plasticizing.Certain physical property measurements canalso be helpfull in quality control and productidentification. A significant color increase canbe important indication of productcontaminations; this could have an adverseeffect on heat or light stability or electrical

Plasticizer from Vegetable Oil Derivatives: A Review (Agus I!aryono)

Table 2. Commonly used plasticizers

DOP migrates at a constant rate from

plastics to various environments. It has beendetected in water, soil and food. It is therefore

considered a widespread environmental

contaminant. While biodegradation of DOPOCClli'S in aerobic, nutrient-rich environments over

weeks, its degradation can be extremely slow(many years) uI1der anaerobic conditions.

DOP is able to migrate to its surroundings,so the fmal destination is food consumers/medical

equipment users. Several effects caused by DOP

are; problem on male reproduction, testicular

plasticizing performance and its provision of

adequate properties for a great manycost-effective, general purpose PVC products. Itpossesses reasonable plasticizing efficiency, fusionrate and viscosity (of great importance for slush

moulding applications) and is used predominantlyin the manufacture of soft PVC articles ranging

trom flooring to cable insulation.In Asia, DOP prices stayed at USD

1030-1 050/mt CFR (code of federal regulations)

in East-Asia. Some 12,000 tonnes of phthalates

are used annually in Australia as plasticizers in tl1emanufacture offlexible PVC products. Commonly

uscd plasticizers can be seen in Table 2.

properties. Specific gravity is also an importantpropeDY of plasticizers, it is sensitive test forquality control and useful in helping to identify

an unknown plasticizer, also important indesigning storage facilities. Viscosity propertyhas a significant effect on dry blending andplastisol rheology, also be of a value in quality

control and helping to identify an unknown

plasticizer and important in the design of storageand handling facilities. Refractive index is of

some value in quality control, mainly in detectinggross contamination or an incorrect products,

it has limited value in helping to identify anunknown product because so many plasticizerslie in a relatively narrow range of refractiveindices. Lastly, flash point and pour point data

are essential in designing storage and handlingfacilities, but they lack sufficient to be much use

in quality control or helping to identify anunknown product.

In worldwide growth rates of plastic

additives period 1998-2003, plasticizers have thegrowth of less then 4% per year. A worldwide

analysis consumption can be seen in Table 1.

Table 1. Worldwide analysis of plasticizerconsumptions by PYC market segments

Market SegmentsWorld

ConsumptionFilm and Coated Fabric

35%

Wire and Cable

19%

Extruded and Molded

12%

Flooring

8%

Adhesives, Sealants, Coatings

7%

Food and Regulated Uses

5%

I Miscellaneous

14%

COMMON USED PLASTICIZERS

The most common plasticizer used in plastic

industries is phthalate compound, especially dioctylphthalate (DOP) or di-2 ethyl-hexyl phthalate

(DEHP). The majority ofDOP is manufactured

for use as a plasticizer for the PVC industry. Thereason for this is that it offers good all-round

plasticizer properties. The widespread sales ofDEHP plasticizer are indicative of its all-round

Group

Phthalic acidesters

Phosporicacid esters

Polyfunctionalfatty acidesters

Miscellaneous

plasticizer

Plasticizer

Butyl benzyl phthalate, Dimethyloxyethyl phthalate, Dibutylphthalate (DBP), Butyl octylphthalate, Butyl isodecylphthalate (DBP), Diisooctylphthalate (DIOP), Dicaprylphthalate (DCP), Di-2-ethylhexylphthalate (DOP), n-Octyl n-decylphthalate (ODP), Diisodecyl

hthalate (DIDP)Triphenyl phosphate, Cresyldiphenyl phosphate, Tricresylphosphate (TCP), 2-ethylhexyldiphenyl phosphateDiisobutyl adipate (DIBA),Tri(ethylene glycol) di-2-ethyl butyrate, Dibutil sebacate(DBS), Diisooctyl sebacate(DOS), Butyl acetoxystearateDi(ethylene glycol) dibenzoate,2,2,4-trimethyl-I,3-pentanedioldiisobutvrate

241

Pros;d;ng S;mpos;um Nas;onal Polimer V ISSN 14/0-8720

~Ii= ri~ci= ~ol~1i2us ~caid

Table 4. Oleo-chemicals for polymers-selected examples

Table 3. World production and uses of vegetable oils(1998) [ace. to Oil World, Hamburg} \

use as polymer materials, polymer additives, andbuilding blocks for polymer (Table 4).

r~oil

~oil.mh\Cf

oil. hrn.uJ oil.oleic

acid

~tr:I1 (II. ~ <il

1irrm:J ("il

Market Sectors·World Production

(million tones)Nutrition

81.7

Chemicals

14.2

Animal feeds

5.2

Market SegmentsWorld Production

(million tones)Soybean Oil

22.4

Palm Oil

17.3

Rapeseed oil

12

Sunflower Oil

8.9-Palm Kernel Oil, 5.5Coconut oil

Other plants oils

14.4

- f&ty aid ester.;.-ooi<ts.-WN:S ILtric:ns

BJilding ~cdsIe.- pJ)1ill"

Considering the total market for polymers

of approximately 150 million tonnes in 1997 theshare of oleochemically based products is relatively

small-or, in otl1erterms-tl1e potential fortl1ese

products is very high. The most significantvegetable oil plasticizer is epoxidized soybean oil

(ESO), which holds 43 percent of the vegetable

oil derived plasticizer market. ESO is used as asecondary plasticizer (plasticizers used at levels

of one to four percent) in flexible rve. ESO is a

higher value product because of benefits sUl:hasits resistance to migration, evaporation and

1\')m:r mucrials

- rdyrnIDuJ ~ nm oil. ~(T oil ci:1~ <ils

- Jrl)11'Ui2I:d lirro.rloil lirdwnf\"i)1m-mti=

- f!X1'i<b

- ~ (lliOi Ca'ln)

These negative traits ofDOP have raised

many research concerned in DOP substitution,one of them used vegetable oil as the resource,

especially in epoxidized forms. Althoughvegetable oil derived plasticizers tend to be moreexpensive on a cost per pound basis thanpetrochemical plasticizers, tl1eyoffer performancebenefits which can make their overall economics

favorable. Petrochemical plasticizers such as

phthalates provide only flexibility, but do notcontribute to heat and light stability. As a

result additional stabilizing additives must

be added to supplement these plasticizers.Metallic stabilizers based on metals like

cadmium, lead and barium are added to

plastics to achieve stability to heat and light. Butthese stabilizers have toxicity, and are unsuitable

for many applications, particularly for food

packaging and medical uses. Vegetable oil

plasticizers achieve a double benefit by eliminatingbotl1tl1ecost and tl1etoxicity of metallic stabilizers.

The final economics of use depe;1d on the specific

plastic formulation and the relative costs of the

plasticizer versus the stabilizers which aredisplaced. In many cases the economic benefits

of using vegetable oil derived plasticizers alonewill justify tl1eiruse. Tables 3 depict the productionand market sectors of vegetable oils in the worldin 1998.

The use of oleo-chemicals in polymers has

a long tradition. One can differentiate between the

EPOXIES AND ESTERS FROMVEGETABLE OILSAS PLASTICIZERS

damage (NTP-CERHR [National ToxicologyProgram - Center for The Evaluation of risks tohuman Reproduction, 2000); reproductive &developmental toxicant; DOP is a potential

carcinogen (DHHS [The Department of Healthand Human Services], US Cancer Institute, EPA

(Environmental Protection Agency]); lastly, excessofDOP is capable of producing adverse effectson pituitary gland issue and liver abnormalities. Inmedical devices, DOr is able to migrate in blood

bags, tubings and hoses, Bob Rubin and his friendfound tl1atits migration is 2.5 mg DOPlliter blood

for 24 hours storage.

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Plasticizer from Vegetable Oil Derivatives: A Review (Agus Haryono)

leaching, its low odor, and the stability to light andheat which it adds to PV C. Other epoxidized oilsused by in flexible PVC include linseed oil and

epoxidized tallat<ls,although these account for less

than 9 percent of the vegetable oil plasticizermarket.

Epoxy plasticizers enhance thermal and UV

stability of PVe. They are the only class ofplasticizers that undergo a chemical grafting ontothe PVC polymer at the site oflabile chlorides inthe presence of mixed metal stabilizers. This

chemical family is composed of essentially two

types of epoxidized natural products. Epoxidizedoils, such as soybean oil (ESO) and linseed oil

(ELO) are prepared by the use of peracetic acid,which adds the oxirane structure at unsaturated

(double bond) sites. The parameters of epoxidizedoils can be seen in Table 5. These oils have

molecular weights of approx. 1,000, causing themto perform as low volatility plasticizers. The other

group of epoxy plasticizers is represented by octyl

epoxy tall ate (OET). This product results fromthe epoxidation of tall oil esters, which are theesterified product of tall oil acids. The OET has a

molecular weight of approx. 410, and is amonoester. This causes it to have more limited

compatibility in PVC, and to contribute toward

lower plastisol viscosity and, low temperatureproperties. The primary performance attributes ofepoxy plasticizers are their role in PVC

stabilization, which is accomplished at less than

10 phr levels. Therefore, while they contribute tothe plasticization in PVC, the secondary plasticizer

effects are minimized. A commercial curiosity ofthe epoxidized phthalate-type structure was

found to contribute beneficially to thermal stability,

Tabel5. ESO and ELO Parameter -example

Parameter

Molecular \\cight

Oxirane oxygen (%)

Low-temperature Ilexibility, Tf (0C)Volatility, 24 hours, 90°C (%)

Soapy w.1ter extraction, 24 hours, 900C(%)

n-hexane extraction, 2 hours, 23"C (%)

MineraJ oil extraction. 10 days, 23°C (%)

Migration into foam rubber, 7 days, 6QOC (%)E.xudation, 96 hours, 23°C (%)

Cardboard staining

Epoxidizerl

soybean

oil (ESO)

-10006.8

-20

0.60.19.1

5.94.8

00slight

EpoxidizerlIinseed oil

(ELO)

-10009.0-II0.66.8

3.82.4

2.300

very slight

while otherwise imparting the expected propertiesof the dialkyl phthalate counterpart.

Semsarzadeh, et.al. have conducted

research in dynamic mechanical behavior ofOOP

plasticized PVC-epoxidized soybean oil (ESO),which shows that rheological data reflects theeffects of OOP and epoxidation levels of

soybean oil. The OOP plasticizer forms athermodynamically miscible solution with ESO,

that reduces the rate of fusion ad torque at balanceofPVe. The storage modulus and tan delta ofthe plasticized PVC-ESO have been used to show

the extent of the homogeneity, but the dynamic

mechanical behavior ofPVC-ESO is stronglyinfluenced by OOP and the epoxidation level of

soybean oil. Their research shows that plasticizerblend from OOP and epoxidized vegetable oil isable to give plasticizing effect, although theproperties resulted depend on the levels ofepoxidation of vegetable oil.

Epoxidized esters of palm olein as

plasticizers for PVC were synthesized byalcoholysis, then epoxidations were carried out

in situ by the method ot peroxyformic andperoxyacetic acids. (Gan, et. AI., 1994). Theyemployed alcohols from methanol to dodecyl

alcohol. The esters were evaluated as plasticizers.Long chain epoxy esters were less compatible

while their short chain counterparts were toovolatile for thermal stability. Epoxy butyl esters of

palm olein were found to be most promising asplasticizers for PVe.

Plasticizer which is used in PVC coating

generally OOP which because of the problems inexpense and technology problem, chlorinated

paraffin usually will be used as secondaryplasticizer. Phthalat plasticizer especiallychlorinated paraffin is criticized because of itsharmfulness to environments. This is the reason

why plastic producer started to search alternativeones. Investigation to plasticizer from ester and

its blending to replace phthalate is examined. From

total world production of plasticizer, 90% areabsorbed in PV C industries (husk, floor and wall

cover, etc). So the exploitation of safe alternativeplasticizers is very significant and prospective. Themain obstacles to increasing the market for

vegetable oil derived plasticizers is technological.

243

Pros;d;ng S;mpos;um Nas;ona/ Po/;mer V

In most applications plasticizers such as ESO are

suiTable for use only as secondary plasticizers.At higher levels, they may not mix properly into

the plastics formulation, or may cause plasticsformulations to become brittle. At current levels

of technology, the markets for vegetable oilderived plasticizers are mature, and are likely to

experience growth only with the growth of theplastics market. The American SoybeanAssociation is i:westigating ways to improve the

properties of vegetable oil derived plasticizers. Thisresearch could lead to their use as primaryplasticizers, which are used at levels of up to forty

percent by weight in some flexible plastics. If thiscan be achieved, the potential market for vegetable

oil plasticizers, such as ESO, could be as high as50 thousand tons.

ESTERS COMPOUNDS FROMVEGETABLE OILS AS PLASTICIZERS

Another class of vegetable based

plasticizers are esters. Esters are derived from the

reaction of an alcohol with a fatty acid. Fatty acids

are the main component of vegetable oils. Estersof fatty acids can be fonnulated to produceplasticizers with a range of desirable properties.

Several fatty acids are important in the plasticizermarket. Stearic and oleic acids are available from

a variety of vegetable oils, including coconut,

canola, and soybean, and are used in plasticizers

for polystyrene and cellulosic polymers like

celluloid and ethyl cellulose. Myristic and palmitic

acids, derived primarily from palm oil, are also

used as plasticizers in cellulosic polymers. Sebacicacid, a component of castor oil, is used in

plasticizers for pve. Ester base,<!plasticizers varyconsiderably in price, ranging from $0.60 to

$1.70 per pound, depending on the vegetable oiland alcohol raw materials, and the purity ofthe

plasticizer.

In production, monoesters are synthetized

by reaction of a short chain alcohol and

triglycerides. The catalyst can be Na or Khydroxide, metal alcoholates, metal hydroxyde,metal carbonates, metal acetates, and different

acids. Na and K hydroxyde are the least

expensive. The quantity is around 0.6 %of total

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ISSN 1410-8720

amount of reactants. Diesters are produced bytwo monohydric alcohols with a dicarboxylic acidor a diole and a monocarboxylic acid. It isessential to remove the produced water. The estersynthesis from dicarboxylic acids is more

commonly used than ester production from diols.

Polyol esters are produced in the reaction betweenpolyhydric alcohols and mono-dicarboxylic acids.

Investigations in of castor oil, linseed oil,

risin-oleic acid as plasticizers have beenconducted, just like the usage ofRME (rapeseed

methyl esters) as plasticizer. Wehlmann, et al. hadconducted a research in the usage of RME as

secondary plasticizer in spread-coating dan prosesroll-melting processes.

THE MECHANISM OF THE PLASTICI­ZATION TO THE VINYL POLYMER

For a plasticizer to be effective, it must bethoroughly mixed and incorporated into the pvepolymer matrix. This is typically obtained byheating and mixing until either the resin dissolves

in the plasticizer or the plasticizer dissolves in the

resin. The plasticized material is then molded orshaped into the useful product and cooled.Different plasticizers will exhibit differentcharacteristics in both the ease with which they

form the plasticized material and in the resulting

mechanical and physical properties of the flexibleproduct.

Several theories have been developed toaccount for the observed characteristics of the

plasticization process. A significant review of the

theoretical treatment of plasticization is describedby Sears and Darby. In this treatment,

plasticization is described by three primarytheories, with some modifications. According to

the Lubricating Theory of plasticization, as the

system is heated, the plasticizer molecules diffuseinto the polymer and weaken the polymer-polymerinteractions (van der Waals' forces). Here, the

plasticizer molecules act as shields to reduce

polymer-polymer interactive forces and preventthe formation of a rigid network. This lowers thepve Tg and allows thc polymer chains to move

rapidly, resulting in increased flexibility, softness,and elongation.

Plasticizer from Vegetable Oil Derivatives: A Review (Agus Haryono)

The Gel Theory considers the plasticizedpolymer to be neither solid nor liquid but anintennediate state, loosely held together by athree-dimensional network of weak secondarybonding forces. These bonding forces actingbetween plasticizer and polymer are easilyovercome by applied external stresses allowingthe plasticized polymer to flex, elongate, orcompress.

Free Volume is a measure of the internal

space available within a polymer. As freevolume is increased, more space or freevolume is provided for molecular or polymerchain movement. A polymer in the glassy statehas its molecules packed closely but is notperfectly packed. The free volume is low andthe molecules cannot move past each othervery easily. This makes the polymer rigid andhard. When the polymer is heated to above

the glass transition temperature, Tg, thethermal energy and molecular vibrationscreate additional free volume which allows the

polymer molecules to move past each otherrapidly.This has the effect of making the polymersystem more flexible and rubbery. Free volumecan be increased through modifying the polymerbackbone, such as by adding more side chains orend groups. When small molecules such as

plasticizers are added, this also lowers the Tg byseparatingthe pve molecules,adding tree volumeand making the pve soft and rubbery.MoleculesofPVe can then rapidly move past each other. Ifthe plasticizer unifonnly went into the pve, itwould behave similarly to an uncured rubber,withlots of creep and high compression set. Forexample, uncured tires do not hold their shape;they require a crosslinking cure to give themdimensional stability. Likewise, a thennoplasticelastomer such as pve requires physicalcrosslinks which are melTable to make them

thennoplastic. These melTable crosslinks are thepve crystalliteswhich give pve a physical cure.Therefore, the plasticizer must not be a powerfulsolvent forall the pve parts, butmust be selectivein entering the amorphous pve part and must notenter and destroy the crystalline part ofPV C.

The plasticization mechanism of esters

compound in pve occurs in two steps. The first

step isphysicalmechanism in which the plasticizermixes and soaked in resin particles, continued bythe second step, chemical mechanism, theinteraction between polar groups of plasticizerand resin. The mechanism depicts in Figure 1.

Figure I. Plasticization Mechanism

The mechanisticexplanationofplasticizationconsiders the interactions of the plasticizerwith the pve resin macromolecules. It

assumes that the plasticizer molecules arenot permanently bound to the pve resinmolecules but are free to self-associate and

to associate with the polymer molecules at certainsites such as amorphous sites.As these interactionsare weak, there is a dynamic exchange processwhereby, as one plasticizer molecule becomesattached at a site or center, it is readily dislodgedand replaced by another. Different plasticizersyield different plasticization effects because of the

differences in the strengths of the plasticizerpolymer and plasticizer-plasticizerinteractions.Atlow plasticizer levels, the plasticizer-PVeinteractions are the dominant interactions, whileat high plasticizer concentrations plasticizerplasticizer interactions can become moresignificant.This can explain the observationof anliplasticization, wherein low plasticizer levels« 15 phr) increase rigidity in pve, as measuredby modulus, tensile strength, elongation and lowtemperature properties.

PROPERTIES OFTHE VINYL POLYMERAFTER PLASTICIZATION

The pr~vious section summarized keyplasticizer families and associated perfonnancecharacteristics. Within each family, there are a

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Prosiding Simposium Nasional Polimer V

varietyof isomeric structures and homologues thatcontribute measurable variations in perfonnance.The phthalate family includes a great variety ofisomers and homologues that are useful asplasticizers for PVC. This, then, is an appropriateplasticizer family for the evaluation of the effectsof chemical structures in PVC.

Generalizations derived from phthalatestructures appear to translate into other chemicalfamilies as well. Performance plasticizers (PP)contributing low volatility include those havingmolecular weights greater than that ofDIDP (446)and those ofless branching (oxidative resistance).Linearalkyl structurescontribute low temperatureproperties as well as lower volatility.All aliphaticdibasic esters, such as the adipates, contributeexceptional low temperature properties. Thechemical structures that contribute improved lowtemperature properties typically impart lowerplastisol viscosities, due to their own lowerviscosity; likewise, their reduced tendency forsolvation ofPVC resin contributes to improvedviscositystabilityunder storage conditions. On thenegativeside, the lowtemperature typeplasticizersimpair compatibility in PVC and diffusion­controlled plasticizer loss in end use applications.Octyl epoxy tallate (OET) and tri(2-ethylhexyl)phosphate demonstrate performancecharacteristics similar to those oflow temperatureplasticizers.

Performance plasticizers having strongsolvating characteristics include phthalateshaving higher polarity and aromaticity. Thesestructural features also contribute increased

volatility due to smaller non-polar tails. Non­phthalate plasticizers having strong solvency arehighly aromatic (benzoates, TCP) or other morepolar structures such as sulfonates. Epoxyplasticizers contribute the unique feature ofenhancing thermal stability, and also contributeplasticization properties consistent with theirmolecularstructure.That is, epoxidized oils ( about1,000 molecular weight) enhance low volatility,while monoester OET enhances low temperatureperformance.

Disciplined studies of carefully controlledmodel fonnulations, sample preparation, andconditioninghave shown littlecorrelationbetween

246

ISSN 1410-8720

neat plasticizer properties and their perfonnancein PVC. Key physical properties appear tocorrelatewithplasticizerperfonnance in PVC onlywhen the comparisons are restricted tohomologues of a given chemical family. Furthercorrelation of physical properties of the neatplasticizer with performance in PVC isconfounding; a summary of key physical andperformance properties of plasticizers for PVCverifiesthepoint Theonlymildchemicalinteractionbetween plasticizers and PVC polymers allowsfor the calculation of predicted specific gravity ofthe plasticized PVC compositions. Yet thischemical association precludes quantitativepredictionof plasticizerlossesdue to volatilization(i.e.,usingvapor pressure),or diffusion-controlledmigration.Oxidativeor hydrolyticdegradation,onthe other hand, have the opposite effect whenattempting to predict plasticizer transience nomPVC.

The color of plasticized PVC compositionsis typically not altered by the plasticizer. This isbecause most commercial grade plasticizers arenear "water-white" in color. Highly colored(amber-brown) plasticizers would, of course,impart undesired color to flexible PVCcompositions.

The translation of this basic information to

specific property requirements of flexible PVCproducts is enhanced by an awareness of somegeneralizations relevant to properties influencedby plasticizer chemical structure as well as level(phr) in the PVC, as follows:- Hardness (softness) is significantly influenced

by plasticizer level, as well as type ofplasticizer, which controls plasticizerefficiency.Tensile strength and ultimate elongation (%extension at failure) are influenced by

plasticizer level, but these properties are notsignificantly altered as function of plasticizertype with rvc formulated to specified roomtemperature hardness.Modulus (stiffness, flexibility) values varysignificantly as a function of plasticizer level,and are somewhat influenced by plasticizertype (efficiency) when measured at room

Plasticizer from Vegetable Oil Derivatives: A Review (Agus Haryono)

temperature and formulated to specifiedhardness.

- Low temperature properties, both lowtemperature modulus and brittleness, aresignificantlyinfluencedbyplasticizerlevel(phr)and type.

CONCLUSIONS

Petroleum based plasticizer start to bereplacedwith vegetableoil-basedplasticizer,whichis safer and derived from renewable resources,since the former plasticizer is able to migrate to itssurrounding media, and if it enters into humanmetabolism, it will cause several adverse effects,especially endocrine disruption. Plasticizers tromvegetable oil are in two forms, epoxides andesters. Common resources for epoxidizedplasticizer are soybean oil and linseed oil, which ifcompared to plasticizer from petroleum, theseepoxies are able to contribute in heat and lightstability. Palm oil is also prospective, since palmoil production in Indonesia is number 2 in theworld. So, in the plastic formulation will no needdangerous metal stabilizer. Esters plasticizersusually derived from fatty acids, which can beformulated to produce plasticizers with a range ofdesirable properties, especially stearates,myristates, palmitates and oleates.

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[5]. LEONARD, G KRAUSKOPF, ALLENGODWIN, PVC Handbook, ChapterPlasticizers.

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