PVC Handbook

Charles E. Wilkes, Charles A. Daniels, James W. Summers
ISBN 3-446-22714-8

Vorwort

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Preface

In this single handbook the editors aim to give a diverse audience of readers a complete account of all aspects of PVC – from monomer manufacture to polymerization; the gamut of such additives as stabilizers, lubricants, plasticizers, impact modifiers, fillers and reinforcing agents; blends and alloys; compounding and processing; characterization; combustion resistance and weatherability; product engineering design; applications; environmental and safety; and finally the PVC industry dynamics. Jim Summers’ Introduction presents a good historical background on PVC and several of the individual chapters give a historical perspective to the technologies therein. The handbook contains both practical formulation information as well as a mechanistic view of why PVC behaves as it does. The authors are from both industry and academia. Not surprisingly, many of the industry authors are from the former BF Goodrich laboratories, where much of the industry’s technology was developed. Overall, however, about ten PVC and chemical- supplier companies are represented by the authors. When I joined the BF Goodrich laboratories from graduate school in the mid-sixties, PVC research was one of the many challenges there. I had the great privilege of many conversations with Dr. Waldo Semon, who was still roaming our halls at that time. One of his quotes that will always stick with me was: “Chuck, you’ll find that PVC is perhaps the most inert chlorine compound in existence.” His words preceded by decades the health and safety concerns with chlorinated materials in general. But they are true today. PVC is a very safe material when used and disposed of properly. I probably wouldn’t have agreed to take on this daunting task if it weren’t for tremendous contribution of my co-editors, Jim Summers and Chuck Daniels. With the addition of their broad network of PVC experts, we were able to organize this sterling group of authors. And, they made many detailed technical enhancements to the diverse chapters. Thanks also to Christine Strohm and coworkers at Carl Hanser Publishers for soliciting outside recommendations regarding the make-up of the handbook and for many enhancements in the chapters’ readability. Many of the fundamental technology discoveries related to PVC were made in the 1930’s through the 1950’s. Since those times, continuous improvement, broadening of applications, and process improvements for cost reduction and safety have been the mainstay of PVC research. The billions of pounds of PVC made today still use the free radical catalysts discovered in the ‘30’s. On the innovation front, some readers will be familiar with the PVC Technology Consortium organized by the Edison Polymer Innovation Corporation and carried out over the period 1998 to 2005. I have been privileged to direct this consortium of twenty one sponsor companies from fourteen countries who funded 12 research projects in six universities. I’d like to point out a few highlights of results from that consortium. Rich Jordan University of Chicago), Bill Brittain (University of Akron) and Tony Rappe (University of Colorado) and coworkers gained great understanding toward the metallocene polymerization of vinyl chloride, but in the end were unsuccessful. Their very excellent work has been published and will hopefully stimulate future success in some laboratory. On the other hand, Virgil Percec (University of Pennsylvania) and coworkers have succeeded in living radical polymerization

XII

Preface

of vinyl chloride. This technology has produced narrow molecular weight distribution homopolymers as well as a range of block copolymers (both high Tg and low Tg). Several publications and patents have resulted from this landmark work. Bill Starnes (College of William & Mary) and coworkers have discovered a family of new non-metal PVC stabilizers. Chapter 4 herein and several publications and patents describe the results. Jim White and coworkers (University of Akron) have published and patented new high performance alloy technology, including new block-copolymer compatibilizers. Joe Kennedy and coworkers (University of Akron) have published and patented some novel modifications of PVC via anionic polymerization. Kyonsuku Min and coworkers (University of Akron) published on the preparation of PVC-polyurethane alloys by their reactive formation in a twin screw extruder. Eric Baer and Anne Hiltner (Case Western Reserve University) published excellent fundamental studies of toughness, creep and fatigue resistance in PVCs. Jerry Lando and Morty Litt (Case Western Reserve University) attempted to modify PVC stereostructure by polymerization additives. And, Miko Cakmak (University of Akron) published on the characterization of chemical and morphological changes in PVC compounds during extrusion processing by online measurements. I personally hope that this body of published and patented knowledge will result in a renaissance for PVC – resulting in many new applications and continued good growth. Charles E. Wilkes Akron, Ohio April 2005

Charles Daniels

Charles Wilkes

James Summers

PVC Handbook
Charles E. Wilkes, Charles A. Daniels, James W. Summers
ISBN 3-446-22714-8 Leseprobe 1

Weitere Informationen oder Bestellungen unter http://www.hanser.de/3-446-22714-8 sowie im Buchhandel

with the three largest producers being ExxonMobil Chemical. Throughout the period from 1970 to 1995.2 million metric tonnes (5 billion pounds) produced annually. plasticizer consumption was about one million metric tonnes (2. and Eastman Chemical Company as the major producers. 5. the average growth rate in those regions has ranged between 2 and 3%. Sunoco.2 Historical Developments Several authors have documented the historical developments of plasticizers and their use in PVC. with projected growth rates of only 1–2%.3 million metric tonnes (2. A plasticizer may reduce the melt viscosity. with approximately 90% applied as plasticizers for PVC. Aekyung Industrial Co. workability. and BASF. In 2003. the major producers being Nan Ya Plastics.1 Introduction In 1951. The Far East is not only the largest market for plasticizers but continues to show the highest growth rates. and LG Chemical..8 billion pounds). Sears and Darby [1] provide an extensive review.. the worldwide plasticizer markets grew at rates above the various GNPs. with approximately 2. This rapid growth in China has also contributed to the decline in growth rates in many other parts of the world. In recent years. In North America. BASF. including citations of the use of water and other liquids as “quasi-plasticizers” in non-polymeric materials. or lower the elastic modulus of the product. however this trend has started to decrease in North America and in Europe. Weinberg [2] . The region of the world with the largest plasticizer production is the Far East. The use of plasticizers in PVC and other polymers originated as extensions from low volatility solvents. the International Union of Pure and Applied Chemistry (IUPAC) developed a universally accepted definition for a plasticizer as a substance or material incorporated in a material (usually a plastic or an elastomer) to increase its flexibility. with ExxonMobil Chemical. the worldwide market for plasticizers was more than 4. KRAUSKOPF. Oxeno. lower the temperature of a second-order transition.2 billion pounds).6 million metric tonnes (10 billion pounds). as Chinese imports have displaced locally produced materials. Dahin Co. The plasticizer market in Europe is about 1. Union Petrochemical Corp. There are numerous plasticizer producers in that region. with the Chinese plasticizer market reported to have grown in excess of 12% in 2002. or distensibility.5 Plasticizers LEONARD G. ALLEN GODWIN 5.

which he accomplished via fused plastisol coatings on wire mesh secured to tank interiors. As free volume is increased. of B. Free Volume is a measure of the internal space available within a polymer. elongate. These bonding forces acting between plasticizer and polymer are easily overcome by applied external stresses allowing the plasticized polymer to flex. it must be thoroughly mixed and incorporated into the PVC polymer matrix. . and diisodecyl phthalate (DIDP). Different plasticizers will exhibit different characteristics in both the ease with which they form the plasticized material and in the resulting mechanical and physical properties of the flexible product. A polymer in the glassy state has its molecules packed closely but is not perfectly packed. 5. with some modifications. A significant review of the theoretical treatment of plasticization is described by Sears and Darby [6]. the plasticizer molecules diffuse into the polymer and weaken the polymer-polymer interactions (van der Waals’ forces).3 Mechanisms of Plasticization For a plasticizer to be effective. F. originated the use of plasticized PVC using plastisols (dispersion of PVC particles in plasticizers). Goodrich. In 1968. Changes in costs and availability of raw materials that serve as plasticizer feedstock have caused a significant reduction in the number of plasticizer suppliers and plasticizer products in use. Krauskopf [3] reviewed plasticizers used in polymers. about 80% of the worldwide consumption is comprised of three plasticizers.174 5 Plasticizers [References on Page 198] points out that Waldo Semon. diisononyl phthalate (DINP). Several theories have been developed to account for the observed characteristics of the plasticization process. and elongation. more than 550 different materials were listed as commercial plasticizers. Semon’s objective was to apply corrosionresistant linings to metal storage tanks. According to the Lubricating Theory of plasticization. plasticization is described by three primary theories. or compress. beginning with the use of camphor in nitrocellulose (1868) by the Hyatt brothers and up to Gresham’s patented use of DOP (di-2-ethylhexyl phthalate) in PVC [4] in the early 1940s. In this treatment. The use of DOP prevailed as the preferred general-purpose plasticizer for PVC until the late 1970s. loosely held together by a three-dimensional network of weak secondary bonding forces. the plasticizer molecules act as shields to reduce polymer-polymer interactive forces and prevent the formation of a rigid network. The plasticized material is then molded or shaped into the useful product and cooled. Although there are still approximately 70 different plasticizers available. The Gel Theory considers the plasticized polymer to be neither solid nor liquid but an intermediate state. di-2-ethylhexyl phthalate (DOP). This is typically obtained by heating and mixing until either the resin dissolves in the plasticizer or the plasticizer dissolves in the resin. softness. more space or free volume is provided for molecular or polymer chain movement. as the system is heated. Here. available from over 75 suppliers in the USA [5]. This lowers the PVC Tg and allows the polymer chains to move rapidly. resulting in increased flexibility.

This makes the polymer rigid and hard.5. This can explain the observation of “anti plasticization”. they require a crosslinking cure to give them dimensional stability. it can destroy PVC crystallites. an aromatic ring. there is a dynamic exchange process whereby. the non-polar portion could be the aliphatic side chain of an ester. When the polymer is heated to above the glass transition temperature. elongation and low temperature properties. Tg. with lots of creep and high compression set. Molecules of PVC can then rapidly move past each other. Examples of polar components would be the carbonyl group of carboxylic ester functionality or. As these interactions are weak. adding free volume and making the PVC soft and rubbery. but must be selective in enterring the amorphous PVC part and must not enter and destroy the crystalline part of PVC. For a plasticizer to be effective and useful in PVC. if a plasticizer is too polar. compatibility problems can arise. These meltable crosslinks are the PVC crystallites which give PVC a physical cure. Useful tools in estimating plasticizer compatibility are the Apolar/Polar Ratio method developed by Van Veersen and Meulenberg [7] and the solubility parameter methods [8–11]. . as measured by modulus. tensile strength. while the non-polar portion of the molecule allows the PVC interaction to be controlled so it is not so powerful a solvator as to destroy the PVC crystallinity. Therefore. the plasticizer-PVC interactions are the dominant interactions. It also adds free volume. wherein low plasticizer levels (< 15 phr) increase rigidity in PVC. contributes shielding effects. At low plasticizer levels.3 Mechanisms of Plasticization 175 The free volume is low and the molecules cannot move past each other very easily. a thermoplastic elastomer such as PVC requires physical crosslinks which are meltable to make them thermoplastic. Free volume can be increased through modifying the polymer backbone. polar and apolar. It assumes that the plasticizer molecules are not permanently bound to the PVC resin molecules but are free to self-associate and to associate with the polymer molecules at certain sites such as amorphous sites. as one plasticizer molecule becomes attached at a site or center. The balance between the polar and non-polar portions of the molecule is critical to control its solubilizing effect. Different plasticizers yield different plasticization effects because of the differences in the strengths of the plasticizerpolymer and plasticizer-plasticizer interactions. For example. such as by adding more side chains or end groups. it must contain two types of structural components. The polar portion of the molecule must be able to bind reversibly with the PVC polymer. uncured tires do not hold their shape. This has the effect of making the polymer system more flexible and rubbery. If the plasticizer uniformly went into the PVC. to a lesser extent. The mechanistic explanation of plasticization considers the interactions of the plasticizer with the PVC resin macromolecules. the thermal energy and molecular vibrations create additional free volume which allows the polymer molecules to move past each other rapidly. the plasticizer must not be a powerful solvent for all the PVC parts. while at high plasticizer concentrations plasticizerplasticizer interactions can become more significant. When small molecules such as plasticizers are added. Likewise. it would behave similarly to an uncured rubber. if it is too non-polar. it is readily dislodged and replaced by another. thus softening the PVC. and provides lubricity. this also lowers the Tg by separating the PVC molecules.

Table 5.1 as “Low diffusivity”. Specialty plasticizers impose even higher costs than PP grade plasticizers. Attempts to correlate neat plasticizer properties with performance characteristics were unsuccessful.. there is no implication of chemical structure or physical properties of the plasticizer per se. Such properties are shown in Table 5. Few phthalates meet these special requirements.176 5 Plasticizers [References on Page 198] 5. therefore. Polyester plasticizers provide low volatility and low diffusivity. which relates in part to their molecular weight. Specialty Plasticizers (SP): provide properties beyond those typically associated with flexible PVC designed for general purpose or specialty characteristics.4 Types of Plasticizers Plasticization is achieved by incorporating a plasticizer into the PVC matrix through mixing and heat. coherent databases of properties measured on flexible PVC as a function of a broad range of plasticizer levels (i. while imposing somewhat higher costs. variations in isomeric structure and homologues within any given chemical family contribute performance variations that have been measured in flexible PVC compositions. and “Flame resistance”. These are dialkyl phthalates ranging from diisoheptyl (DIHP) to diisodecyl (DIDP). along with low smoke (in the absence of aromaticity) under fire conditions. The IUPAC definition of a plasticizer is entirely focused on performance characteristics when combined with a polymer. phosphates and halogenated plasticizers provide fire retardant properties. Early technical publications. depending on their synthesis steps.1 shows the major chemical families of PVC plasticizers vs. “Low temperature” and “Low volatility”. “Stability”. key performance criteria. These include specific phthalates and other types of plasticizers. It is preferred to categorize plasticizers on the basis of their chemical structure and associated performance when employed in PVC. such as aliphatic dibasic esters. are less solvating and have higher diffusivity.e. Plasticizers may be classified as either monomeric or polymeric plasticizers.1 identifies these key performance criteria as “Strong solvaters”. Low volatility requires high molecular weight plasticizers. generalizations became possible only after development of large. 20–90 phr) for many commercial and experimental plasticizers [12]. along with low cost oils called “extenders”. Table 5. Epoxy plasticizers provide adjuvant thermal stability to PVC. presented rather vague categorizations based on observed performance properties. An orderly comparison of plasticzers is facilitated by separating all plasticizers types into three subgroups relating to their performance characteristics in PVC: General Purpose (GP): plasticizers providing the desired flexibility to PVC along with an overall balance of optimum properties at the lowest cost. . Performance Plasticizers (PP): contribute secondary performance properties desired in flexible PVC beyond the GP type. Strong solvaters have higher polarity and/or aromaticity. These exceptional characteristics are typically a function of specific chemical plasticizer families and may vary as a function of isomeric structure and/or homologues. such as trimellitates and polyesters (polymeric). low temperature types. In addition. The key performance properties are influenced by plasticizer level (phr) as well as the chemical type. Conversely.

Phthalate esters: prepared by the esterification of two moles of a monohydric alcohol with one mole of phthalic anhydride. diisooctyl (C8). while phthalate esters prepared from alcohols greater than C13 have limited compatibility. Phthalates are the most widely used class of plasticizers in PVC. Although phthalate esters can be prepared from many different alcohols.1 indicates the primary performance characteristics associated with each chemical family by “X”. Phthalate esters prepared from alcohols below C4 are too volatile.4 Types of Plasticizers 177 Table 5. or combinations thereof.5.1 Plasticizer Family/Performance Grid Family General purpose Performance plasticizers Strong solvent √ Low temp √ √ X X √ √ √ √ Specialty plasticizers Low Low Stability Flame volatility diffusion resistance √ X √ √ √ Phthalates Trimellitates Aliphatic dibasic esters Polyesters Epoxides Phosphates Extenders Miscellaneous X X X X X X X X X = Primary performance function √ = Secondary performance function Table 5. or blends of linear heptanol. as indicated by the “√”. As shown.5 through 5. Many commercial grade phthalates are prepared using a mixture of monomeric alcohols. which is prepared from 2-ethyl hexanol. Note that the family of phthalate plasticizers show an offering in all of the performance categories. Performance comparisons of these materials are reviewed in Sections 5. the range of alcohols used to make plasticizers for PVC applications is generally limited from C4 to C13 alcohols. their cost and availability supports their preference. diisononyl (C9) and diisodecyl (C10) phthalates. and so forth. Formulating refinements in plasticizer performance and cost constitute the selection of preferred isomers and homologues of any given chemical family. the current market for GP plasticizers includes dialkyl phthalates that are slightly different homologues of DOP. such as butanol with 2-ethylhexanol. While historically DOP – di(2-ethylhexyl) – phthalate has been the product of choice. establishes the standard against which other plasticizers may be compared. Extenders: shown in the general purpose plasticizer category because they are most commonly employed with phthalates to reduce costs in general purpose flexible PVC. In addition. nonanol. Di-2-ethylhexyl phthalate (DOP). such as diisoheptyl (C7). they contribute the most complete array of required performance properties in flexible PVC. . while “√” denotes secondary functions associated with products in that class of plasticizers. and undecanol.9. their combined usage totals more than 80% of the worldwide plasticizer market.

are a result of increased polarity and/or aromaticity. strong solvaters. while aliphatic hydrocarbons are limited to less than 10%. The plasticizers with lower chlorine content have lower specific gravity.9. 911P. Thus. which is also reflected in low vapor pressure. these plasticizers also contribute to volatile fuming during processing and volatilization in end use applications. “PP-LV”s are low volatility plasticizers primarily because of their high molecular weight. Plasticizer structural relationships with low temperature performance will be reviewed in Sections 5. strong solvator. all shown in Table 5. Di-2-ethylhexyl adipate (DOA) is the standard and most widely used plasticizer in this class. These lessbranched alkyl groups contribute improved low temperature properties in all the chemical families of plasticizers. and DUP. . “PP-LT”. In addition to selected phthalate candidates.. “PP-SS”s. UDP. and “PP-LV”. for example. naphthenic hydrocarbons may be used up to 35 weight% in dialkyl phthalate plasticizers.178 5 Plasticizers [References on Page 198] These low cost oils have limited compatibility in PVC. low volatility. there are non-phthalate plasticizers of high aromaticity that serve as strong solvators. octyl (BOP). High molecular weight phthalates that serve as “LV” plasticizers include those having molecular weights greater than DIDP (446). di-2-ethylhexyl sebacate (DOS).2.5 through 5. “PP-LT”s are low temperature phthalates made with normal or “linear” alcohols. viscosity. This maintains the apolar/polar ratio required to provide PVC compatibility along with low temperature properties. but are commonly employed as secondary plasticizers worldwide. and vice versa. High molecular weight phthalates having low volatility and compatibility with PVC include DIUP. Chlorinated paraffin extenders are not widely used in the U. and color. “Performance Plasticizers” have three subgroups: “PP-SS”. Increasing the molecular weight of phthalates increases the ratio of apolar/polar functionality until loss of PVC compatibility occurs at molecular weights greater than that of DTDP (530). These secondary plasticizers are used to reduce cost and to improve fire resistance. The entire family of aliphatic dibasic esters contributes exceptional low temperature properties. such as adipic or azelaic acid. They are prepared by the esterification of one mole of dibasic carboxylic acid. DTDP. Two chemical families are noted for their use as low volatility plasticizers – trimellitates and polyesters (also referred to as polymerics). Di-2-ethylhexyl azelate (DOZ). such that the total carbon content per molecule ranges between C18 and C26.S. Higher molecular weight phthalates are less tolerant of extender levels due to their reduced compatibility in PVC. In addition. Lower molecular weight alcohols are used with higher molecular weight acids. Chlorinated paraffins are produced by chlorination of hydrocarbons up to a chlorine content in the range of 30–70%. as well as butylbenzyl (BBP) phthalate fall into this category. Such materials are benzoate esters and tri(cresyl) phosphate. lower molecular weight phthalates such as dihexyl (DHP) and butyl. with two moles of monohydric alcohols. and diisononyl adipate (DINA) are used for low temperature applications requiring lower plasticizer volatility. other chemical structures contribute desired performance attributes. low temperature. while higher chlorine content imparts increased fire resistance.

05 1.00 0.16 1. 365 334 362 390 390 390 418 446 474 ca.01 NA 1. benzyl butyl.86 1.98 butyl. C10) di(n-nonyl) di(linear nonyl) di(linear C7. C12. 2-ethylhexyl di(isohexyl) di(isoheptyl) di(2-ethylhexyl) di(isooctyl) di(2-normal-octyl) (aka capryl) di(isononyl) di(isodecyl) di(isoundecyl) di(iso C11.96 0.4 Types of Plasticizers 179 Table 5.99 1.10 1. 502 530 278 ca.21 1. 446 474 ca.14 1. C9) di(2-ethylhexyl) di(isooctyl) di(isononyl) .06 1.27 0. C11) di(linear C11) tri(n-C8. Chemical Compositions. 370 370 370 398 Subst.94 0. C8.12 1.93 0.19 1.27 0.99 0. and Substitution Factors Acronym Phthalates BBP BOP DHP DIHP DOP DIOP DCP DINP DIDP DIUP UDP DTDP Linear phthalates DBP 79P NHDP(610P) DNNP L9P 7911P 911P DUP Trimellitates NODTM TOTM TIOTM TINTM Adipates 79A DOA DIOA DINA Chemical structure Molecular weight ca.* factor 0.17 1.94 0. 418 ca.00 1. C11) di(linear C9.94 0. 418 418 418 ca. 312 ca.94 0.90 0. C13) di(isotridecyl) di(n-butyl) di(linear C7.97 1.00 1.2 Plasticizer Acronyms. C9. 592 546 546 588 ca. C10) tri(2-ethylhexyl) tri(isooctyl) tri(isononyl) di(linear C7.5. C9) di(n-C6. 390 ca.

diphenyl tri(2-ethylhexyl) tricresyl 2-ethylhexyl epoxy tallate epoxidized soybean oil di(2-ethylhexyl)terephthalate di(isononyl) cyclohexane-1.96 1. and “SP-FR” for fire resistance in PVC. Polyethylene copolymers (EVA’s. 410 ca. etc.000.000. Polyesters are prepared by the esterification of propylene glycol or butylene glycol with aliphatic dibasic acids. contributes higher molecular weight. But the polyester family is noted for its outstanding performance in this category. on the other hand they are more susceptible to oxidative attack.000 390 422 Subst.9 phr).180 5 Plasticizers [References on Page 198] Table 5.00 1.* factor 0. Glutarate polymerics reportedly have a proven history of providing good weathering resistance [13]. and are sometimes used in combination with more costly diffusion-resistant plasticizers. “SP-Stab” for stabilizing function.10 1.96 1. or molecular weight. The polarity. . also impacts extraction resistance of the polymerics. the greater its permanence. Lower polarity materials exhibit better extraction resistance towards polar extraction fluids such as soapy water. Polymeric plasticizers composed of branched structures are more resistant to diffusivity losses than those based on linear isomeric structures. 1.000 to 8.2-dicarboxylate * Substitution factor = PHR required for 80A Durometer hardness at room temperature vs.03 NA isodecyl.) and terpolymers can range up to > 500. The greater the plasticizer viscosity. with a molecular weight range from 1. “Specialty Plasticizers” are also divided into three subgroups: “SP-LD” for low diffusion. Trimellitates are the product of three moles of monohydric alcohols and trimellitic anhydride (TMA). Diisodecyl phthalate (DIDP) and diisotridecyl phthalate (DTDP) impart improved resistance to diffusion-controlled plasticizer losses. required DOP level (52. VAE’s.31 0. Polymeric plasticizers are typically polyesters.2 (continued) Acronym Phosphates DDP TOF TCP Epoxides OET ESO Others DOTP DINCH Chemical structure Molecular weight 390 435 368 ca. the third ester group contributes sufficient polarity to maintain PVC compatibility. The third alkyl group. Low diffusivity is contributed by high molecular weight and highly branched isomeric structures. compared to phthalates. or the oxygen-to-carbon ratio.

8 reviews the performance . while otherwise imparting the expected properties of the dialkyl phthalate counterpart [15]. respectively. Hercoflex® 600 is the pentaerythritol tetraester and 707 is a mixture of tetra and hexa esters. A combination of phosphate plasticizers. they are esterified with a stream of straight chain fatty acids to make plasticizers. Pentaerythritol esters are a type of “miscellaneous” plasticizers that impart both low volatility and diffusivity.000. which are the esterified product of tall oil acids. the trimellitate plasticizers demonstrate improved resistance to diffusivitycontrolled losses only under certain conditions. and is a monoester. which is accomplished at less than 10 phr levels. but generates high smoke under fire conditions. A commercial curiosity of the “epoxidized phthalate-type” structure was found to contribute beneficially to thermal stability. using a mixture of pentaerythritol and dipentaerythritol. while they contribute to the plasticization in PVC. most typically 2-ethylhexanol. This chemical family is composed of essentially two types of epoxidized natural products. which can cause crazing of the ABS door liner. The highly aromatic tricresyl phosphate (TCP) is the most effective fire retardant. “Phthalate-like” esters include DOIP [di (2-ethylhexyl) meta (called “iso”) phthalate]. Section 5. and zinc borate yields a superior flame retardant grade of PVC for demanding applications such as plenum cable jacketing and electrical insulation [16].4 Types of Plasticizers 181 Interestingly. and similar materials. Pentaerythritol and dipentaerythritol are tetra and hexa alcohols. 1. causing them to perform as low volatility plasticizers. which adds the oxirane structure at unsaturated (double bond) sites. Their molecular weights are approximately 600 and 750. Phosphate plasticizers may be combined with phthalates to reduce formulating costs. and to contribute toward lower plastisol viscosity and low temperature properties. They are the only class of plasticizers that undergo a chemical grafting onto the PVC polymer at the site of labile chlorides in the presence of mixed metal stabilizers [14]. such as soybean oil (ESO) and linseed oil (ELSO) are prepared by the use of peracetic acid. antimony trioxide. Trialkyl phosphates (like TOF) are less efficient in fire resistant properties. and DOTP [di (2-ethylhexyl) para (called “tere”) phthalate]. Therefore. which are isomeric structures of DOP. and efficiency. pentaerythritol esters. DOTP is commercially available at similar costs to DOP. This product results from the epoxidation of tall oil esters. Epoxy plasticizers enhance thermal and UV stability of PVC. These oils have molecular weights of approx. This causes it to have more limited compatibility in PVC. respectively. Commercial phosphate plasticizers use combinations of aryl and C8 and C10 alkyl groups to offer a balance of fire reduction. The other group of epoxy plasticizers is represented by octyl epoxy tallate (OET). The OET has a molecular weight of approx. Brominated phthalate esters are produced by the esterification of tetrabromophthalic anhydride with various alcohols. Trimellitates in combination with polyester plasticizers control migration from PVC refrigerator gaskets. Epoxidized oils. volatility. benzoates. which contributes to both low volatility and diffusivity. Phosphate plasticizers which may be considered as “inorganic esters” are prepared by the slow addition of phosphorous oxychloride to alcohol or phenol. the secondary plasticizer effects are minimized.5. citrates. Flame resistant plasticizers include halogenated (preferably brominated) phthalates and the phosphate family. However. sulfonates. trimellitates fail to provide reduction of plasticizer diffusivity under oil immersion tests. The primary performance attributes of epoxy plasticizers are their role in PVC stabilization. Miscellaneous plasticizers include “phthalate-like” esters. 410.

Linear alkyl structures contribute low temperature properties as well as lower volatility. it is described as the phenyl cresyl esters of pentadecyl sulfonic acid. owing to its strong solvating strength. This. Performance plasticizers (PP) contributing low volatility include those having molecular weights greater than that of DIDP (446) and those of less branching (oxidative resistance). Esterification with benzoic acid yields the mixed ester. usually diols.182 5 Plasticizers [References on Page 198] characteristics of DOIP and DOTP. except for having less solvency for PVC. Within each family. Its preferred use is in vinyl sheet flooring. citrate plasticizers are tetraesters. Preferred glycols are dipropylene glycol and butane diols. Hexamoll® DINCH is di (isononyl) cyclohexane-1. is an appropriate plasticizer family for the evaluation of the effects of chemical structures in PVC.2-dicarboxylate [17]. 5.5 Plasticizer Performance The previous section summarized key plasticizer families and associated performance characteristics. These sensitivities are also addressed with the recent introduction of a novel triester plasticizer completely devoid of carbon ring configurations. Mesamoll® is a product of Bayer. It is reportedly resistant to hydrolyses and diffusion controlled plasticizer losses. its performance characteristics in PVC are expected to be similar to the phthalate counterpart. One commonly used benzoate is dipropylene glycol dibenzoate (DPGDP. The phthalate family includes a great variety of isomers and homologues that are useful as plasticizers for PVC. All aliphatic dibasic esters. commercially Benzoflex® 9-88). Sulfonates also exhibit strong solvency for PVC. the hydrogenated product of the corresponding di C9 phthalate ester(DINP). and it reportedly controls plasticizer bleeding into asphalt adhesives. Generalizations derived from phthalate structures appear to translate into other chemical families as well. Benzoflex® 1046 is a mixed ester of benzoate ester of Texanol®. DINCH has recently been introduced by BASF as a candidate for applications with sensitivity for peculiar health and environmental concerns. where the benzoate enhances processing. The chemical structures that contribute improved low temperature properties typically impart lower plastisol viscosities. while the low molecular weight contributes a hardened. there are a variety of isomeric structures and homologues that contribute measurable variations in performance. likewise. resulting from the reaction of one mole of an organic acid (with the single alcohol group) and three moles of alcohol. Therefore. contribute exceptional low temperature properties. Texanol is an “ester-ol” resulting from the Aldol and Tischenko condensation reactions of three moles of isobutyraldehyde. As indicated [15]. then. which esterify the three acid groups. due to volatilization. stain resistant surface. However. Citrates are promoted for plasticized PVC applications facing exceptional toxicological and/or environmental constraints. such as the adipates. their reduced tendency for solvation of PVC resin contributes to improved viscosity stability . neat citric acid does not meet PVC compatibility requirements. due to their own lower viscosity. Its preferred use is in PVC flooring products. it is claimed for use in medical applications and “low smoke” grade PVC electrical insulations [18]. Benzoates are the esterification products of benzoic acid and selected glycols.

have the opposite effect when attempting to predict plasticizer transience from PVC. as follows: . This example shows typical properties for general purpose PVC containing DINP levels ranging from zero (rigid vinyl) to about 600 phr (parts per hundred resin. The color of plasticized PVC compositions is typically not altered by the plasticizer. by weight). at about 600 phr. This is because most commercial grade plasticizers are near “water-white” in color. The average consumption of plasticizers in flexible PVC stands at 50 phr. a summary of key physical and performance properties of plasticizers for PVC verifies the point [15]. raw materials. sample preparation. while monoester OET enhances low temperature performance. Useful commercial products typically range from about 20 to 100 phr. fishing lures. Performance plasticizers having strong solvating characteristics include phthalates having higher polarity and aromaticity. Highly colored (amber–brown) plasticizers would. The effects of a wide variation in plasticizer level on the mechanical properties of PVC compounds are listed in Table 5. Oxidative or hydrolytic degradation.5 Plasticizer Performance 183 under storage conditions. and conditioning have shown little correlation between neat plasticizer properties and their performance in PVC [19–22].5. That is. are an exceptional product. and also contribute plasticization properties consistent with their molecular structure. epoxidized oils (about 1. using vapor pressure). The only mild chemical interaction between plasticizers and PVC polymers allows for the calculation of predicted specific gravity of the plasticized PVC compositions. Such procedures have been described [12]. Reliable generalizations of plasticizer structure/performance relationships require extensive evaluations using disciplined model formulations. or diffusion-controlled migration [19. impart undesired color to flexible PVC compositions. and conditioning in the measurement and cataloging of the data. Epoxy plasticizers contribute the unique feature of enhancing thermal stability. 23. the low temperature type plasticizers impair compatibility in PVC and diffusion-controlled plasticizer loss in end use applications. Disciplined studies of carefully controlled model formulations. Yet this chemical association precludes quantitative prediction of plasticizer losses due to volatilization (i. On the negative side. Other publications have utilized these data to provide analyses and comparisons of various commercial and experimental plasticizers [15.3. 26–28]. sample preparation. Non-phthalate plasticizers having strong solvency are highly aromatic (benzoates. 23–25]. The translation of this basic information to specific property requirements of flexible PVC products is enhanced by an awareness of some generalizations relevant to properties influenced by plasticizer chemical structure as well as level (phr) in the PVC.000 molecular weight) enhance low volatility. Octyl epoxy tallate (OET) and tri(2-ethylhexyl) phosphate demonstrate performance characteristics similar to those of low temperature plasticizers.e. of course. Key physical properties appear to correlate with plasticizer performance in PVC only when the comparisons are restricted to homologues of a given chemical family.. TCP) or other more polar structures such as sulfonates. These structural features also contribute increased volatility due to smaller non-polar tails. Further correlation of physical properties of the neat plasticizer with performance in PVC is confounding. on the other hand.

Modulus values vary significantly as a function of plasticizer level. Nass. siding. due to variations in test methodology forces of extension.700 21 3. but these properties are not significantly altered as function of plasticizer type with PVC formulated to specified room temperature hardness. (Eds. Shades.02 < 10 – – – – – – – Fishing lures b Bottles. 15 s Flexural stiffness at 23 °C MPa psi Tensile strength MPa psi Elongation (%) Brittleness °C °F Examples c b a Semirigid 34 25 Flexible 50 33 Very flexible 80 44 Extremely flexible 600 86 0 0 1. in Encyclopedia of PVC. L.Boots. A.17 66 3.100 295 –32 –26 1. produce wrap Wall-cover. p. binders. The three different techniques for determination of modulus at room temperature result in significantly different absolute values. Modulus (stiffness.184 5 Plasticizers [References on Page 198] Table 5. 2nd ed. which controls plasticizer “efficiency”.26 94 69 10. Tensile strength and ultimate elongation (% extension at failure) are influenced by plasticizer level. 20/20 °C Hardness Durometer A.4 500 14 2.40 – > 900 > 130. Marcel Dekker (1988). and are somewhat influenced by plasticizer type (efficiency) when measured at room temperature and formulated to specified hardness. flexibility) may be measured under tensile stress (ASTM D 882) at a specified strain level. ing. as well as type of plasticizer.3 Typical Properties of General Purpose Vinyl Plastic Products Rigid DINP. and shear. L.500 225 –16 +3 1.. book.000 < 15 > 23 > 73 1. records thin films. pipe. or under flexural stress (ASTM D 747). phr Wt% of composition Typical properties Specific gravity. C. 149 (reprinted with permission) Hardness (softness) is significantly influenced by plasticizer level. and Heiberger. garden hose a b c ASTM D 747 ASTM D 882 ASTM D 746 Source: Krauskopf. water beds upholstery. compression.. shoe heels.000 31 4.000 > 41 > 6.). . or under torsional stress (ASTM D 1043). N.22 84 12 1.000 400 –47 –53 1. G.gloves.

and impart improved low temperature properties and volatilization and oxidative resistance [29. a specific product available in Europe.5.. “Moderately branched” nonanol is the hydroformylation product of mixed olefins generated by the dimerization of a mixture of propylene and normal butene feeds. These configurations are a function of the starting materials and processes used to produce the plasticizer-grade alcohols. and stability to thermal and oxidative degradation. Krauskopf [31] differentiated plasticizer performance effects as a function of five different degrees of branching using commercial grade di(C8). except for a limited amount of commercial products based on mixtures of normal C6. Commercially. and octenes. Variations in isomeric structure are primarily imparted by the nature of the alkyl moiety.00). These variations in degrees of branching demonstrate measurable effects on PVC properties with respect to plasticizing efficiency. are significantly influenced by plasticizer level (phr) and type. NOTE: Reliable measurements of failure properties require that test specimens be completely free of surface imperfections (nicks/cuts). these were grouped as: Normal: 100% unbranched. The resultant olefin is a mixture of hexenes. Low temperature modulus values are determined by ASTM D 1043 (Clash-Berg. Moderately branched (MODBR): primarily dimethyl or monoethyl (i. while showing increased resistance to diffusivity. Slightly branched (SLBR): primarily a mixture of monomethyl and dimethyl branched alcohols. Highly branched (HIBR): triple methyl branched. these serve as the major type in “General Purpose” plasticizer category.F. volatility. 2-ethylhexyl) branched. The resultant alcohol is approximately a 70/30 molar ratio of normal/2-methyl branched isomers.) of 0.F.di(C9). the “linear” phthalate is only slightly deficient to the normal nonyl phthalate with respect to low temperature . The “highly branched” nonanols are the hydroformylation product of trimethyl branched pentenes which are a product of dimerized isobutene. When compared at equivalent hardness in PVC. 30]. while brittleness temperature is determined by ASTM D 746 (TB).5 Plasticizer Performance 185 Low temperature properties. These are notably susceptible to oxidative attack. The octenes are hydroformylated to give nonanol mixtures primarily composed of dimethyl substituted C7 backbones. Linear: a mixture of normal and monomethyl branched alcohols.5. both low temperature modulus and brittleness. C8. The normal C9 phthalate has a substitution factor (S. Tf). completely fused and conditioned at room temperature (ASTM conditions preferred) for at least 24 hours following preparation of specimens. while the plasticizing efficiency of the “linear” nonyl phthalate is equivalent to that of DOP (S. = 1. These “linear” alcohols are produced by the hydroformylation (Oxo process) of normal alpha olefins. and C10 alcohols.94.e. primarily an academic product. which are separated by distillation. The resultant alcohol (nonanol) is a random mixture of monomethyl octanols and dimethyl heptanols. diffusivity. low temperature properties. and di(C10) phthalates. Plasticizers made with more linear (less branched) molecular structures are more efficient. the “slightly branched” alcohols are the hydroformylation products of octenes that are dimerized normal butenes. heptenes. the resultant alcohol is primarily 3.5-trimethyl hexanol.

186 5 Plasticizers [References on Page 198] properties and volatility.06) and a deficiency in low temperature properties and volatility vs. The “moderately branched” (MODBR) DINP shows less plasticizing efficiency (S. the DINP (MODBR) provides equivalent low temperature properties with significantly lower volatility. E. Compared to DOP performance at specified room temperature hardness. in this example.9 56. Wadey studied a series of designed isomeric variations of DINP and the effects on plasticizer performance in PVC [30]. (Ed. the normal nonyl phthalate. in Handbook of PVC Formulating. 95 90 Shore A Durometer hardness (15 s) 85 80 75 70 65 60 55 50 20 30 40 50 60 70 80 90 100 Plasticizer phr 52.F. the hardness values are compared for DINP (MOD-BR) to DOP [di-2-ethylhexyl phthalate] plasticized PVC. J. 5. DOP (Source: Krauskopf. G. p. courtesy John Wiley.2 DINP DOP Figure 5. reprinted with permission) . New York.1 graphically portrays quantitative determination of plasticizer efficiency. Wickson.1 Durometer A hardness of DINP vs. Figure 5. The performance of the “slightly branched” (SLBR) DINP is essentially equivalent to a 50/50 mixture of di (normal nonyl) phthalate and moderately branched DINP (MODBR).. The conclusions are consistent with the generalizations cited above. L. 171. expressed as “Substitution Factor” (SF). Similar comparisons may be made for other mechanical properties.) (1993) Wiley. but hardness test reliability and the common practice of a designated room temperature hardness value supports its use to quantify plasticizing efficiency. = 1.6 Plasticizer Efficiency Plasticizer “efficiency” may be quantified as a function of PVC Durometer hardness.

while 56. DOP is 1. it is found that when compared at equivalent hardness. the DINP-MODBR plasticized PVC will have preferred low temperature properties as well as significantly less plasticizer loss due to volatilization and diffusivity.4 and 5. Table 5. It should be noted that end-use products require low temperature tests to be conducted on whatever form. Most commercial grades. the trimellitate family provides similar or only slightly improved low temperature properties vs. along with acronyms. impart significantly improved low temperature properties (by about –25 to –35 °C) versus their phthalate counterparts.5 shows low temperature properties at equivalent plasticizer levels (50 phr.5 show low temperature flex (Tf) and brittleness (TB) for PVC using different plasticizers.9 phr DOP.2 lists relative plasticizing efficiency values determined for commercial grade plasticizers. The more linear alkyl structures in the plasticizer contribute improved low temperature properties (by about –5 to –7 °C) vs.7 Low Temperature Tables 5. then. in order to achieve the same hardness or softness.7 Low Temperature 187 It is shown that 80 Durometer A hardness is provided by 52. In other words. DINP needs to be added at a level 6% higher than the DOP level.5. It is shown that for given alkyl structures. rests on comparative formulating costs and other critical properties provided at the specified room temperature hardness. Table 5. have been evaluated in PVC over a wide range of levels (phr). They also have lower substitution factors (higher plasticizing efficiency) to meet room temperature hardness. in a recipe commonly used for “screening” plasticizer performance.06. due to the lower plasticizing efficiency of trimellitates versus phthalates. on the other hand.4 compares low temperature properties when formulated to equivalent room temperature hardness (80A Durometer). The disciplined cataloguing of the performance properties allows for easy comparisons of cost effective formulating options at specified hardness values as well as at specified plasticizer levels. Table 5. and many experimental plasticizers. the substitution factor (SF) for DINP vs. Adipate plasticizers. because of the need for higher plasticizer levels to provide the target room temperature hardness. as shown in Equation 5. the phthalate counterparts. by weight). the branched isomers. 5. It has been found that this ratio (substitution factor) is consistent over plasticizer levels ranging from about 20 to 90 phr. In general. the product has. A computer program includes optimizations as a function of filler content as well as plasticizer selection and predicted properties in PVC [22].1) The “SF” indicates that DINP-MODBR is 6% less efficient than the plasticizing efficiency of DOP.2 phr DINP ⎞ Substitution Factor (SF) = ⎜ ⎟=⎜ ⎟ 52. The question of acceptability. and molecular weights. .00) in providing target room temperature hardness. chemical compositions.2 phr DINP is required to provide the same hardness. in spite of the fact that they are more efficient (substitution factors of < 1. Thus.1: ⎛ phr plasticizer at Durometer 80 ⎞ ⎛ 56. or shape.9 ⎠ ⎝ phr DOP at Durometer 80 ⎠ ⎝ (5.

8 –61. stearic acid 0.8 –42.0 –37.1 –32.5 –31.4 –39.5 –29.8 –43. plasticizer (concentration adjusted to yield a shore A of 80).5 –35.7 –27.1 PVC formula by weight: PVC-100.9 –34.4 –47.0 a TB (°C) –12.8 –24.2 –42.6 –53.4 –66.7 b –39.4 –10.8 –38.8 –37.4 Low Temperature Properties of Unfilled.7 –25.8 –37.8 –39.9 –37.9 –45. Formulated to Meet 80 A Durometer Hardness at Room Temperature Tf (°C) Phthalates BBP BOP DIHP DOP DIOP DOTP DINP DIDP DIUP UDP DTDP 610P 79P 7911P L9P 911P DUP Trimellitates TOTM TIOTM TINTM Adipates DOA DIOA DINA 79A –50. Liquid Ba/Cd/Zn stabilizer – 2.7 –63.2 –44.8 –36.5 –40.7 –34.6 –32. General Purpose PVC.6 –52.3 –51.9 –32.2 –32.9 –49.2 –64.3 –36.188 5 Plasticizers [References on Page 198] Table 5.1 –31.25.6 –27.2 –31.0.8 –41.1 –35. a ASTM D1043 b ASTM D746 .9 –29.5 –31.4 –27.

5 –32.3 –31.6 –23.3 –11.9 –23.4 –31.5 –38.6 –24. a ASTM D1043 b ASTM D746 .3 –33.9 b –31.5.7 –63.2 –42.5 –63.9 –32.0 –40.8 –67.6 –22.8 –31.0 –33.8 –30.9 –17.1 –43.3 –34.9 –31.8 –49.3 –19.3 a TB (°C) –12.9 –24.9 –62.2 –15.8 –27. General Purpose PVC at 50 PHR Plasticizer Tf (°C) Phthalates BBP BOP DIHP DOP DIOP DOTP DINP DIDP DIUP UDP DTDP 610P 79P 7911P L9P 911P DUP Trimellitates TOTM TIOTM TINTM Adipates DOA DIOA DINA 79A –52.25.7 Low Temperature 189 Table 5. stearic acid 0.7 –32. plasticizer – 50 Liquid Ba/Cd/Zn stabilizer – 2.4 –20.5 Low Temperature Properties of Unfilled.5 –32.0 –26.6 PVC formula by weight: PVC-100.3 –32.1 –27.8 –50.0 –34.5 –55.8 –29.9 –30.0.4 –33.4 –45.7 –23.5 –43.9 –23.

or otherwise damaged. in that they undergo chemical grafting onto PVC in their role as stabilizers. Copolymers for example. Thus. Quackenboss determined that two controlling mechanisms (other than effects of degradation) are at play under conditions that contribute to loss of plasticizer. solvency strength for the polymer and oxidative degradation. but do not undergo a chemical reaction that causes bonding. water. For example. oils. Thus with copolymers. when not grafted or copolymerized. specimens may experience undue failure in mechanical property testing.8 Permanence (Transience) of Plasticizers Plasticizers have a strong affinity for PVC polymers. the plasticizers. but these are generally not considered as traditional “external” plasticizers. The crystallites are the physical cross-links that hold the structure together as a thermoplastic elastomer. any significant level of co-monomer will disrupt the syndiotactic PVC structure and disrupt the ability to form crystallites. and therefore exhibit surface-controlled loss rates under aqueous environments. most plasticizers have extremely low solubility in water. However. 5. Volatile losses of plasticizer are influenced by vapor pressure. as well as the ambient airflow rate in the test chamber.000) and of bulky molecular structures show excellent permanence because of low diffusivity. while ditridecyl phthalate is useful for PVC applications under .190 5 Plasticizers [References on Page 198] Thus. These are the rate of loss that occurs at the surface of the specimen vs. For example. surface rubbing. 24. Investigations of plasticizer transience found that quantitative predictions were confounded by “compatibility”. that epoxy plasticizers are an exception. or grafting. properly prepared PVC insulation for electrical conductors typically meets low temperature mandrel bend testing at temperatures approximately –15 °C lower than the predicted brittleness (TB by ASTM D 746) values of formulated PVC. 20. But at the same time. performance test results measured on finished commercial PVC plastics may be influenced by factors other than the formulating predictions. to the polymer. Polymeric plasticizers of high molecular weight (≈1. Other functional additives are known to graft and/or polymerize in the PVC matrix. compression set increases. the translation of catalogued values may require experience. However. creep increases. and long-term elasticity is lost. Dialkyl phthalate plasticizers range in molecular weight from 278 (dibutyl) to about 530 (ditridecyl). Plasticizer losses due to extraction by oily media (in which plasticizers are highly soluble) are controlled by diffusivity rates. may be separated from the PVC matrix due to extraction by solvents. 25]. or degradation mechanisms. For example. It is known that test chamber atmospheres saturated with plasticizer vapor allow for reversed absorption of plasticizer into the test specimens. Note. however. which was difficult to quantify [19. this family of plasticizers is also noted for sensitivity to hydrolytic degradation in aqueous atmospheres.000 to > 500. migration into adjacent media. can lower PVC’s Tg as plasticizers do. volatility. replacing labile chlorides [14] in addition to their role of acid absorption. the slowest rate is the controlling factor. incompletely fused or improperly conditioned. Commercial experience has shown that dibutyl is unacceptably volatile (except in some adhesive applications). Likewise. the rate at which the plasticizer diffuses to the surface.

Two isomers of DOP have been found to have novel resistance to migration into F2 nitrocellulose lacquer finishes [32. Their overall performance in PVC Is similar to that of DOP. or compatibility of plasticizers – and other reagents – in PVC are confounded by the simultaneous effect of diffusibility. except for a slight indication of being less compatible.9 Solvency. This characteristic often dictates the preferred choice of the general purpose plasticizer for given applications. 35] showed the following relationships. this novel performance trait of DOIP and DOTP remains largely a technical anomaly. However. and abide by the three-dimensional solubility parameter concept of Hansen [10. trimellitates and polyesters are typically even lower in volatility. Diffusion-controlled transience is poor for the aliphatic dicarboxylic diesters. such as top coating technology and/or the use of polyester plasticizers.218 · (Viscosity) – 10.2) . and aliphatic dicarboxylic diesters that are used as plasticizers in PVC.08 · (Specific Gravity) (5. gelation temperatures. their presence is responsible for the energy required to molecularly combine plasticizers with PVC resin (up-take or swelling) and to hold them together (compatibility for duration of the application). Dry Blend Times @ 88 °C = 10. 34]. but good for branched phthalates. or Compatibility 191 high temperatures for extended periods. but significantly better than the aliphatic dicarboxylic diesters. or compatibility (phase separation). while DOP has an intermediate molecular weight at 390. These are known as DOIP [di 2-ethylhexyl meta (called “iso”) phthalate] and DOTP [di 2-ethylhexyl para (called “tere”) phthalate]. Di(linear alkyl) phthalates impart lower volatility and improved oxidative resistance vs.9 Solvency. while DIHP is significantly more volatile than DOP in most applications. trimellitate. Bench scale methods designed to measure the solvency. All phthalate. Preferred “General Purpose” plasticizers range in molecular weight from 362 (DIHP) to 418 (DINP). Equation 5.05 + 0. Oil extraction resistance of trialkyl trimellitates is not good compared to that of phthalates. and aliphatic dicarboxylic diesters show excellent resistance to hydrolytic attack under exposure to aqueous environments.2 expresses dry blend time as a function of plasticizer viscosity and specific gravity for phthalates. 33]. the systems behave as solid solutions. Miscibility. their branched counterparts. While the solubility forces are extremely small (units are (cal/cm3)1/2). This interfering mechanism is present when attempting to measure plasticizer take-up. or Compatibility These terms are essentially interchangeable with respect to liquids and other lower molecular weight reagents added to PVC. This is apparently due to their lower plasticizing efficiency as well as to the increased proportion of alkyl moieties in the molecular structure. Whether rigid or flexible. linear dialkyl phthalates are measurably less resistant than the branched phthalates. miscibility. A statistical analysis of independent plasticizer variables versus take-up rates in PVC [11. Miscibility. trimellitates. 5. The “mar resistant” feature may also be imparted to flexible PVC by alternate practices. The volatility of DINP is significantly less than that of DOP.5.

initial and final gelation temperatures (influenced by plasticizer selection) influence processing of plastisols. specific gravity is specific gravity of the plasticizer at 20 °C.282 · (Viscosity) – 0.067 + 0. Equation 5. MW is molecular weight of the plasticizer. centistokes (cS). Equation 5. HIR is the distance between PVC resin and the plasticizer on Hansen’s three-dimensional solubility parameter grid. plasticizer fuming (volatility) is of concern. Thus. In addition. fusing. plasticizer selection influences dry blend rates. As shown in Section 5. °C = 71. That study found that the statistical confidence for evaluating plasticizer take-up is significantly improved by limiting the analyses to the eleven commercial grade phthalates tested. final gelation temperature for plastisols. is influenced by plasticizer characteristics. the rheology of plastisols (dispersions of PVC in plasticizer) critically impacts the ease of shaping and controlling thickness of end products.118 · (MW) + 0. to the exclusion of plasticizer solubility parameters.3 expresses dry blend time as a function of plasticizer viscosity (distinctly) for dialkyl phthalates: Dry Blend Times @ 88 °C = –0. Melt viscosity. The mixing. [36]. Initial Gelation Temperature = –8. [36].4 shows initial gelation temperatures are a function of plasticizer molecular weight and solvency strength for dialkyl phthalates. δ is Hansen’s Interaction Radius (HIR). and shaping of the vinyl involves the application of elevated temperatures.35 + 0.3) Similar relationships were developed for gelation temperatures. The investigation that developed plastisol gelation values [36] indicated that the ultimate fusion temperature is a function of the PVC resin. up to about 160 °C to 170 °C. viscosity is plasticizer viscosity at 88 °C.30 · (δ) (5. ref. °C. Smaller values of δ indicate stronger interaction forces.012 (Viscosity – 8)2 (5. further. ref. °C. fluxing.48 + 39.4) Final Gelation Temperature. during “hot compounding” processes. 5. while Equation 5.192 5 Plasticizers [References on Page 198] Where: Dry Blend Times are minutes using ASTM D 2396.5 shows that dialkyl phthalate plasticizers influence final gelation temperature exclusively as a function of solvating strength.001 · (MW – 450)2 + 21. including solvency .9.10 Processability The ease with which various processes combine the liquid plasticizer with PVC polymer is a function of the physical and chemical properties of the plasticizer as well as the polymer characteristics.4 · (δ) (5.5) Where: Initial gelation temperature for plastisols.

sheeting. plastisol viscosity. sulfonates. resilient vinyl sheet flooring. with DOP meeting this requirement in most parts of the world. 911P. L9P. DINP is the preferred plasticizer choice based on the above criteria and factoring in regulatory issues regarding the use of DOP. the majority of plasticizer consumed is for products produced in calendering operations. For coated substrates prepared through a coating process.11 Plasticizer Markets 193 for the PVC resin. Coatings 7% Flooring 8% Food & Regulated Uses 5% Extruded & Molded 12% W ire & Cable 19% Film & Coated Fabrics 35% Figure 5. There are basically three types of products: vinyl tile. If greater permanence is required.2 depicts a worldwide analysis of plasticizer consumption by PVC market segments. In North America and Europe. and DUP may be used. and vinyl backed carpeting or carpet squares. Higher molecular weight plasticizers typically offset volatility while imposing constraints on ease of processing. benzoates. The primary factors in plasticizer selection are low cost and ease of processing. Many investigators have studied these characteristics. For products that need a slight reduction in gelation or fusion temperature. Sealants. The largest market segment is film.2 End use markets for plasticized PVC . The most commonly used plasticizers in floor tiles are DOP and DINP. and coated substrates. DINP is found to give a more consistent.5. Figure 5. plasticizers such as DIDP. Volatility is typically the limiting factor on use levels of strong solvating plasticizers. gelation or fusion behavior. Floor tiles are comprised of about 80% calcium carbonate held together by the fused flexible PVC binder. such as aryl-alkyl phthalates. while Miscellaneous 14% Adhesives. and so forth.11 Plasticizer Markets Plasticizers are used to produce flexible PVC products for many different end uses or market segments. In this segment. Commercial practice includes the use of up to 10–20% of the plasticizer system as “strong solvating” type plasticizers. and emissions are all-important concerns. stable viscosity than DOP while reducing emissions. DIHP (diisoheptyl phthalate) or BBP can be used to replace a small portion of the primary plasticizer. 5. Vinyl flooring is another major market for plasticized PVC.

de/3-446-22714-8 sowie im Buchhandel . Summers ISBN 3-446-22714-8 Leseprobe 2 Weitere Informationen oder Bestellungen unter http://www.hanser. Wilkes.PVC Handbook Charles E. James W. Daniels. Charles A.

10 Flexible PVC WILLIAM COAKER 10. lacquers. but Griesheim-Elektron let them expire in 1926. Use of other additives. Goodrich then patented some of these formulations and commercialized coated fabrics and films made from them and trade-named them Koroseal® [4. fibers. These include stabilizers. Fritz Klatte. in addition to plasticizers. [3]. Between 1926 and 1933. is essential to making successful flexible PVC products. anti-microbials. Shortages of conventional materials during World War II led to practical uses for both flexible and rigid PVC in wartime Germany. 2]. e. Klatte had shown promising leads but his team had not identified good enough plasticizers. oil cloth. working for Chemische Fabrik Griesheim-Elektron. he determined that basic silicate of white lead was an adequate stabilizer to make processable flexible PVC formulations plasticized with TCP or DBP. Klatte was then commissioned to find uses for the hard. Other German companies then took up the challenge and had developed commercial PVC formulations by 1939. Many of these have turned out to be commercially useful and cost competitive. which sought volume uses for acetylene. depending on formulation) that can be lowered by plasticizing entities to produce semi-rigid and flexible items. and many specialty additives such as fire retardants. found that acetylene can react with HCl to form vinyl chloride monomer (VCM). fillers. some were empirical and others the results of classical theory-driven research. 5]. coatings generally. and so forth.0 · 105 psi). pigments.5–6. which in turn. He obtained several patents [1.. In addition. and antistats for particular applications.g. To put the development of flexible PVC in perspective. In Germany prior to World War I. Of the seminal discoveries leading to successful flexible PVC products. Post-war allied studies of German industry publicized these world-wide. horny intractable PVC resin. Waldo Semon at BFGoodrich in the United States discovered that tricresyl phosphate (TCP) and dibutyl phthalate (DBP) were effective plasticizers for PVC. UV-screeners. the development of electric lighting resulted in a large excess of calcium carbide as acetylene lamps were phased out. can be polymerized to PVC using free-radical initiators. Supplementing the antecedent German work.1 Origins Polyvinyl chloride (PVC) homopolymer is a semi-crystalline polymer with a relatively high room temperature tensile modulus of 2400 to 4140 MPa (3. some historical facts are of interest. Carbide and Carbon in the United States sought outlets for their large excess of ethylene dichloride . lubricants. heat stabilizers and process aids to make superior PVC replacements for celluloid. Space allows only a few of these milestones to be described here.

After World War II. or from approx.2 Types of PVC Resins Used in Flexible Applications The largest volume PVC resin type used in flexible and semi-rigid applications is aqueous suspension PVC homopolymer. made to have sufficient porosity in the particles to absorb enough plasticizer to meet the desired flexibility and hardness specifications of the intended end-product.40ml/g or more for highly flexible items made with monomeric plasticizers and for items flexibilized with polymeric plasticizers. L. In 1933. reflecting their resistance to ignition compared to the then-standard flexible insulations and sheathings made from natural rubber. For most flexible uses. it is common to require about 0. By normally accepted conventions this means from approx. the resins range from medium to high molecular weight. General Electric developed plasticized PVC insulation and jacketing for electric wires and cables. 0. it was Monsanto’s air-oxidation process for making inexpensive phthalic anhydride. In 1930. Specialty soft plasticized PVC compounds requiring excellent compression-set properties call for the use of ultra-high molecular weight PVC resins with high porosity.000 number average molecular weight. it became obvious that many of the substituted plasticized PVC products had performance properties and costs superior to those of the natural items they had replaced. a patent covering the PVC plasticizer di-2-ethyl hexyl phthalate (known as DEHP or more often DOP) was issued to Lucas Kyrides of Monsanto Chemical Company [6].000 to approx. they found that they could produce pure VCM by treating EDC with caustic soda.and co-polymers from the VCM and supplied samples to Waldo Semon and others. and about 0. They trade-marked these Flamenol®.57 to 1. This was driven by shortages of rubber. In addition to pore volume. 51 to 71 Fikentscher K [8]. Larger pore diameters contribute to faster uptake of plasticizers.30ml/g or more for resins used for moderately flexible items made with monomeric plasticizers. leather. 10. T. which was a by-product of their ethylene chlorhydrin manufacture. 30. Monsanto sold the patent to Union Carbide. . They made PVC homo. In terms of commonly used tests based on dilute solution viscosity. Ironically. Just as in Germany. World War II stimulated the development of uses for flexible and semirigid PVC in the United States.000 number average. because at the time Monsanto was more interested in developing plasticized polyvinyl butyral interlayers for automobile windshields and windows than in plasticized PVC. this means from approx. which later made low cost DOP a reality in the United States [7]. Gresham at BFGoodrich ran extensive tests and identified DOP as the best available plasticizer for PVC homopolymers used for making flexible PVC. Great Britain. 60.316 10 Flexible PVC [References on Page 361] (EDC).10 inherent viscosity. and other allied countries. Many became established as accepted items of commerce. and other naturally derived raw materials. These may exhibit molecular weights as high as 150. Using a mercury intrusion porosimeter to measure resin porosity. pore diameter may be measured for PVC resins used in flexible products.

40 mesh sieve. tear strength. a relatively narrow PVC particle size distribution is desirable and is mandated by many users’ specifications.9 mils) square. broad particle size distributions.which otherwise calls for use of a medium molecular weight PVC. Irregular. The aim point for average particle size (APS) is normally between 100 and 80 mesh.4 and in Chapter 9. Chapters 3 and 11). other things being equal. For flexible applications. Plastisol resins are sometimes called dispersion resins. paste resins. For instance.1 to 1. mostly in Europe. Typically. it is necessary to specify a specialty “low gloss” resin offered by a few PVC manufacturers. The distinctions between PVC resins made for use in plastisols and general purpose PVC resins are addressed here.10. tensile strength. The particle shapes. Also. use of higher molecular weight PVCs tends to give lower gloss on a finished product. That is between 149 and 177 microns (5. In the United States.2 Types of PVC Resins Used in Flexible Applications 317 Flexible PVC products injection-molded or extruded at very high shear rates may be made with low molecular weight PVCs having less than 30. 10% maximum by weight retained on a U.0 mils). microsuspension. solid particles ranging in size from 0. Because the particles are solid PVC. Weak agglomerates of the basic emulsion resin particles are formed during drying. The plastisol resins made by emulsion polymerization may be dewatered by spray drying or a combination of coagulation and conventional drying. using PVC resins with such low molecular weights sacrifices physical properties. e. 200 mesh sieve whose openings are 74 microns (2. or special proprietary processes.S. size distribution. a typical specification for general purpose PVC aimed at flexible markets is ≥ 99. they absorb plasticizers quite slowly at typical ambient temperatures. size limits. suspension and mass PVC resins may have their APSs skewed to finer or coarser numbers. the higher the processing temperature needs to be during fabrication in order to achieve optimal fusion.8% particles must pass through a U. However. These are normally broken up to a substantial degree in grinding procedures before use of the . and internal porosities of the PVC grains formed during suspension or mass polymerization processes are functions of many factors dealt with in other chapters of this book (see. For special purposes. The differences between mixing and processing methods for general-purpose flexible PVC and plastisol techniques for making flexible PVC products are described in Section 10. these resin particles provide large surface area due to their small diameters. whose openings are 250 microns (9. For flexible applications. and high particle porosity tend to give low bulk density and poor bulk flow behavior. In bulk resin. because items made with them are too weak. including compression set. Very low molecular weight resins are not used for highly flexible items. many compromises are often involved in selecting the best resin. and 2% maximum through a U. for a given processing temperature.S. whose nominal openings are 420 microns (16. It is difficult to make ultra-low molecular weight PVC resins having high particle porosities. particle sphericity tends to provide good bulk flow behavior along with efficient particle packing and higher bulk density in dry blends. they contain spherical. They are readily wetted by plasticizers due to their surfactant content and absorb some plasticizer during mixing. When formulating flexible PVC compounds for specific exacting uses. elongation at failure.8 mils) square. or.9 and 7. knobby resin particles.g. and fatigue resistance.5 mils) square.1 microns in diameter. If low gloss is required on an extruded product.000 number average molecular weight. 60 mesh sieve.S. the higher the molecular weight of the chosen resin.. They are made by emulsion.

Third. Some of them are specialty copolymers designed for blending with specialty homopolymers aimed to achieve particular performance results. which is the size of the 325 mesh screen openings. low moisture sensitivity of the end products. Second. Specialty PVC resins are made for producing flexible PVC items by rotational molding from powders and powder-coating of pre-heated parts. Another class of PVC resins made for use in plastisols is called plastisol-extender resins. often referred to as . Solution vinyl resins are a specialty dealt with in dedicated texts [9]. have relatively low bulk densities compared to general purpose PVCs. and offered by Vinnolit (which was formed by the merger of Hoechst and Wacker’s PVC operations). The systems used for bulk handling of plastisol resins are specially designed for this purpose and usually are dedicated to particular plastisol resins. use of extender resin in a plastisol usually gives a rougher surface finish with lower gloss when this is desirable. Their APS is thus equal to or less than 44 microns (1. Most PVC plastisol resins are fluffy. 9. The particle architectures of other PVC resins are covered in Chapters 3. This is important in sheet flooring constructions and plastisol-coated metal siding.7 mils). plastisol resins are often bagged by the manufacturer before shipment to the customer. they have to be given antistatic treatments to get them to flow satisfactorily in bulk handling systems. In the early years of the PVC industry. An example is Vinnol VK 801 listed as having 50% EVA content. standard screens.6% through 140 mesh. and only used in large volume applications. they contribute to more efficient particle packing in a plastisol when used in conjunction with a standard plastisol resin.S. The rationale for the use of such resins in plastisols is at least threefold. due to their coarser particle size on average. a common problem in the manufacture of flexible PVC items by calendering and extrusion was the occurrence of gel particles. for instance. Microsuspension PVC resins used in plastisols differ from their emulsion-polymerized counterparts both in particle size distribution and emulsifier content. This allows higher PVC content in a plastisol of given viscosity. and little or no contribution to fogging in automobile interiors. and 11 of this book. These are solid particle resins made by suspension polymerization with particles finer than general purpose resins. Their emulsifier content is lower than that of most emulsion resins and this contributes to higher clarity in clear formulations. they are less expensive to make than true plastisol resins. 10. In most cases. 5% maximum on 200 mesh and > 65% through 325 mesh.318 10 Flexible PVC [References on Page 361] resins. First. and poor bulk flow properties. Consequently.3 Particulate Architecture of PVC Resins Used in Flexible Products This section deals with general purpose PVC resins made for use in flexible products. using U. Typical screen analyses for plastisol extender resins are: > 99. but coarser than microsuspension plastisol resins. Graft copolymers constitute another type of resin used for making vinyl TPEs and unplasticized flexible vinyl articles or lightly plasticized low extractibles flexible PVC.

because the most frequent cause of fisheyes in PVC is inadequate cleaning of polymerization reactors between batches. and 12 of this book. depress the melting temperatures of the crystallites. which do not absorb plasticizer as readily as the other resin particles in the formulation and which do not fuse readily at the processing temperatures used. The melting and recrystallization behavior. A critically important part of PVC resin morphology is its semi-crystalline nature. agglomeration of multiple insulations within a cable. As the technology of polymerizing VCM has improved. creep. of which dioctyl adipate (DOA) is an example. thus requiring higher processing temperatures than fast fusion or general purpose plasticizers. Their melting and reformation is affected by the kind of plasticizer present.10. They believed that only cross-linked rubbers could be soft and flexible enough and still maintain their integrity under harsh conditions of use and testing. and heat distortion. They asserted that no thermoplastic such as plasticized PVC would replace cross-linked rubbers. It was after this happened that many of the reasons why plasticized PVC fulfilled these requirements were elucidated. which are both thermoplastic and resistant to compression-set. which are interspersed between amorphous regions. Rational terminology describing the morphology of PVC suspension. Numerous thermoplastic elastomers (TPEs) have since been developed. “Low temperature” plasticizers.3 Particulate Architecture of PVC Resins Used in Flexible Products 319 “fisheyes”. produce resins with unacceptable content of gels. abrasion. The lower end of Geil’s size hierarchy also applies to emulsion. Table 10. cut-through. But based on its physical and flammability properties. which melt and reform over a range of temperatures. When plasticized PVC started replacing rubbers in insulation and sheathing for electrical wire and cable. is complex because PVC contains several different kinds of crystallites. insoluble PVC to interfere with normal fusion. 9. rubber technologists asserted that no thermoplastic composition flexible and soft enough to satisfy wire and cable flexibility requirements could meet the required specifications for resistance to thermal distortion. and thermal distortion. The crystalline microdomains in plasticized PVC. This is responsible for the resistance of flexible PVC to heat distortion. and compression set. Large fisheyes are the most objectionable. primarily plasticize the amorphous regions of the PVC and have little effect on crystallite melting temperature. compression distortion. The seminal discoveries of the micro-morphology of rigid and flexible PVC are dealt with in detail in Chapters 3. however. abrasion resistance.1 is adapted from Geil. However. Most of these crystallites melt at processing temperatures and re-form during cooling of fused plasticized PVC melts. compression-set. compression-set. the occurrence of fisheyes in flexible products has become a less frequent or severe problem. These are relatively solid PVC particles. “fast fusing” plasticizers. thus promoting fusion at lower processing temperatures.and microsuspension-polymerized PVC resins. except that they are thermally reversible. act like cross-links in rubbers in resisting creep. But it still exists. plasticized PVC took over most of the indoor wiring insulation and jacketing market in developed countries.and mass-polymerized resin particles was proposed by Geil [10]. who try to save money by reducing the frequency and diligence of reactor cleaning. PVC particles that go through two or more polymerization batches tend to have reduced porosity for absorption of plasticizers and to contain enough cross-linked. a terminology rationalizing the behavior of plasticized PVC is presented here. and so forth. . PVC manufacturers. of which butyl benzyl phthalate (BBP) is an example. creep. For instance.

to a moderate extent with general purpose plasticizers. and much less with low temperature plasticizers.01 µm spacing Secondary crystallinity 0. fusion. Berens and Folt [14]. which maintain integrity of primary particles and span between primary particles in well fused PVC Crystallites re-formed during cooling of a fused PVC melt Domains Microdomains 0. . Summers [19. But this range varies with plasticizer efficiency. small. Van der Waals forces. Pezzin [16]. which occurs at higher plasticizer levels. Collins and Daniels [17]. which is reduced by as little as 1 phr of most plasticizers or plasticizing stabilizers. localized increases in molecular order. 12].1 Size Hierarchy of PVC Particulate Phenomena Term Grain Agglomerates of primary particles Primary particles Size 70–420 µm diameter 3–10 µm diameter 1 µm diameter Description Free-flowing powder produced in suspension or mass polymerizations Formed during polymerization by coalescing of primary particles Formed at single polymerization sites by precipitation of newly-formed polymer into discrete molecular aggregates Observed after certain types of mechanical working of the PVC Crystallites capable of holding portions of tie molecules. It is observed at plasticizer concentrations of approx. Many authors have contributed to understanding the relationships between PVC particle morphology. This is the stiffening effect of low levels of some plasticizers. which takes place after fusing and cooling a formulation. and decreased free volume [11. Lyngaae-Jorgensen [18].320 10 Flexible PVC [References on Page 361] Table 10. It must be noted that these extra crystallites are of the low melting type and do not raise the heat distortion temperature of PVC. Their original findings relate to both rigid and flexible PVC. Some of these are Collins and Krier [13]. and Rosenthal [21].1 µm diameter 0. Antiplasticization is explained as being mainly caused by the promotion of crystallite formation by low levels of plasticizers without an offsetting plasticization of the amorphous regions. 1 to 15 parts per hundred resin (phr). steric hindrance. and the processing rheology of PVC. Singleton and Isner [15]. Other factors discussed in the literature as contributing to antiplasticization effects are hydrogen bonding. 20].01 µm spacing Antiplasticization by plasticizers is a phenomenon that PVC formulators must take into account. It occurs most often with fast fusing plasticizers. such as the thiotins.

For flexible PVC formulations using liquid plasticizers. it is necessary to heat them during mixing to facilitate absorption of the plasticizers into the resin and to avoid loss of product through formation of undesirable lumps of wetted pigments and fillers. after cooling. While studying the Flory-Huggins interaction parameter. and other ingredients. resins with sufficient porosity to absorb the liquids are intermixed with the other ingredients to get them mutually well dispersed down to the particulate level. The pressure stain test is a way of predicting when this state has been reached while the blend is still hot and in the blender. also known as “powder mixing”. Diffusion of liquid plasticizers into PVC resin particles is a kinetic process whose rate varies inversely with the viscosity of the plasticizer [22]. jacketed ribbon blenders and various other kinds of available mixing equipment were used. During dry blending. For most formulations. From a practical viewpoint. Anagnostopoulos et al. Historically. This correlates with the small-scale laboratory dry time test ASTM D2396. A dry blend is a non-fused mixture of PVC. flows well through a funnel or an extruder hopper and does not cake during storage. The most common processing type is “dry blending”. This depends on the particular plasticizer or plasticizer mixture being used and the molecular weight of the PVC resin. χ. developed a microscope hot-stage fusion test.10. The desired resulting product is a freeflowing powder. plasticizer. liquid plasticizers penetrate the amorphous matrix surrounding the crystallites in the PVC resin particles. Commercial blenders are stopped during a cycle and a “thief” is used to take small samples for testing. than a blend made with a shorter dry blending cycle. More than 85% of suspension and bulk PVC resins are initially processed by dry blending. such as extrusion. The crystallites remain intact because of the thermodynamic barrier which prevents fusion until a certain temperature is reached. The main drawbacks to the large ribbon blenders were that cycle times were surprisingly long to achieve good blend uniformity and it required considerable technical effort of a largely empirical nature to determine the optimal order and timing for addition of individual ingredients. It was not unusual to produce a fair amount of off-grade product during the process of mixing cycle optimization when new formulations were introduced. Much theoretical work has been done on dry blending of flexible PVC formulations. Dry blends of plasticized PVC formulations are over-dried if they are dusty and fuse with more difficulty in subsequent processing operations. which determines the point in a commercial dry blending cycle at which the blend no longer stains brown paper or cigarette paper sheets between which it is pressed. [23]. for various plasticizers with PVC. Park published a method for running the pressure stain test for PVC dry blends [24]. whereby the temperatures at which PVC resins of different molecular weights fuse in particular plasticizers are readily measured. which is slightly damper and less dusty. but still has good bulk flow and non-caking behavior. . large volume.4 Favored Processing Methods for Flexible PVC 321 10. These fusion temperatures are higher than dry blending drop temperatures.4 Favored Processing Methods for Flexible PVC The natures of the PVC resins and other additives used in flexible PVC compounds have conditioned the selection of efficient material handling procedures for making the primary mixes. a dry blend cycle is complete when the dry blend.

and fusion systems made by Coperion. Welex. By running the drive shaft at speeds appropriate for the particular formulations being mixed.322 10 Flexible PVC [References on Page 361] Low speed dry blending mixers are generally of the ribbon mixer type. high intensity. Leistritz. which may turn at 40 to 70 rpm. dry blends are conveyed to fluxing devices. In many factories the cooled dry blend is air conveyed to interior storage before being fed to fabrication equipment or intermediate processing units. fluxed . Reifenhauser. Buss Ko-Kneaders. Typically. which can be run fast enough to achieve fluidization of the PVC during blending. Krauss-Maffei. One or more sets of mixing blades are attached to the drive shaft. The hot. These are bulky semicylindrical horizontal mixers supplied with a jacket surrounding the side and bottom surfaces through which heat or cooling can be applied. A baffle penetrates the top of the mixer. Typical batch capacities are 80 to 200 kg (176 to 440 lb). batch high speed. radial blades are mounted on a horizontal rotating shaft. polyolefin elastomers (POEs). which can be tightly sealed to the drum. and Littleford. mixing occurs with the generation of sufficient frictional heat to raise the batch temperature to a desired drop temperature. These intensive mixers all have Froude numbers* much greater than 1. and many others. and compatibilizers. such as 105 °C in 4 to 8 minutes. Papenmeier. Farrel Continuous Mixers. freezing brines are not used in these cooler jackets. these consist of a vertical drum with a dish bottom through the center of which a drive shaft penetrates. From interim storage. * Froude number = R ω2 g where R = blade radius ω = angular velocity. for example. and it must flow readily and uniformly in the feed hoppers of equipment such as extruders and proportioning devices. dry blending mixers are used for flexible PVC. Typical shaft speeds are 500 to 1200 rpm with blade tip speeds between 10 and 50 m/s (33 and 164 ft/s). radians/s g = gravitational acceleration in consistent units Trade names for typical intensive mixers are Henschel. It must not “cake” during storage. The high speed mixers generally dump their batches into lower speed jacketed rotary coolers having Froude numbers less than 1. those used for color control operations. To shorten mixing cycles. For mixing. such as compounding extruders. Banbury mixers. Some of these mixers are designed to sustain high vacuum or air purge during mixing for removing traces of unwanted volatiles such as moisture or residual vinyl chloride monomer [25]. To avoid adventitious condensation of moisture from the ambient air. high viscosity plasticizers (polymeric liquids) are normally preheated before addition to the mixer. The coolers introduce little frictional heat and cool by conduction into their cold water jackets. The PVC and other ingredients are fluidized during blending in these mixers. Intermediate speed dry blenders generally consist of a horizontal cylindrical jacketed chamber with axially mounted blades. Where the investment can be justified. Specialty dedicated blending procedures are used for flexible PVC compounds made with solid plastifiers.

involving a flexible backing covered with a foamable plastisol on which a design is printed with some inks containing a foaming inhibitor and overlaid by a clear plastisol wear layer. a set of tentative needs is “guesstimated”. such as Underwriters’ Laboratories or suppliers’ or customers’ laboratories. odor. calenders. pony mixers. and three-roll mills are typical of the mixers used for manufacture of plastisols. modified plastisols. these are listed and used as guidelines.5 and Chapter 11. In some cases. and other ingredients. Specifications and necessary qualification tests must be defined. and organosols. whose economics are close together. are developed and parts or items submitted to field trials.5. electrical and toxicological requirements. high speed Cowles Dissolvers.5 Designing Flexible PVC Compounds 323 PVC may then go to pelletizing units and be sold as compound pellets. decorative. which are dedicated for use in plastisols. stability to heat and light. and so forth. Many of these flooring constructions are sophisticated. to prevent heat-induced viscosity build-up and other changes in their desired rheology caused by aging. density. whose properties bracket the tentative needs. They involve physical and optical properties. and other additives such as stabilizers. discussed later in Section 10. .1 Designing Flexible PVC Compounds Formulation Development There are two general approaches to formulating flexible vinyl materials. In most cases. air release agents and thinners. The process is iterated until a satisfactory product is developed or the project is abandoned as impractical or too costly. preferably at or below 23 °C (73 °F). fillers. The total cost of the development program and the potential profitability of the new product need to be estimated to justify proceeding with development. This is done in liquids mixing equipment using plastisol grade PVC resins. Plastisol-derived sheet flooring is the largest volume use for plastisols. Alternatively. In developed countries. Inverted conical Nauta mixers. several plastics and plastic alloys. When a project involves a novel untried concept for which the technical requirements of the product are unknown.5 10. pigments. suitable plasticizers. or injection molding presses. allowable cost. When the technical and economic requirements for the new product are known and considered feasible using flexible PVC. Another type of mixing for preparing flexible PVC goods involves compounding of liquid plastisols. These may include viscosity modifiers. including needs to run field trials at customers or evaluations at outside testing services. 10. Plastisols are fabricated into end-use items by liquids-forming procedures followed by gelling and fusion in ovens. plastisols are de-aerated after mixing and stored at controlled temperatures. Trial formulations. medium speed Ross Power Mixers.10. are competing and flexible PVC is simply defending or increasing its market share. it may be fed directly to fabricating equipment such as extruders. the existing markets for flexible PVC are defined and competitive.

reverse roll coating.). it is industry practice to refrain from submitting a defective vinyl part for trial. over which flexible PVC has some clear-cut advantages. But after . In the case of plastisols and organosols.5. When more than one company is involved in developing a product. or dispersion and mixed into the base latex under gentle agitation. There should be at least a 50% probability of success to justify submittal of trial items. emulsion. The compounded latex is then applied to the substrate to be treated by common latex application methods. the term compounding has meanings specific to whether it is applied to solid or liquid systems. then fluxing the dry or wet blend until it will flow properly in forming equipment. After some of the clocks were sold it was found that the HIPS cases had all been marred by migration of plasticizer from the cord jackets. 10. this binder exhibited exemplary non-migratory behavior. The maker of the cords had not been told that their jackets were going to be in direct contact with HIPS. and finally succeeded by cooling before the product loses its desirable form and shape. dip coating. Initially. An example of a product failure. When placed in contact with photocopy inks this binder “lifted” the inks and ruined the copy’s appearance. An example with vinyl-coated bookbinders was one in which the vinyl coating was plasticized with di-hexyl phthalate. which was corrected. impregnation. The problem was solved at a modest increase in cost of the cords by replacing the commodity phthalate originally used with a blend of higher molecular weight phthalate and trimellitate and modifying the packaging procedure. compounding means mixing the solid resin and other solid ingredients uniformly into liquid plasticizers and other liquid ingredients so as to achieve a targeted rheology suitable for follow-up liquids-forming operations (reverse roll coating. and cooling the hot product before it loses its desirable shape.324 10 Flexible PVC [References on Page 361] In undeveloped countries. so that it does not coagulate the latex or mixture of latexes. flexible PVC has many opportunities to improve the standard of living of the people by satisfying unfulfilled needs and replacing natural materials. spread-coating. strand coating. The water is then evaporated and. The vinyl industry has sometimes been victimized by callous formulators. When the technical requirements for a new product cannot be satisfied by flexible PVC. or mixing a wet blend. was the manufacture of a large number of electric alarm clocks with high-impact polystyrene (HIPS) cases around which the vinyl-jacketed cords were tightly wound before packaging them. the steps generally are mixing a dry blend from solid and liquid ingredients. the importance of accurate and complete inter-company communications cannot be over-emphasized. the product is fused and cooled. followed by fusion in a suitable oven or microwave treatment. spraying. if necessary. spray coating. shaping the melt into an end product. such as dipping. coagulation.2 General Problems in Formulation Development In the flexible PVC industry. For PVC latexes. who make items from the cheapest formulation that satisfies initial requirements without providing suitable in-use and aging behavior. ingredients are normally added in waterborne solution. For solids. etc. injection molding. rotational molding. and so forth. A second example was a “non-migratory” binder plasticized with epoxidized soy bean oil (ESO) as sole plasticizer at about 50 phr.

fluxing. retention of elongation after oven aging. which could cause very expensive damage to the finishing rolls of the calender. and other raw materials.5 Designing Flexible PVC Compounds 325 about a year of exposure to fluorescent light and some sunlight. the binders with this composition were ruined by tacky exudates which gave them a surface like fly paper. In calendering plants producing thin gauge films. K. A strainer designed for highly flexible formulations tends to overheat rigid stocks at typical desired throughputs. Versatility can be achieved by stocking a range of parts for compounders. plasticizer extraction by oils or fats. Non-availability of optimal raw materials at competitive cost is a problem frequently faced by vinyl compounders. and environmental stress-cracking of rigid plastics in contact with a flexible PVC part often can be corrected by switching to higher molecular weight PVC resins in the rigid PVC. slow dry blending may be causing a production bottleneck caused by the use of a polymeric plasticizer or a slow dry blending monomeric plasticizer. and R. Equipment designated to the manufacture of diced or pelletized compounds also needs to be suited to the rheology of the range of compounds being manufactured in order to achieve optimal through-puts. Compounder B has more extensive storage facilities and greater purchasing power for getting special deals on resins. higher molecular weight plasticizers. continuous compounding mixers need to be designed for the rheology and the throughput of the stocks they are handling. plasticizers. has an advantage as long as he confines himself to his niche markets. abrasion resistance. For instance. One approach is to reformulate. it is common practice to optimize throughput by selecting raw materials. the formulator usually has to adjust the stabilizer and lubricant systems to accommodate higher stock temperatures. Similarly. pelletizers. more porous PVC resin. For these situations. In competitive situations. In older plants. along with as much process aid that economics allow. End-product performance failures in terms of resistance to compression-set. compounders may need to modify their mixing and fluxing procedures or upgrade their equipment. To maintain throughput in spite of higher melt viscosity. and/or introducing specialty additives such as process aids or “plastifiers” in place of part of the plasticizer system in the flexible PVC. For instance. due to his lower overhead costs. and L along with plasticizers P. and dicers. fatigue after repeated flexing. compounders use the lowest molecular weight PVC resin that satisfies end-use requirements. and as fast-fusing a plasticizer system that is consistent with end product requirements. compounder A may have bulk storage for PVC resins J. it is normal to pass the fluxed feed through an extruder-strainer to eliminate adventitious metal contamination. but the bottleneck may be more readily eliminated by pre-heating the plasticizers before adding them to the mixer and/or use of a faster blending. These strainers need to be designed for the rheology and throughput of the stocks run on the calender. such as DTDP. The problems were solved at some increase in formulation cost by using a combination of medium molecular weight polymeric plasticizer and a high molecular weight phthalate for the nonmigratory binder and just a high molecular weight phthalate for the regular binder. . and forming equipment are all optimized for the products being manufactured. Q. It is a luxury to work in a plant where the mixing. This may limit the flexibility of calender lines with regard to switching back and forth from flexible to rigid stocks.10. But compounder B’s products have better cost/ performance in other markets due to his superior raw materials situation and more versatile compounding equipment. Compounder A.

injection molding. including mill rolls. calender roll. the fusion characteristics of the resin-plasticizer system must be matched to the behavior of the blowing agent-kicker-stabilizer in order to achieve manufacture of good quality uniform cell-size closed-cell foams. liquid. then proceeds to build up by occluding solids from the formulation such as colorants. fillers. either by plastisol coating or laminating. such as coated fabrics or carpets backed with flexible vinyl materials. calender rolls. This often causes severe degradation before the calender can be shut down. Suitable low fusion temperatures can often be achieved in the vinyl composition by using copolymer resins and fast-fusing plasticizers such as BBP or DHP. it may lead to catastrophe such as “shipwreck” on a fast-running calender. The initial plateout. For consistently satisfactory results. Lippoldt [26] published an extensive study of plate-out. This occurs when the calender web stops releasing from the final calender roll and folds back into the calender nip. excellent control of the rheology and time-temperature profiles is essential. . or die. This is critical with some polyolefin fibers. the fusion temperature of the vinyl must not exceed the tolerance of the fiber in the fabric or carpet. extruder screws. Raw materials suppliers should be consulted about persistent plate-out problems. an operation plagued by plate-out has to be shut down and the affected metal surface manually or operationally cleaned. thermoforming. Extrusion. Pollution regulations differ so widely from country to country and region to region that general rules for coping with them are meaningless. Processors need to dispose of solid. calendering. If ignored. Often. Plate-out is caused by precipitation and transfer of oxidation and/or hydrolysis products from components of the formulation (usually the stabilizer and lubricant system).326 10 Flexible PVC [References on Page 361] For composite products. paint oven temperatures dictate selection of low-fusing resins and plasticizers. in the formulation. such as talc. For vinyl automobile undercoats and sealants. and smoke.and flame-retardants. Poorly fused undercoats fail prematurely. and compounding processes are sometimes marred or shut down by a phenomenon known as plate-out. if not observed and eliminated. particularly in regions where roads are heavily salted in winter. plate-out can be eliminated “on the run” by temporarily increasing the amount of an abrasive. This comprises the formation of sticky deposits on the hot surfaces of processing machinery. An expensive and labor-intensive clean-up always follows a calender “shipwreck”. and so forth. The surface appearance of finished goods deteriorates in the early stages of a plate-out problem. If this is not recognized and corrected. whether they use hot melt or plastisol technology. Plate-out is prevented in some formulations by including a small amount of a scouring agent such as talc or some grades of silica. Products marred by plateout usually exhibit poor printability. and gaseous wastes and vapors generated in the processing of flexible PVC in compliance with local regulations (see Chapter 18). Sometimes. dies. molds. In flexible PVC products which are foamed during processing. Fully fused vinyl undercoats survive considerable abuse and prolong the life of a vehicle. or lubricant such as stearic acid. the plateout eventually stops the plastic product from releasing from the hot/coated metal or releases a badly marred product from a coated mold.

PVC is considered flexible Above 85 phr DOP.8 MPa (3300 psi). (E = 6. boot and shoe soles. but also on resin molecular weight. 100% Modulus. Outside the United States. However. the simplifying assumption is made that E = 3 G. Results are reported as weight loss per 1000 cycles under conditions agreed to between the interested parties.5 Designing Flexible PVC Compounds 327 10. see Chapter 5 for more details. Abrasion resistance of flexible PVC is often measured by the Taber Abrasion Test (ASTM D 4060). PVC is called highly flexible. This test is run on films 10 mils (0. the flex temperature. substitution factors (SFs) compared to DOP are generally used. Sometimes the D scale is used on semi-rigid compounds with plasticizer levels at or below 40 phr DOP equivalent. which do not correlate exactly with 100% modulus. However. regarded as the upper end of a material’s useful temperature range. defined as tensile stress at 100% elongation. which is the temperature at which the material is considered to have lost most of its elastomeric properties. mine belts. With a medium-high molecular weight PVC. DOP is generally recognized as the benchmark plasticizer for PVC.5.3 Properties Often Specified for Semi-Rigid and Flexible PVC Products Tensile strength and elongation at failure (ASTM D638) depend primarily on the level and type of plasticizer or other flexibilizer in the formulation.5.000 psi). because it is relatively easy to measure accurately and reproducibly. Conditioning of test specimens at the test temperature is critical. To convert G to E. This is explained as being due to the slowness with which PVC crystallites reform after processing. 85 phr DOP (100% modulus 4. G. the angular deflection may extend beyond the elastic limits of the plastic at lower temperatures. Results are important for automobile undercoatings. The brittleness temperature of flexible PVC is generally measured by ASTM D-746. at 23 °C. The hardness of flexible PVC materials is commonly measured by Shore Hardness (ASTM D 2240) using the A scale. floor coverings.25 mm (75 ± 10 mils) thick. Between 35 phr DOP and approx.10. In commercial laboratories the low temperature properties of flexible PVC are often estimated from stiffness measurements run by ASTM D 1043.000 psi) is reported as Tf. as measured by ASTM D 747. the results are sensitive to the direction of sampling and the direction of fold due to the molecular orientation effects of calendering. When comparing the efficiencies of different plasticizers. is also reported. For historical reasons. some people prefer to use the Masland Impact Test (ASTM D1790). at different temperatures.9 ± 0. and electrical cords for use under harsh conditions. which is a cold impact test run on specimens punched from standard test sheets 1. Academic laboratories generally use more precise methods of measuring moduli as functions of temperatures. DOP at 25 phr gives a 100% modulus of about 22. The temperature at which E = 931 MPa (135. which is classified as semi-rigid. on calendered PVC films.90 MPa or 10.48 MPa or 650 psi). so that the result is “apparent” rather than an actual modulus of elasticity. Aging after processing is also very important. Higher molecular weight resins in fully fused formulations give higher tensile strength and elongation at failure. E. is a useful measure of the stiffness of plasticized PVC. For accurate . local testing procedures may be preferred. which measures apparent modulus of rigidity. which is only true if Poisson’s Ratio for the material under test conditions is 0.25 mm) or less in thickness under specified impact conditions. most authors calculate these from Shore hardness measurements. Sometimes T4. In this test. The way D1043 is run.

For niche products. many commercial laboratories use 10 second Shore hardness. They specify definite aging and conditioning periods of usually less than a day. formulations can be devised to meet stringent flammability requirements. The fire resistance of most flexible PVCs is less than that of rigid PVC. weatherability.328 10 Flexible PVC [References on Page 361] results. Other tests used on flexible PVC products include retention of elongation after oven aging. For vinyl plastics. Hardness readings increase with age after molding or other processing. Test sample thickness is critical. because many laboratories have the equipment. because the heat flux to which samples are exposed can be varied from about 10 to 100 kW/m2.25 in) thickness.S. can be used to rank small samples of flexible vinyl materials for rate of heat release after ignition. It is discussed in Chapter 13. This test correlates well with 15 s Shore A hardness in the sense that a plot of Shore A hardness against British Standard softness is a straight line.64 cm thickness. For flexible PVC compounds used as primary insulation on electrical wires and for electrical tapes. ease of ignition. the UL-94 Test run in the horizontal or vertical modes. such as those for plenum cables. the DOT 302 MVSS Test for materials used in automobile interiors. stain resistance. Rate of heat release. sample mass loss rate. many laboratories stack several thicknesses. On calendered or extruded films and sheets. Cone calorimeter results are acknowledged to be more meaningful. . and volume and surface resistivity (ASTM D 257). ASTM E1354. These require enough flexibility for installation in confined spaces and must also pass the UL-910 (NFPA 262) test [27]. For smoke evolution. In commercial quality control testing. ASTM specifies using specimens molded to 0. Physical and electrical testing of PVC are discussed in Chapter 12. the NBS Smoke Chamber Test (ASTM E662) is still used. along with general flammability testing issues. The Underwriters’ Laboratories Insulation Resistance Test is specified for insulation compounds to be used on wires slated for use in wet locations. dielectric strength (ASTM D149). operators never wait until Shore hardness has stabilized before testing. at least one week of aging at 23 °C (73 °F) is recommended. British Standard Softness (B. Other flammability tests often used on flexible PVC products include: the UL-VW-1 Vertical Wire Flame Test. but this is less precise than using specimens molded to 0. Tests commonly used include dielectric constant (ASTM D150). The test is versatile. and emission of obscurational smoke. and smoke are measured or calculated from measured parameters. the UL Vertical Tray Flame Test (UL 1581 for tray cables). resistance to extraction of plasticizers by chemicals. The same considerations regarding aging and conditioning of flexible PVC specimens apply as for Shore Hardness testing. many other specialized tests are used. and the UL-1666 Test for riser cables. electrical properties are critical. Measuring the toxicity of smoke from burning PVC is complex and has been controversial. In the United Kingdom. 2782:32A) is generally specified. the Oxygen Index Test (ASTM D2863). ASTM specifies taking Shore A hardness readings after 15 seconds. However. Note also that Shore hardness readings drop rapidly during the first several seconds after specimen contact.64 cm (0. The Cone Calorimeter Test. However. and effects on taste and odor of foods packaged in flexible PVC.

.6 10. low in color. low in toxicity. When used as sole flexibilizer for PVC. dipole moments. workability. stable. which include compatible nitrile rubbers. and must not interact unfavorably with other needed formulating ingredients or otherwise compromise the end-use properties of the product in which it is employed.10. or distensibility. for use in applications such as plenum cables. and solubility parameters can be used to predict compatibility with PVC. low in odor.6. the correlations between pragmatic performance parameters and scientific measurements on idealized systems become too loose to maintain the latter as standards for predicting the performance of plasticized PVC in the marketplace. low in volatility. A few additional practical comments will be offered in the following. They are low volatility liquids whose polarity and other characteristics are such that they are sufficiently compatible with PVC not to be readily squeezed out of plasticized PVC by moderate pressure [28]. Plasticizers for PVC and theories of plasticization are discussed in detail in Chapter 5. and some poly-acrylates. Many people refer to these materials as PVC “plastifiers” to distinguish them from liquid plasticizers. compatible polyesters. but which exude if used as sole plasticizer. The volume cost of these plastifiers is higher than that of most plasticizers.1 Additives Used in Flexible PVC Compounds Liquid Plasticizers and Solid Flexibilizers Primary plasticizers are the principal additives responsible for flexibilizing PVC. readily dispersible in PVC. compatible polyurethanes. In comparison. some with low flammability and low smoke evolution. Chlorinated paraffins are common examples of secondary plasticizers for PVC. calculated or measured entities such as hydrogen bonding parameters. However. epoxy. ethylene-carbon monoxide-vinyl acetate terpolymers. There are several types of solid flexibilizers for PVC. compatible with PVC. Flory-Huggins interaction parameters. on individual new plasticizer candidates. A plasticizer may reduce the melt viscosity. When mixtures of plasticizers of different chemical families are used. lower the temperature of a second order transition. plastifiers give compounds with higher melt viscosity than corresponding plasticized compounds of equivalent hardness and flexibility. have good permanence. Plasticization theory works reasonably well in quantifying the behavior of single plasticizers in PVC. dielectric constants. These are classified as monomeric.6 Additives Used in Flexible PVC Compounds 329 10. Practical requirements for a successful plasticizer for PVC are that it be cost-effective. These solid materials are chiefly used in PVC thermoplastic elastomer (TPE) compounds and specialty PVC materials. a process aid improves processability without necessarily reducing melt viscosity or the stiffness of the product. or lower the elastic modulus of a product. polymeric. Secondary plasticizers are low volatility liquids whose compatibility with PVC is such that they can be used along with primary plasticizers as part of the plasticizer system. used because they are low in cost and less flammable than most primary plasticizers. The definition of plasticizers adopted by IUPAC in 1951 is still generally accepted: a substance or material incorporated in a material (usually a plastic or elastomer) to increase its flexibility. and specialty flame-retardant plasticizers.

Trimellitate ester plasticizers are made by reacting trimellitic anhydride with plasticizer-grade alcohols. The 2003 Modern Plastics World Encyclopedia lists 402 plasticizers of which 279 are indicated to be compatible with PVC. aliphatic carboxylic diesters. 1. Increasing the degree of branching in the alcohol gives a plasticizer with higher volatility. poorer low temperature properties. epoxides.330 10 Flexible PVC [References on Page 361] Primary plasticizers used in PVC fall into the followingchemical families: dialkyl orthophthalates. such as the phthalates. Most polyester-type polymeric plasticizers are condensation products of glycols with dibasic organic acids. The chief disadvantages are higher cost. ease of processing. Tri-2-ethyl hexyl trimellitate is known as TOTM. if it is attained in PVC plasticized with their products. Di-2-ethylhexyl adipate is known as DOA. Acid-terminated polymeric plasticizers are less environmentally stable than their alcohol-terminated analogs. alkyl sulphonic esters of phenol and cresol. Dialkyl ortho-phthalate esters are the most frequently used plasticizers in PVC applications. Hence. The azelates and the adipates do not lower the melting points of PVC crystallites as much as the corresponding phthaltates do.000. several plasticizer suppliers calculate the exact concentrations of their plasticizers required with a standard PVC resin to produce a desired set of physical properties. The chief advantage of polymeric plasticizers over general purpose monomeric plasticizers is greater permanence. and may be linear or branched. poorer low temperature brittleness in PVC. In addition to making recommendations on how to use plasticizers based on their experience. .and 105 °Crated electrical wire insulations and jackets and other applications requiring plasticizers volatility lower than is attainable with higher molecular weight phthalates. These esters represent the state-ofthe-art in low volatility monomeric plasticizers. phosphate esters. but they flexibilize the amorphous regions of the PVC more efficiently. The alcohols range from hexyl (C6) to tridecyl (C13). Forty suppliers are listed. alkyl benzyl phthalates. Di-2-ethyl hexyl phthalate. toxicological regulation (if required).3 buylene glycol and adipic acid are the most often used starting materials. and they are lower in molecular weight and specific gravity. The dibasic acids have carbon numbers varying from C5 (glutaric) to C10 (sebasic). The selection of the best phthalate plasticizer to use for a particular application is guided by economics. benzoate and dibenzoate esters. C8 or C10 alcohols are commonly used for terminating the polymerizations at average molecular weights between 1. and/or active microbial cultures. are generally identified by acronyms. they impart higher flexibility weight-for-weight and better low temperature properties. is the industry standard general purpose (GP) plasticizer against which other dialkyl phthalates and PVC plasticizers generally are compared via efficiency factors (EF). Their principal uses are in 90 °C. lower plasticizing efficiency. and miscellaneous types. Adams reviewed the status of trimellitate plasticizer use in the United States [29]. polyester-type polymerics. and reduced environmental stability of end products exposed to combinations of warmth. and higher volume resistivity in formulated PVC. also known as DEHP or DOP. humidity.000 and 8. Aliphatic carboxylic diesters. UV light. Practical formulations often contain mixtures of polymeric and monomeric plasticizers. They are based on aliphatic dibasic acids esterified by alcohols ranging from C7 to C10. trimellitate esters. and performance in end-use. DOA is regulated by FDA for use in produce-wrap and meat-wrap films. DOA is less compatible with PVC than DOP and is considerably more volatile. greater susceptibility to oxidation. dialkyl tere-phthalates.

Polymerizable plasticizers are available for specialty applications such as insulation on electrical wires. Mainly due to pressures from environmentalists. Citrates are also used in toys produced by the plastisol process. which are used mostly in stain-resistant flooring. naphthenic hydrocarbons. alkylated aromatics. which have to be connected by soldering and where retraction of the insulation due to heat must not occur. Secondary plasticizers. They are more expensive than phthalate esters. Specialty flame-retardant plasticizers are exemplified by Great Lakes DP-45. Texanol Isobutyrate® (TXIB) is used as a volatile. such as acetyl tri-n-hexyl citrate and butyryl tri-n-hexyl citrate. Several miscellaneous plasticizers are used enough to be worth mentioning. The principal use of phosphate esters is in flame-retarded and smoke-suppressed formulations. They are used as co-stabilizers along with suitable mixed metal stabilizers and some of the newer types of stabilizers. and some linear paraffins.6 Additives Used in Flexible PVC Compounds 331 Epoxy plasticizers have oxirane oxygen groups in their molecules formed by the epoxidation of olefinic double bonds in their starting raw materials: O O O // / \ // R–CH = CH– + CH3–C–O–OH ⎯⎯→ R–CH–CH– + CH3–C–OH cat. R1. have excellent compatibility with PVC. find specialty uses in some blood bags and food wraps. Some citrate esters. and R3 are alkyl or aryl moieties. Alkyl sulfonate esters of phenol are sold in Europe under the trade name Mesamoll®. Use of higher levels of ESO or ELO risks formation of tacky “spew” resulting when the oxirane oxygen is photo-oxidized or hydrolyzed. some bacteria.6. and fungi. viscosity-reducing plasticizer/diluent in plastisols for flooring sheet-goods and coil coatings.2 Lead-Based Stabilizers Stabilizers have been used in flexible PVC compositions to prevent degradation during processing and forming into finished shapes.10. . some formulators use epoxy resins even though these cost more than ESO or ELO. They have the disadvantage of being food nutrients for molds. Phosphate ester plasticizers made from phosphorus oxychlorides have the general structure: (R1O)(R2O)(R3O)P = O Where. and burn with lower heat release than phthalates. Dipropylene glycol dibenzoate exemplifies the benzoate ester plasticizers. where the toy is intended for use by young children. R2. which is a tetrabromophthalate ester with outstanding fire-retardance and low plasticizing efficiency due to its high molecular weight and high specific gravity. 10. extenders and diluents include chlorinated paraffins. Epoxidized soy bean oil (ESO) and epoxidized linseed oil (ELO) are the most widely used epoxides. Sound formulators use epoxides at low levels because the oxirane oxygen group has a strong compatibilizing action with PVC. To get the stabilizing action of oxirane oxygen without the risk of exudation or microbial attack. Numerous triaryl and alkylaryl phosphate plasticizers are available.

this has been replaced by tribasic lead sulfate (TBLS). they are slightly toxic. but are generally being phased-out due to pressure from environmentalists on the PVC industry to stop using leadcontaining stabilizers. They have to be handled carefully due to their tendency to “dust”. all manufactured as fine white powders. Over the years. lead-based stabilizer systems were the first commercially successful ones for PVC. Atomic chlorine and HCl released from degrading PVC. Historically. in pre-weighed batch charges (each in its own PVC bag). light stable. shelf stable. homogeneous. Even though finely powdered litharge (PbO) was a fairly effective stabilizer for flexible PVC. and dibasic lead phosphite. TBLS has the lowest cost of these three. which are high enough to make them unusable in transparent or translucent applications due to their pigmenting action. They are among the most cost-effective stabilizers for plasticized PVC. Dibasic lead phosphite is the most expensive of the three. They are generally fine particle size basic solids. readily form basic lead chlorides which do not promote further degradation of PVC. A simple way to generalize the action of heat stabilizers in flexible PVC is the following: thermal degradation of PVC molecules starts at defect structures which may take several forms but all involve labile chlorine atoms. environmentally acceptable. pigments. non-staining. in favor of basic carbonate of white lead (BCWL). resistant to oxidation and hydrolysis. but is favored in some applications because it has more light-stabilizing action than TBLS or dibasic lead phthalate. Waldo Semon abandoned it early. tasteless. In the United States. When breathed or ingested by humans. there have been more changes in stabilizers during the last 20 years than in any other aspect of PVC technology. . They should also be low in cost. non-volatile. non-exuding. and non-lubricating or only weakly lubricating. Stabilizers prevent this as follows: | + —C–ClL | labile chlorine on PVC M–S— stabilizer → | —C–S— | stabilized PVC + M–Cl spent stabilizer Desired features for stabilizers used in flexible PVC include that they should preferably be colorless. nontoxic. easily dispersed in PVC. compatible with PVC and other additives. easy processing. which disperse readily in flexible PVC compositions so that there are no significant unstabilized volume elements. dibasic lead phthalate. nonconductive. but only slightly so due to their low solubilities in water or saliva. non-plasticizing. Related theory is covered in Chapter 4. or lubricants.0 and 2. problems of worker exposure to lead have been overcome by handling the powdered lead stabilizers in closed bulk air pallet systems. All these lead stabilizers sulfur-stain on contact with mercaptides or hydrogen sulfide.332 10 Flexible PVC [References on Page 361] but also partly due to the results of fundamental research.25. They have refractive indices between 2.05 mg/m3 [30]. readily available. In the United States. heat stable. odorless. because of its color. a progressive “unzippering” of successive HCl molecules from the PVC is initiated. nonextractible. chemically stable. or in prilled stabilizer-lubricant one-packs. Unless an active stabilizer molecule is close to the site from which labile chlorine releases from PVC. but is sufficiently basic to hydrolyse some polymeric plasticizers. non-migrating. non-chalking. and efficient in stabilizing action. non-plating. the permissible exposure limit (PEL) for airborne lead is 0.

In liquid systems. Today. When lead-stabilized vinyl insulation or sheathing materials are ground to a fine particle size and subjected to EPA’s Toxic Characteristic Leaching Procedure (TCLP). which are expensive. lead stabilizers perform the best.6. Then. Many suppliers have qualified compounds.3 Mixed Metal Stabilizers For many years. Cadmium has been phased out. whose solubility parameters are close to those of PVC and other ingredients such as plasticizers in the formulation.6 Additives Used in Flexible PVC Compounds 333 For building wire insulations for use in damp or wet locations. many mixed metal stabilizers for flexible PVC use zinc compounds. The barium and calcium compounds do not react with the labile chlorine atoms on PVC as actively as the zinc compounds do. they are more soluble if the extractant is buffered to be acidic or alkaline. due to the amphoteric nature of lead. By contrast with lead. The workhorse solids consist of barium or calcium stearate. zinc is backed up by barium or calcium in the stabilizer at a higher level than the zinc. The barium and calcium chlorides are weak Lewis acids and promote PVC degradation much less than zinc chloride does. together with various synergists. use of cadmium has been phased out. Grossman has described low extractable lead stabilizers [31]. are also often used. which is run under acidic conditions and allows a maximum lead concentration in the leachate of 5mg/l. Today. 100 mg/l of barium is allowed in TCLP leachates.10. The zinc chloride formed in these exchanges is a potent Lewis acid capable of catalyzing catastrophic dehydrochlorination of PVC. plus some zinc stearate. early color”. Therefore. This requires immersion in water at 75 or 90 °C for twenty-six (26) or more weeks without significant loss of dielectric properties. the most popular mixed metal stabilizers for flexible PVC were based on barium and cadmium or barium-cadmium-zinc combinations. Alkyl aryl phophites improve clarity and help maintain “good. which exchange their anions for labile chorine atoms on PVC molecules. But cadmium is present in much old flexible PVC rework. Therefore. It is necessary to protect liquid mixed metal stabilizers from exposure to humid air by handling them in closed bulk or semi-bulk systems. Baker and Grossman presented work on cadmium-free mixed metal stabilizers [32]. because it is considered to be a toxicity hazard. barium alkyl phenates and zinc octoate may be used together. lead-stabilized wire and cable PVC scrap is either recovered or sent to secure landfills. and the zinc ceases to be part of a strong Lewis acid. by anion exchange. including palmitates and laureates. Calcium and zinc are not regulated in this test. 10. Phenolic antioxidants such as butylated hydroxytoluene (BHT) and Bisphenol A are included in many formulations. But. Mixed fatty acid salts. TBLS and dibasic lead phthalate and dibasic lead phosphite have low solubilities in water at pH 6 to 8 (neutral). barium or calcium chlorides are formed in the mixed metal system. Mixed metal stabilizers have been used for years in clear flexible PVC formulations. with high boiling solvents compatible with PVC. which pass long-term insulation-resistance testing. Pentaerythritol was found empirically to be beneficial. along with various phosphites and epoxy plasticizers or resins. In 1993. marginal or failing results may be experienced. Other synergistic ingredients include epoxides and phosphite antioxidants. Quite small amounts of water in many mixed . Lead-replacement and low-lead systems continue to be actively evaluated for these uses. The barium-zinc and calcium-zinc stabilizers may be either solids or liquids.

6. They are reported to contain combinations of primary and secondary metals. Recent work carried out in a PE carrier resin confirms this long-accepted fact and shows that coarser grades are more abrasive than fine particle size fillers [36]. Stabilizer technology is covered in Chapter 4. which has aluminum. filler may be any low cost solid. Some of these use hydrotalcites similar to the well-known antacid Maalox®. The flexible PVC industry uses the term “fillers” to refer to inert particulate solids incorporated into formulations for various reasons. and carbonate functionalities. Grades which contain significant fractions of hard silicates are much more abrasive. the specific gravity of calcite is 2. A novel approach using “latent mercaptides” was described by Conroy [34].85 and that of aragonite is 2. metal coordinators. The compositions of most lead-replacement stabilizers are proprietary because of unresolved patent and technical issues.334 10 Flexible PVC [References on Page 361] metal stabilizers are sufficient to cause phase separation and serious loss of properties by hydrolyzing some of the phosphite and adding to a portion of the epoxide. having a Mohs hardness of 3. For instance. and hollow microspheres used to lower specific gravity while achieving other desired filler effects. 10.71. Calcite is soft. For satisfactory foaming. or precipitated calcium carbonate derived from limestone or marble. Regulated phosphites and polyols are used as synergists in these stabilizers. interlocking crystals of calcite. wetground. including hardening. . or gas which occupies volume in a part and reduces its volume-cost. the stabilizer needs to be matched to the desired temperature range for foam formation. and antioxidants. Examples are calcined clays added to wire insulation formulas to raise electrical volume resistivity. and reduction of volume-cost. New calcium-zinc stabilizers were described by Bacaloglu [33]. Since many flexible vinyl products are sold by volume rather than weight. hydroxyl.4 Fillers Generically. Some zinc-containing stabilizers are effective kickers for blowing above 180 °C. such as Rhodiastab 83® or Rhodiastab 50®. but are only used in specialty flexible applications. Promising early work on the stabilization of PVC by “plasticizer thiols” was described by Starnes [35]. metallic chloride deactivators. some lead stabilizers are good “kickers” for blowing in the range 160 to 180 °C (320 to 356 °F). stiffening. β-diketones. For use in volume-cost calculations. which are predominantly calcite. Marble consists of small.95 The most widely used fillers in flexible and semi-rigid PVC are grades of dry-ground. When foaming flexible PVC with azodicarbonamide blowing agents. fumed silica or bentonite clay added to plastisols to increase their yield value. magnesium. some of which are sold as one-pack systems. Therefore. it is advisable to use a stabilizer recommended by the blowing agent manufacturer. Numerous calcium-zinc mixed metal stabilizers are sanctioned by FDA for use in flexible PVC food contact films. are recommended to prevent early discoloration in some lead-replacement stabilizer systems. their volume-cost is the dominant economic parameter. that of true dolomite is 2. inorganic acid acceptors. Organotin stabilizers are very successful in the United States in rigid PVC. liquid. Functional fillers are added to improve specific properties. pure calcium carbonate fillers are low in abrasivity to processing equipment. Particulate solids called fillers must not dissolve in the flexible PVC matrix. This is the stable crystal structure of CaCO3 at ordinary temperatures and pressures.

Typical grades used in non-blocking calendered films are fine-ground so that > 99% passes a 325 mesh screen (with openings of 1. Reinforcements such as glass or metal fibers generally have aspect ratios in excess of 10 : 1. with an RI of 2. which are extruded. Talc may also be dusted at 0.51 and 1. The disadvantage of using high levels of fillers in flexible PVC is the reduction of tensile and tear strength.7 mils). in optimizing end-use properties and minimizing cost. and resistance to attack by moisture and chemicals. Fumed silica may be added to hot-processed compounds as a scrubbing agent and to plastisols to increase viscosity and yield value. require fillers with an average esd of 3 microns or less and coarsest particles of 12 microns diameter (0. with a slightly lower RI (1. reducing coefficients of thermal expansion. but allowance must be made for its high specific gravity (4. Diatomite (amorphous silica) is added to PVC plastisols to increase viscosity and yield value and to reduce surface gloss after fusion. with an RI of 1. Barium sulfate (Barytes). Typical electrical insulations and cable jackets.5).76 for rutile.47 mils). The “packing fraction” (PF) is a measure of how efficiently finer particles fill the voids between coarser particles.10. and whether the particles have had a surface treatment. The high gravity is an advantage for use in sound-absorbing and visco-elastic damping compounds. the average particle size and size distribution. Specific heats per unit volume are comparable for most fillers and many polymers.1 to 0. The average size of filler particles is usually defined in terms of an equivalent spherical diameter (esd). which contributes a high degree of opacity. whether it has been dry-ground or wet-ground or precipitated. The refractive index (RI) of flexible PVC matrices usually ranges between 1. stiffening.7 mils or 44 microns). is a strong pigment. The most used fillers have aspect ratios of less than 4 : 1. Presence of iron oxides such as Fe2O3 in the filler tends to color a compound yellow-brown and will compromise its heat stability unless it is stabilized to withstand the presence of the iron oxide. Cable jackets designed to give low HCl emission on burning generally use precipitated calcium carbonates having 0. The principal advantages of inorganic fillers in flexible PVC include cost reduction. may be used in translucent flexible vinyl compounds. Vinyl floor tile made by calendering tolerates filler particle sizes up to 99% through a U.6 micron esd. The softest non-carbonate filler used in flexible PVC is talc represented as 3 MgO · 4 SiO2 · H2O. Standard 50 mesh screen having 297 micron openings (11. Mica is added to PVC compounds to impart a non-blocking surface and to provide stiffening when that is also desired. is a weak pigment as well as a filler for flexible PVC.48 and 1.6 Additives Used in Flexible PVC Compounds 335 Considerations in selecting a particular grade of calcium carbonate filler include the purity of the original ore.S.55 and that of typical phthalate plasticizers ranges between 1. Calcium carbonate (calcite). The ratio of the average lengths of the major to minor axes of filler particles is called the “aspect ratio”.6) than calcite. High filler levels also compromise processability by increasing melt viscosity. Zero or very low content of asbestos-related minerals is specified for talcs used with PVC. and contributing to better flammability behavior. TiO2.25% onto PVC compound cubes or pellets to improve flow in bulk handling systems and hopper cars.53 because the RI of PVC is 1. toughness at low temperatures. elongation at failure. . Talc is often added to calendering formulations to reduce plate-out on the rolls and to extrusion formulations to reduce plate-out on screws and dies.65.50. The best filler particle sizes for most flexible PVC applications are determined by experience. abrasion resistance. Clear vinyl compounds are generally unfilled.

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