VINYL POLYMERS (PVC) POLY(VINYL CHLORIDE)
James W. Summers The Geon Company One Geon Center Avon Lake, Ohio 44012
September 16, 1996
page 2 POLY(VINYL CHLORIDE) James W. Summers
TABLE OF CONTENTS page
INTRODUCTION DISCUSSION PHYSICAL PROPERTIES Morphology as polymerized Hierarchical structure of PVC Morphology during processing PVC fusion (gelation) Plasticized PVC Morphology PVC physical parameters CHEMICAL PROPERTIES Molecular structure - Monomer addition orientation End groups and branching Stereoregularity Polymerization kinetics of mass and suspension PVC PVC RESIN MANUFACTURING PROCESSES Mass Polymerization Suspension Polymerization Emulsion Polymerization Micro-Suspension Polymerization Solution Polymerization Copolymerization COMPOUNDING Stabilizers Impact modifiers Processing aids Lubricants Plasticizers Fillers Pigments Ultraviolet light stabilizers Biocides Flame retardants Foaming or blowing agents PRODUCTION VOLUME AND ECONOMICS Compound manufacture PVC resin manufacture World demand PVC resin price 4 7 7 7 12 15 17 20 21 22 22 23 24 25 30 30 31 31 33 33 34 36 36 38 40 40 43 47 47 47 48 48 49 50 50 52 54 55
page 3 POLY(VINYL CHLORIDE) James W. Summers
TABLE OF CONTENTS continued
SPECIFICATIONS AND STANDARDS USES AND MARKETS Pipe and fittings Weatherable siding, windows, & doors Profiles Wire & cable Injection molded products HEALTH AND SAFETY FACTORS (TOXICOLOGY) MSDSs available Health Fire and explosion Toxicology Regulatory ENVIRONMENTAL CONSIDERATIONS AND RECYCLING Chlorine, the material used to make PVC Vinyl Solid Waste and Recycling Incinerating PVC Wastes Common misperceptions about vinyl ACKNOWLEDGMENT BIBLIOGRAPHY AND REFERENCES ABSTRACT 57 58 59 60 62 62 63 64 64 64 66 67 68 69 69 71 72 74 79 80 96
It is second in volume only to polyethylene and had a volume sales in North America in 1995 of 6. it acts to inhibit combustion in the gas phase. useful in many building applications as well as many electrical housings and electrical insulation applications. compounds that have stiff melts and little elastic recovery for outstanding dimensional control in profile extrusion. making it possible to produce materials in a range from flexible elastomers to rigid compounds. providing the vinyl with a very high level of combustion resistance. Summers
Poly(vinyl chloride) [9002-86-2] (PVC) has large and broad uses in commerce.page 4 POLY(VINYL CHLORIDE) James W.
PVC has a unique ability to be compounded with a wide variety of additives.5 J/mm at -40°C.
. This large volume of sales can be attributed to several unique properties. See table 1 for volumes of several thermoplastics. materials that are virtually unbreakable with a notched Izod impact greater than 0. Vinyl compounds usually contain close to 50% chlorine. Not only does the chlorine provide no fuel.7 billion pounds) (1).2 billion kilograms (13. or low viscosity melts for thin walled injection molding. materials that are weatherable with good property retention for over 30 years.
ranges from 500 to 3500. (2. Summers
Produced by free radical polymerization. Waldo Semon at BFGoodrich. German workers at Chemische Fabrik GriesheimElectron tried but failed to build machinery that could process PVC and overcome its instability.
The first discovery of PVC was in 1872 when E. while looking for an adhesive to bond rubber to metal for tank liners. PVC has the following structure:
where the degree of polymerization. 3). In 1926. Baumann found that exposure of vinyl chloride to sunlight produced a white solid that resisted attack by potassium hydroxide or water and melted with degradation at above 130°C. finally they gave up their patents (3). thus he invented the first thermoplastic elastomer. n. made it highly elastic (3).
. found that boiling PVC in tricresyl phosphate or dibutyl phthalate. From 1912 to 1926.page 5 POLY(VINYL CHLORIDE) James W.
NORTH AMERICAN TOTAL 0.66 1.25 0.32 2.70
0.34 0.31 0. POLYSTYRENE ABS.78 0.84 2.38 4.66 1.78 0. POLY(VINYL CHLORIDE) HDPE.
BILLIONS OF KILOGRAMS
PVC. LOW DENSITY POLYETHYLENE PP.45 0.15 0.68 0. POLYCARBONATE ACETAL
5.18 6.15 0.20 2.25
1. LINEAR LOW DENSITY POLYETHYLENE LDPE.40 6.29 2. POLYPROPYLENE PS.47 NYLON
.page 6 POLY(VINYL CHLORIDE) James W.81 0. HIGH DENSITY POLYETHYLENE LLDPE. Summers
Table 1.36 5.47
ACRYLIC 0.99 5.22 0.26
4. 1995 SALES VOLUME IN NORTH AMERICA (1).70
3.30 0. ACRYLONITRILE/ BUTADIENE/STYRENE THERMOPLASTIC POLYESTER PC.
In the suspension polymerization of PVC.01 . The morphology formed during polymerization strongly influences the processability and physical properties. particles of PVC deposit onto the membrane from both the monomer and the water sides forming a skin 0.5 . This membrane. Summers
Morphology as polymerized
The major type of polymerization of PVC is the suspension polymerization route.page 7 POLY(VINYL CHLORIDE) James W. Primary particles. isolated by dissolving the PVC in tetrahydrofuran and measured at 0. droplets of monomer 30 . deposits onto the skin from the water side of the membrane (4).5 µm thick that can be observed on grains sectioned after polymerization (4. 6). has been found to be a graft copolymer of polyvinyl chloride and polyvinyl alcohol (4. Mass polymerized PVC has a similar morphology to suspension PVC. 0.02 µm thick. deposit onto the membrane from the monomer side and water phase polymer.150 µm in diameter are dispersed in water by agitation. These
.0. Early in the polymerization.1 µm diameter. A thin membrane is formed at the water/monomer interface by dispersants such as polyvinyl alcohol or methyl cellulose. 5). 1 µm diameter.
Grain ~ 150 µm dia.
Skin ~ 2-5 µm thick
Primary particles ~ 1 µm dia.page 8 POLY(VINYL CHLORIDE) James W. Summers
domain sized water phase particles may be one source of the observed domain structure (7).
. A grain of suspension PVC and its cross-section showing the skin and primary particles.
Mass polymerized PVC also has a skin of compacted PVC primary particles very similar in thickness and appearance to the suspension polymerized PVC skin. however.
. compared in figure 3. Summers
Figure 2.1 µm diameter particles deposited from the water phase. mass PVC would not contain the thin block copolymer membrane (7). Skin of a suspension PVC grain showing 0.page 9 POLY(VINYL CHLORIDE) James W.
Above two percent conversion. The grain shape plays an important role in determining grain packing and bulk density of a powder (9).
In suspension PVC polymerization.page 10 POLY(VINYL CHLORIDE) James W. 10 . droplets of polymerizing PVC. Summers
Figure 3. the shape is quite spherical. the shape can be quite irregular and knobby (9). Cross-sections of PVC grains from a) suspension and b) mass PVC grains showing similar morphologies. With one droplet per grain. These primary particles are stabilized by a negative chloride charge (4.200 µm diameter (8).12). PVC precipitates from its monomer as stable primary particles. agglomerate to form grains at 100 . 13). With several droplets making up the grain. these
. 30 150 µm diameter. slightly below 1 µm diameter (4.
For both suspension and mass polymerizations at less than two percent conversion.
may be the source of some of the domain sized structures. that break down the primary particles further.(17). When PVC is swelled by plasticizer or swelled with a poor solvent such as acetone.
These primary particles also contain smaller internal structures.20).01 µm (22). swelling reaches a limit where the PVC will no longer absorb more plasticizer or acetone (21). The origin and consequences of this structure is not well understood. Plasticizer or acetone only swells the amorphous regions without dissolving the crystallites. Sectioning the PVC grains of either suspension or mass resins readily shows the skins. Also domain sized flow units may be generated by certain unusual and severe processing conditions. This data suggests a structure where the crystallites of about 0.01 µm (18 . Electron microscopy reveals a domain structure at about 0.01 µm spacing. 15.
On an even smaller scale is the microdomain structure at 0.01 µm spacing are tied together by molecules in the amorphous regions. PVC polymerized in the water phase and deposited on the skin. 8.10 µm diameter (4. primary particles at 1 µm diameter. Small angle x-ray scattering reveals a scattering peak (figure 4) corresponding to density fluctuations spaced at about 0. As mentioned earlier. such as high temperature melting at 205°C followed by lower temperature mechanical work at 140 . 16).1 µm diameter (8. 14).150°C. Also electron microscopy shows a spacing in plasticized PVC of 0. Summers
primary particles agglomerate.page 11 POLY(VINYL CHLORIDE) James W. and agglomerates of primary particles at 3 .
70 60 X-ray Intensity 50 40 30 20 10 0 0 0.5
Figure 4. Small angle X-ray scattering pattern from PVC plasticized with 20 parts per hundred resin of dioctyl phthalate (18). PVC has structure which is built upon structure which is built upon even more structure. Also figure 5 examines a model of these hierarchies on three scales. A summary of these structures is listed in table 2. 2 Θ
Hierarchical structure of PVC
As we have just discussed. These many layers of structure are all important to performance and are inter-related.5 1 1.page 12 POLY(VINYL CHLORIDE) James W.
Made up of a billion molecules. In mass polymerization it is the free flowing powder.10 µm diameter 0.page 13 POLY(VINYL CHLORIDE) James W. It is usually a graft copolymer of PVC and the dispersant such as polyvinyl alcohol. Summary of polyvinyl chloride morphology.01 µm spacing Secondary 0.200 µm diameter 0.150 µm diameter 0. Feature
30 .01 . it is often the melt flow unit established during melt processing.5 µm thick 1 µm diameter
The dispersed monomer during suspension polymerization.150°C. The shell on grains made up of PVC deposited onto the membrane during suspension polymerization. the free flowing powder that is usually made up of agglomerated droplets. The membrane at the monomer-water interface in suspension PVC. Formed during polymerization by the merging of primary particles.1 µm diameter
Microdomains 0. In emulsion polymerization it is the emulsion particle.5 .01 µm crystallinity spacing
. Formed as a single polymerization site in both suspension and mass polymerization by precipitation of polymer from the monomer. In mass polymerization it is PVC compacted on the surface of the grain.02 µm thick 100 . Crystallite spacing. After polymerization. Summers
Table 2.0. Formed under special conditions such as high temperature melting at 205°C followed by lower temperature mechanical work at 140 . Crystallinity that is re-formed from the amorphous melt and is responsible for fusion (gelation).
Agglomerates of primary particles Domains
3 . Water phase polymerization also produces domain sized structure.
The hierarchical structure of PVC.page 14 POLY(VINYL CHLORIDE) James W.
PVC resin. intensive mixing above the glass transition temperature. During this process. First the skin is torn. If a large amount of plasticizer is added.page 15 POLY(VINYL CHLORIDE) James W. However the grains of PVC are largely unchanged and are not grossly deformed nor are they broken down to smaller particles (23). the grains of PVC are broken down. Then the grains are broken down to agglomerates of primary particles. intensive mixer.
In plasticized PVC. then to primary particles
. fillers. sheared. Continued heating increases the diffusion rate of plasticizer into the PVC mass where the excess liquid is eventually absorbed and the powder dries.
PVC powder compounds are heated. and deformed during melt processing. liquid plasticizers first fill the voids or pores in the PVC grains fairly rapidly during powder mixing. This increase in apparent bulk density is due to the smoothing and rounding of the irregular surface. Summers
Morphology during processing
The first step in processing is usually powder mixing in a high speed. the excess plasticizer beyond the capacity of the pores. and pigments are added to the powder blend for distributive mixing. stabilizers. plasticizers. initially remains on the surface of the grains making the powder somewhat wet and sticky. lubricants. For both suspension and mass PVC resins. results in a progressive increase in apparent bulk density with higher mixing temperatures (23). processing aids. exposing the PVC grain’s internal structures (24).
1. 33).1 nm) (21. made of syndiotactic structures. A model of the crystallite is drawn in figure 6.32). The crystalline structure of PVC is found to be an orthorhombic system. two monomer units per unit cell. The primary particles seem to be persistent and fairly stable structures in the melt (25 .
.page 16 POLY(VINYL CHLORIDE) James W. The primary particle is about a billion molecules of PVC held together by a structure of crystallites and tie molecules (21).
The PVC crystallites are small (average 0.53 specific gravity (34 37). and are packed laterally to a somewhat greater extent (4.7 nm = 3 monomer units) in the PVC chain direction.44 . and 1. This processing window of stable primary particles exists even with continued melt processing. Summers
as the melt flow units.
which can entangle at the flow unit boundary. Summers
Figure 6. The crystallite structure of PVC. 38). This process is known as fusion or gelation.7 nm
4. forming secondary crystallites.
The strength created by the fusion process is strongly dependent on the previous processing temperature and the molecular weight of the PVC (38 .page 17 POLY(VINYL CHLORIDE) James W. These entangled molecules can recrystallize upon cooling.1 nm
PVC fusion (gelation)
The PVC primary particle flow units (billion molecule bundles) can partially melt. The entrance pressure in capillary rheometry is often used as a measure of the fusion strength
4. The degree of fusion or gelation is measured in several ways. free some molecules of PVC.
0. and tie the flow units together into a large three dimensional structure (21.44).
creep rupture strength. and cut resistance. Fusion has also been assessed based on scanning electron microscopy of fractured surfaces (29. In plasticized PVC.page 18 POLY(VINYL CHLORIDE) James W. 56 . A model for accounting for molecular weight effects and processing temperature effects on PVC fusion is presented in figure 7. Summers
(40.41). Differential scanning calorimetry also is often used as an indication of previous melt temperature and the amount of crystallinity melted and reformed as secondary crystallinity (54.59). this large three dimensional structure (also dependent on molecular weight and previous processing temperature) determines tensile strength. 42. 30. Sometimes the acetone swollen specimens are sheared between glass slides to further establish the strength of the three dimensional structure (59). In these cases both the melt temperature during processing and the PVC molecular weight play a large role in the Izod and creep rupture (38 . 55). and even flow in rigid injection molding.
. X-ray defraction has been used to measure gelation (55). creep.53).
The strength of this large three dimensional fused (gelled) structure has been shown to be critical in determining Izod impact. 45 . Acetone or methylene chloride swelling and observation of structural break-down is widely used as a qualitative measure of fusion (44. 46). And inverse gas chromatographic measurements have also been useful in accessing the degree of fusion of PVC (60).
a) Unfused PVC primary particles.page 19 POLY(VINYL CHLORIDE) James W. Summers
Figure 7. accounting for molecular weight effects and processing temperature effects.
b) Partially melted PVC primary particles.
d) Partially melted then recrystallized low molecular weight PVC. showing strong three dimensional structure. showing weak three dimensional structure.
. Model for PVC fusion.
c) Partially melted then recrystallized high molecular weight PVC.
45).page 20 POLY(VINYL CHLORIDE) James W. Partial melting allows entanglement at the flow unit boundaries.
Plasticized PVC Morphology
While most of the discussion has been on rigid PVC. The grains break down to 1 µm primary particles which become the melt flow units (44). 56). 56. except that plasticizer enters the amorphous phase of PVC making the tie molecules elastomeric. This has been shown to be caused by melt fracture. however some observations show a fall off in impact properties with higher melt temperatures (42. The crystallites are not destroyed by plasticizer (21). they can also be responsible for roughness when improperly handling regrind (63). These flow units of fused multiple primary particles can lead to surface roughness during extrusion. plasticized PVC has the same structures as rigid PVC. in both rigid and plasticized PVC (44. 62). Summers
PVC normally improves in properties with increasing fusion (or increasing melt temperature).
. when PVC fuses and flows as large melt flow units of multiple primary particles (61). followed by recrystallization upon cooling to form a strong three dimensional elastomeric structure (38.
value 23°C.42 120 0.54 83°C. PVC PROPERTY Crystallographic data VALUE orthorhombic 2 monomer units/cell a b c 1.25 80 0.39 23 0.508 nm 19% 4.5 REFERENCE
commercial PVC single crystal Percent crystallinity as polymerized from the melt Density (uncompounded) whole crystallites Oxygen permeability
64 65 37 66
Poisson ratio (rigid PVC) Refractive index Glass transition temperature Coefficient of linear thermal expansion (unplasticized) Specific heat rigid PVC
plasticized PVC (50 phr DOP)
Thermal conductivity (unplasticized) Dielectric strength Solubility parameter
.41 1.06 0.53 grams/cc. 0. temp.51 nm 1.page 21 POLY(VINYL CHLORIDE) James W. 238 e-13.35 120 0.37 50 0.2 X 10-4 cal/cm sec °C.524 0.5 Kvolts/mil 20 Kvolts/mm. 9. 7 X 10-5/°C. Summers
PVC physical parameters
Table 3.024 0. 50 0./cm3]0.54 0. 0.40 80 0.45 4.22 cal. 1.39 grams/cc./gram °C.9% 1. PVC physical parameters.3/RT cc/cm sec cm2 cm Hg 0.75 (average) [cal.
then 13.Monomer addition orientation
The addition of vinyl monomer to a growing PVC chain can be considered to add in a head-to-tail fashion. resulting in a chlorine atom on every other carbon atom. Summers
Molecular structure . resulting in chlorine atoms on adjacent carbon atoms. proving the head-to-tail structure of PVC (71). tail-to-tail structure would be expected to go to 100% completion.5% of the chlorine should remain at the end of reaction. Dilute solutions of PVC treated with zinc. tail to tail fashion.
. removes 87% of the chlorine.page 22 POLY(VINYL CHLORIDE) James W. If dechlorination of head-to-tail structure starts at random positions. (-CH2-CHCl-CH2-CHCl-CH2-CHCl-CH2-CHCl-)n
or in a head-to-head. (-CH2-CHCl-CHCl-CH2-CH2-CHCl-CHCl-CH2-)n
Dechlorination of head-to-head.
made by mass or suspension polymerization at 50 . about 60% of the chains have unsaturated chain ends (72) and the percentage of chain ends containing initiator fragments is low (73).
PVC polymerization has a high chain transfer activity to monomer. Conventional PVC resins.2 to 2 branches per 100 carbon atoms (65. Chain transfer to polymer leads to branching.
. -CHCl2 .
-CH2-CHCl-CCl=CH2 . Branching in PVC has been measured by hydrogenating PVC. removing chlorine with lithium aluminum hydride. 73).page 23 POLY(VINYL CHLORIDE) James W. Summers
End groups and branching
Both saturated and unsaturated end groups can be formed during polymerization by chain transfer to monomer or polymer and by disproportionation.90°C. -CH2Cl . The ratio of methyl to methylene groups is measured by infrared spectroscopy using bands at 1378 and 1350.
-CH2-CHCl-CH=CHCl . Some of the possible chain end groups are shown: -CH3 . or 1370 and 1386 cm-1. contain 0.
page 24 POLY(VINYL CHLORIDE) James W. Then the ratio of propagation rates for syndiotactic to isotactic. Thus with decreasing polymerization temperature. 75).
The addition of monomer fixes the tacticity of the previous monomer unit.8.2 . Syndiotactic structure has the adjacent chlorine atoms oriented to opposite sides of the carbon-carbon-carbon plane. Isotactic structure has the adjacent chlorine atoms oriented to same side of the carbon-carbon-carbon plane. The potential energy for syndiotactic conformation is 4. 77). ks/ki.4 kJ/mol (1-2 kcal/mol) lower than for isotactic conformation (74. the degree of syndiotacticity in PVC should increase. Measured amounts of syndiotacticity are illustrated in figure 8 (76. must increase with decreasing temperature.
page 25 POLY(VINYL CHLORIDE) James W.
Polymerization kinetics of mass and suspension PVC
The polymerization kinetics of mass and suspension PVC are considered together because a droplet of monomer in suspension polymerization can be considered to be a mass polymerization in a very tiny reactor. During polymerization.
Percent Syndiotactic Diads
80 70 60 50 40 30 -50 -25 0 25 50 75 100 Polymerization Temperature. The precipitated polymer remains swollen with monomer. the polymer precipitates from the monomer when the chain size reaches 10 . This leads to a higher concentration of radicals in the polymer gel and to an increased polymerization rate at higher polymerization conversion. but has a reduced radical termination rate. The Syndiotactic Structure of PVC. C. Summers
.20 monomer units.
3 X 1010 L/(mol sec). ) = a polymer chain radical in the polymer gel phase. kp. ) + M (R(M) . -→
Reactions in the polymer gel: propagation (R . ) -→
where R . ) -→ (P) + M .. and kt are reaction rate coefficients for initiation.. + M -→ R.page 26 POLY(VINYL CHLORIDE) James W. propagation and termination. (M) = monomer molecule in the polymer gel phase. = a polymer chain radical in liquid monomer. Summers
Reactions in the liquid phase:
ki -→ M . and kt at 60°C are 1. + R . ) + (R .
kp R .. Values for kp. M = monomer molecule. respectively (78). -→ P + M .23 X 105 and 2. P = polymer in monomer. and ki.
. + M
chain transfer to monomer
kt R . (R . R(M) .
chain transfer to monomer
(R . ) + M -→ (R . (P) = polymer gel.
.84). creating a higher concentration of radicals.38 X 10-3 at 70°C and a general expression is Cm = 5. Thus the polymerization rate increases with conversion to polymer. The lack of mobility in the polymer gel phase. The chain transfer constant to monomer.78 e-2768/T.25 X 10-4 at 30°C and 2. Summers
Polymerization in two phases. the molecular weight increasing with lower polymerization temperature as indicated in figure 9. and thus creating a higher polymerization rate. Thus temperature of polymerization strongly influences PVC molecular weight. Cm. is the ratio of the rate coefficient for transfer to monomer to that of chain propagation. chain transfer to monomer happens once in every 1600 monomer propagation reactions and at 70°C. Cm = 6. the liquid monomer phase and the swollen polymer gel phase.81).
Chain transfer to monomer is the main reaction controlling molecular weight and molecular weight distribution. chain transfer happens once every 420 monomer additions (80. reduces termination. form the basis for kinetic descriptions of PVC polymerization (79 . At 30°C. The polymerization rate is slower in the liquid monomer phase than in the swollen polymer gel phase due to the greater mobility in liquid monomer which allows for greater termination efficiency.page 27 POLY(VINYL CHLORIDE) James W. 82 .
and weight average molecular weight (Mw) for commercial grades of PVC are shown in table 4 (85).page 28 POLY(VINYL CHLORIDE) James W. K values are used. In Europe. number average molecular weight (Mn). Weight average molecular weight 120000 100000 80000 60000 40000 20000 45 55 65 75 85 Polymerization temperature. The relationship between inherent viscosity. measured at 0.
PVC molecular weights are usually determined in the USA using inherent viscosity or relative viscosity measured according to ASTM D1243.2 grams/100 ml of cyclohexanone at 30°C.
Figure 9. K value. 0.5% in cyclohexanone. C. PVC molecular weight as influenced by polymerization temperature.
Weight average molecular weight Mw (X 10-3) 30.83 0.5 89.16 1.23 1.0 52.0 107.1 58.3 51.57 0.1 69.0 61.5 68.9 77.78 0.9 64.80 Relative viscosity.40 1.30 1.0 22.0 20.09 1.0 78.5 81.32 1.21 1.20 1.62 0.30 1.42 0.0 67.0 55.3 53.7 83.0 27.0 47.0 195.0 128. Inherent viscosity.0 47.0
.2 71.14 1.0 36.88 0.6 56.24 1.43
K value.08 1. (Fikentscher: DIN 53726) 45.page 29 POLY(VINYL CHLORIDE) James W.0 50.0 38.27 1.60 1.8 96.1 49.0 62.5 25.5 141.5 33. Summers
Table 4.0 44.0 40.0 82. ASTM D1234 1.5 73.92 0.18 1.17 1.98 1.0 18.0 168.10 1.0 36.52 0.13 1.5 57.2 60.47 0.25 1.73 0.03 1.5 117.0 50.3 74.5 41.0 93.8 90.9 67.0 45.12 1.5 62.7
Number average molecular weight Mn (X 10-3) 15.5 30. ASTM D1234 0. Quick reference for commercial PVC molecular weights.11 1.38 1.13 1.0 101.0 72.5 95.67 0.5 80.22 1.19 1.
While the mass process saves drying energy.
In the second stage polymerizer. Heat removal is achieved. Unreacted monomer is removed by vacuum. 30% by the jacket. The reaction proceeds through the liquid stage and at about 25% conversion. causing a high polymerization temperature and broad molecular weight distribution (86). At high conversions the mixture becomes extremely viscous. The number of grains remain constant throughout this polymerization (87). becomes a powder. and 10% by the cooled agitator shaft (88). a larger horizontal vessel.10% conversion. more monomer and initiator are added. impeding agitation and heat removal. The first stage of the process is carried out in a prepolymerizer with flat blade agitator and baffles to about 7 . Suspension Polymerization
PVC RESIN MANUFACTURING PROCESSES
Mass or bulk polymerization of PVC is normally difficult.page 30 POLY(VINYL CHLORIDE) James W. 60% by a condenser. it has remained a minor process when compared to the suspension process. This first stage forms a skeleton seed grain for polymerization in a second stage. This vessel is equipped with a slow moving agitator blade running close to the vessel wall. A two stage process that overcomes these problems was originally developed by Saint Gobain (France).
Termination takes place in the growing micelle by the usual radical-radical interactions.
Emulsion polymerization takes place in a soap micelle where a small amount of monomer dissolves in the micelle.
Kinetics of suspension PVC are identical to the kinetics of mass PVC. and the resin is dried with hot air.6 power of the
. Polymerization takes place when the radical enters the monomer swollen micelle (91. A theory for true emulsion polymerization postulates that the rate is proportional to the number of particles [N]. increasing in rate with conversion (90). the slurry is steam stripped in a column to a residual monomer level of about 0.0001 % (10 ppm). excess water is centrifuged off. N depends on the 0. Suspension stabilizers act to minimize coalescence of droplets by forming a coating at the monomer-water interface. Summers
Suspension polymerization is carried out in small droplets of monomer suspended in water. The hydrophobic-hydrophilic properties of the suspension stabilizers are key to resin properties and grain agglomeration (89). 92).page 31 POLY(VINYL CHLORIDE) James W. excess monomer is recovered. The initiator is water soluble. After polymerization to about 80-90% conversion. The monomer is first finely dispersed in water by vigorous agitation. Additional monomer is supplied by diffusion through the water phase.
page 32 POLY(VINYL CHLORIDE) James W. accounts for a strong deviation from true emulsion behavior. where the physical crosslinks are PVC crystallites. Plastisols are dispersions of PVC in plasticizer.
. printing inks. Summers
soap concentration [S] and the 0.0005 to 0.
Emulsions of up to 0. [N] depends on [S]. the kinetics of PVC emulsion does not follow the above theory. Other versions. 95).1 (95). The high solubility of vinyl chloride in water. the average number of radicals per particle is 0. and finishes for paper and fabric. but the relationship varies with the emulsifier type (96. 97).
However. 0. are used as plastisol resins.3 to 10 µm diameter and dried by spray drying or coagulation. 0. Heat allows fast diffusion of plasticizer into the PVC particle followed by fusion (gelation) to produce a physically crosslinked elastomer.6 weight %.5 (93). The rate shows the same increasing behavior with conversion as mass polymerization (94. However the rate is nearly independent of [N] (95).4 power of initiator concentration [I]. The average number of radicals per particle is low. 0. Also PVC’s insolubility in its own monomer accounts for some behavior such as a rate dependence on conversion.2 µm diameter are sold in liquid form for water based paints.
In solution polymerization a solvent for the monomer is often used to obtain very uniform copolymers. Polymerization rates are normally slower than for suspension or emulsion PVC. This makes a uniform copolymer.
. etc. The monomer is homogenized in water along with emulsifiers or suspending agents to control the particle sizes.page 33 POLY(VINYL CHLORIDE) James W. free of suspending agents. and sometimes maleic acid are polymerized in a solvent where the resulting polymer is insoluble in the solvent. seals. vinyl chloride. Heating allows plasticizer to uniformly diffuse into the PVC particles and at higher temperatures. barriers. the plasticized particles fuse. that is used in solution coatings (99).3 to 1 µm diameter are used to make plastisols for flooring. Micro-suspension blending resins at 10 to 100 µm diameter are used as extenders to paste resins in plastisols (98). microsuspension polymerization uses a monomer soluble initiator. These plastisols are also dispersions of PVC in liquid plasticizer and are cured by heating. For example. Summers
While emulsion polymerization uses a water soluble initiator. Micro-suspension paste resins at 0. vinyl acetate.
Copolymers are used in flooring and coatings. Summers
Vinyl chloride can be copolymerized with a variety of monomers. Copolymers of vinyl chloride with maleates or fumerates are used to raise heat deflection temperature. non-woven fabric binders. adhesives. Copolymers with olefins improve thermal stability and improve melt flow at some loss of heat deflection temperature (100). and coatings.page 34 POLY(VINYL CHLORIDE) James W. This copolymer sometimes contains maleic acid or vinyl alcohol (hydrolyzed from the polyvinyl acetate) to improve the coating’s adhesion to other materials including metals.
. Vinyl acetate is the most important commercial comonomer [9003-22-9]. Copolymers of vinyl chloride with acrylic esters in latex form are used as film formers in paint. Copolymerization parameters are listed in table 5. Copolymers with vinylidene chloride are used as barrier films and coatings. It is used to reduce crystallinity which aids fusion and allows lower processing temperatures.
96 -1.026 0.02 1. 101 102 103 104 101 105 106 107 104 108 104 109.78 -0.21 4.33 0.04 0.4 0.07 0.4 1.17 7.23 2.12 2.14
ref.77 1.3 2.8 0.4 10 4.15 0.20 -0.8 0. Copolymerization Parameters of Vinyl Chloride.25 1. 110 111 101 112 113 114 105 115. 60 60 50 45 60 50 50 60
M2 acrylic acid acrylonitrile butadiene butene n-butyl acrylate diethyl fumarate dimethyl itaconate diethyl maleate ethylene ethylhexyl acrylate isobutylene isoprene maleic anhydride methacrylic acid methacrylonitrile methyl acrylate methyl methacrylate octyl acrylate propylene styrene vinyl acetate N-vinylcarbazole vinyl chloride vinyl laurate vinylidene chloride vinyl isobutyl ether N-vinylpyrrolidone
r1 0.68 0.8 2.22 -1.12 0.74 0.65 0.03 0.20 0.4 0.2 3.015 0.27 0.21 0.12 0.80 -0.42 0.23 4.002 1.14
Q 1. temperature °C.22 0.0 0.20 -1.16 2.35 0.21 4.34 -0.22 2.053 0.0 0.08
e 0.15 0.77 3.40 0. 110 116 117 118 104 119 120 121
Table 5.3 17 0.61 1.36 -1.06 1.107 0.68 0.60 2.53
r2 6.035 3.60 0.07 -0.034 0.1 0.page 35 POLY(VINYL CHLORIDE) James W.7 8.044 0.4 0.05 1.50 0.296 0.38
75 60 60 50 68 45
60 60 50
60 50 50
.25 0.86 0.02 0.009 0.3 0.008 23.39 0.47 5.033 3.34 0.8 0.0 0.8 4.
including for pipe. PVC’s are tailored to the requirements using sophisticated additives technology. particularly tribasic lead sulfate is commonly used in plasticized wire & cable compounds because of its good non-conducting electrical properties (122).page 36 POLY(VINYL CHLORIDE) James W. packaging and injection molded parts.. Without additives. fittings. Examples of effective tin compounds are di-alkyl tin dilaurate. Certain grades of methyl tins and octyl tins are used in food contact applications. siding profiles.
. cost-efficient materials in the world. windows. nickel and molybdenum.
Organotin stabilizers are commonly used for rigid PVC. and mono-/di-alkyl tin diisooctlythioglycolate. This produces stability at least an order of magnitude better than without stabilizer. Steel. These repair unstable sites on PVC removing unstable chlorine and replacing it with a ligand from the tin stabilizer molecule(123 . literally hundreds of commonly used PVC products would not exist.
Lead stabilizers. chromium.125). Many materials are useless until they undergo a similar modification process. Summers
The additives found in PVC help make it one of the most versatile. contains among other things. for instance.
Barium-zinc stabilizers have found use in plasticized compounds. and wire coatings. Its disadvantage is it cross-stains with sulfide based tin stabilizers(122). organophosphites. water bottles.
Calcium-zinc stabilizers are used in both plasticized PVC and rigid PVC for food contact where it is desired to minimize taste and odor characteristics. and medical uses. replacing barium-cadmium stabilizers. profiles. Several organic co-stabilizers are quite useful with barium-zinc and calcium-zinc stabilizers. These are used in moldings. hindered phenols. epoxies.
Many stabilizers require co-stabilizers. Summers
Antimony tris(isooctylthioglycolate) has found use in pipe formulations at low levels. They are beta diketones.page 37 POLY(VINYL CHLORIDE) James W. and polyols (122). Cadmium use has decreased because of environmental concerns surrounding certain heavy metals. Applications include meat wrap.
It was therefore quite desirable to develop technology to produce tough plastics. thus allowing the PVC to absorb large amounts of energy.page 38 POLY(VINYL CHLORIDE) James W. This can result in cavitation and/or cold drawing. Impact modifier choices are listed in table 6. In the early 1950s. Summers
In the early days of plastics.
. The Geon Company (then a part of BFGoodrich) began adding rubbery polymers to PVC to improve toughness (126). Rubbery particles act as stress concentrators or multiple weak points. leading to crazing or shear-banding under impact load (127). This gave plastics a cheap reputation. many unplasticized PVC products were brittle.
page 39 POLY(VINYL CHLORIDE) James W. Summers
Table 6. Impact modifiers used for various PVC applications (128). acr m-acr ABS CPE EVA MBS MABS siding windows gutters pipe & conduit irrigation pipe fittings interior trim foam interior profiles clear film clear bottles credit cards furniture appliances housings acr = m-acr = ABS = CPE = EVA = MBS = MABS = X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X
X X X
X X X
X X X X
X X X X X X X X X X all acrylic modified acrylic acrylonitrile/butadiene/styrene chlorinated polyethylene ethylene/vinyl acetate methyl methacrylate/butadiene/styrene methacrylate/acrylonitrile/butadiene/styrene
page 40 POLY(VINYL CHLORIDE) James W. Summers
PVC often flows as billion molecule primary particles. Processing aids glue these particles together before the PVC melts, thus acting as a fusion promoter. Processing aids also modify melt rheology by increasing melt elasticity and die swell, or, some reduce melt viscosity, and they reduce melt fracture. Some processing aids lubricate to reduce PVC sticking to metal. And processing aids affect dispersion of fillers, impact modifiers, and pigments (129). The most common processing aids are high molecular weight acrylics based primarily on polymethylmethacrylate copolymers.
Many authors classify lubricants as “internal” or “external” (130 - 134). Internal lubricants were considered to be soluble in PVC, or considered to have little effect on fusion, or they reduce melt viscosity; external lubricants were considered to retard fusion or to promote metal release. This system of classifying lubricants has too many conflicting measurements to be consistent and useful. Others have shown classifications based on synergy between various lubricants (135, 136), but did not explain the nature of that synergy. A model for the lubrication mechanism has been developed which explains synergy between certain lubricants (62). This model treats lubricants as surface active agents. Some lubricants have polar ends which are attracted to other
page 41 POLY(VINYL CHLORIDE) James W. Summers
polar ends and to polar PVC flow units and to polar metal surfaces. These also have non-polar ends which are repelled by the polar groups. Synergy happens when non-polar lubricants are added, which are attracted to the non-polar ends and act as a slip layer. This model is shown in figure 10.
A model of PVC lubrication mechanism (not to scale) showing a) PVC adhesion to metal without lubricant. c) non-metal releasing character of just paraffin.page 42 POLY(VINYL CHLORIDE) James W. and d) synergy between calcium stearate and paraffin (62). Summers
calcium stearate metal c) d) paraffin wax PVC PVC PVC
paraffin wax calcium stearate
. b) surface activity of calcium stearate.
possessed unusual elastic properties when cooled to room temperature (137). linear alcohol based phthalates offer good low temperature flexibility and also have reduced volatility. A few plasticizers impart specific properties for particular applications. Thus PVC was the first thermoplastic elastomer (TPE). 138 . thus making it rubbery. Polymeric plasticizers do not migrate easily but suffer from poor low temperature flexibility. This unusual behavior is due to unsolvated crystalline regions in the PVC that act as physical crosslinks. Aliphatic diesters offer good low temperature flexibility. This rubber-like material has stable properties over a wide temperature range (32. Summers
In 1926 at The Geon Company (then BFGoodrich). For example. trimellitates have low volatility. solutions of PVC. prepared at elevated temperatures with high boiling solvents. and also have good low temperature properties. elastic. are used for high temperature applications. phosphates improve flame resistance. lowering its Tg to well below room temperature.140). Epoxy plasticizers
. and exhibit a high degree of chemical inertness and solvent resistance. and chlorinated hydrocarbons impart flame resistance and good electrical properties.page 43 POLY(VINYL CHLORIDE) James W. but allow the PVC to accept large amounts of solvent (plasticizers) in the amorphous regions. citrate esters are used in food contact applications. benzoates are used for stain resistance. Such solutions are flexible.
are also good plasticizers with low volatility and they act as costabilizers.page 44 POLY(VINYL CHLORIDE) James W. improving the thermal stability of PVC.
meat wraps and other highly credible uses.page 45 POLY(VINYL CHLORIDE) James W. DEHP (di-2-ethylhexyl-phthalate) has been used worldwide in applications such as blood bags. there has been much debate over that impact due to the differing
. Common PVC plasticizers. however. Summers
Table 7. saline solutions. Plasticizer Aliphatic ester di(2-ethylhexyl) adipate di(2-ethylhexyl) azelate di(2-ethylhexyl) sebacate Phthalate di(2-ethylhexyl) diisooctyl diisodecyl butylbenzyl butyloctyl diisononyl ditridecyl diundecyl linear C7-C11 di(2-ethylhexyl) terephthalate Phosphates trioctyl cresyl diphenyl tricresyl triphenyl tri(2-ethylhexyl) Trimellitates tris(2-ethylhexyl) triisooctyl Epoxies epoxidized soybean oil epoxidized linseed oil epoxy stearate 2-ethylhexyl epoxytallate Abbreviation DOA
DOP or DEHP DIOP DIDP BBP BOP DINP DTDP DUP 711 phthalate DOTP TOP CDP TCP TEHP TOTM TIOTM ESO
Plasticizers and stabilizers in particular have been researched at length to determine their potential impact on human health and the environment.
DEHP-plasticized PVC is used in medical applications like blood bags where it is known to actually protect red blood cells from deterioration. While the U. 142). Because the evidence indicates the response is an artifact to that species and not a true indication of human hazard. Food & Drug Administration. National Toxicology Program and the International Agency for Research on Cancer have classified the plasticizer DEHP as a possible human carcinogen. their methodologies have been criticized for potentially inaccurately ascribing results obtained with rodents to humans (141. Flexible PVC film is considered the most desirable material for wrapping meats. as it is oxygen-permeable and maintains the bright red color needed to make meats salable to consumers. as well as extending the shelf life of meats. DEHP is not regulated as a carcinogen by the U. which has long governed the plasticizer's use in medical devices and in food contact applications. (Please note that additional information is rapidly becoming available and the reader may want to update this information in the years following publication of this article).
.S.page 46 POLY(VINYL CHLORIDE) James W. a number of regulatory bodies do not consider DEHP to pose a hazard to man. The Specialized Experts Working Group of the European Commission for instance.S. Summers
methods used to evaluate them. has concluded that there is no evidence to warrant the classification of DEHP as a carcinogen (143). Mechanistic studies indicate that the carcinogenic response which DEHP produces in rodents is directly related to physiologic and metabolic changes that are specific to that species.
Fillers are used to improve strength and stiffness. to lower cost. The carbon black is a stronger absorber than titanium dioxide and can therefore be used at lower levels in PVC for protection. Glass fibers. Both titanium dioxide and carbon black are strong ultraviolet light absorbers and effective in protecting the PVC.
A variety of pigments are added to PVC to give color. but at a loss in ductility. The most common filler is calcium carbonate. It ranges in size from 0. Some forms are treated with a stearic acid coating. improve electrical properties. talc.page 47 POLY(VINYL CHLORIDE) James W. such as calcined clay. and mica improve tensile strength and stiffness. For ultraviolet light absorption in transparent PVC or to improve pigmented systems.07 to well over 50 µm. including titanium dioxide and carbon black.
Ultraviolet light stabilizers
One form of stabilization is to absorb the ultraviolet light. and to control gloss. various derivatives of benzotriazole are used such as
plasticized PVC with >30% plasticizer. are available for a balance of stability. plasticized PVC. in specific applications such as flashing and sealing boots on roofs. are effective (144). Where tin carboxylate stabilizers are used instead of tin-mercaptide stabilizers. Not only is chlorine not a fuel. the compound combustibility is also increased. and swimming pools. it is inherently flame retardant.
Since PVC contains nearly half its weight of chlorine.
Although PVC itself. weatherability. may require a flame retardant such as antimony oxide. may need protection.page 48 POLY(VINYL CHLORIDE) James W. hindered amine light stabilizers. 146). often containing arsenic compounds. or chlorinated or brominated hydrocarbons (145. particularly with ultraviolet absorbers. Summers
2-[2’-hydroxy-3’. and biocidal effectiveness. shower curtains. compatibility. For example. When PVC is diluted with combustible materials.5’-(di-t-butyl)phenyl]benzotriazole. but it acts chemically to inhibit the fast oxidation in the gas phase in a flame.
. Many biocides. and rigid PVC compounds are resistant to attack by microorganisms. a phosphate type plasticizer.
which decomposes with heat to release nitrogen gas. are capable of producing foams at down to 0.page 49 POLY(VINYL CHLORIDE) James W. when used with a copolymer PVC. incorporating a gas under pressure or incorporating a physical blowing agent into the melt. not all chlorofluorocarbons are acceptable and newer types of physical blowing agents are becoming available which minimize ozone depletion.
The most common chemical blowing agent is 1.03 grams/cc. such as whipping air into a plastisol. or using a chemical blowing agent which releases a gas when it decomposes with heat. Because of the damage to the ozone layer in the stratosphere. Physical blowing agents.4 grams/cc. Typically the closed cell foams of rigid PVC range down to a density of 0. Summers
Foaming or blowing agents
Cellular PVC can be made by a variety of techniques.1’-azobisdicarbonamide. such as chlorofluorocarbons which volatilize without changes in the chemical bonds.
1500 lbs. These compounds are available in bulk railcars containing 80 tons (160. from compound manufacture to melt extrusion. Summers
PRODUCTION VOLUME AND ECONOMICS
Compound manufacture All PVC must be compounded before it is used. to an extent that compounding can be integrated into the process. Other businesses that integrate compounding to some extent are window
. Pipe and siding manufacturing are such processes where compounding is integrated in with the extrusion process. These businesses are not included in the following chart of merchant compound producers. it can be economical to streamline the process.page 50 POLY(VINYL CHLORIDE) James W. boxes containing 600 kg (1200 .). The total volume is not publicly available. or bags containing 23 kg (50 lbs.000 lbs.). Some resin manufacturers are integrated to supply these compounds.). Suppliers of merchant compound sold in North America are listed in figure 11 according to their approximate share (147). For the wide variety of requirements where PVC performs. Often processors and original equipment manufacturers (OEMs) will purchase compound.). in bulk trucks containing 20 tons (44.000 lbs.
For businesses specializing in a large market with a limited product line. already balanced to meet the range of properties required and to do the best job economically. it is usually not feasible to maintain a technical compounding knowledge at the user level.
and wire & cable manufacturing. barrier & packaging film manufacturing.
.page 51 POLY(VINYL CHLORIDE) James W. Summers
manufacturing. int. North American merchant compound sales . = integrated PVC resin and compound manufacturing.1995 (147).
5 billion pounds of resin are manufactured in North America and 53 billion pounds world wide. About 14. boxes containing 600 kg (1200 . Summers
PVC resin manufacture
PVC resins are manufactured and sold for a wide variety of applications.
. or bags containing 23 kg (50 lbs.).1500 lbs.000 lbs. These resin manufacturers are broken down in figures 12 and 13.).).page 52 POLY(VINYL CHLORIDE) James W. These resins are available in bulk railcars containing 80 tons (160.000 lbs.). in bulk trucks containing 20 tons (44.
N. Europe 9% W.6 billion Kgrams.page 53 POLY(VINYL CHLORIDE) James W. 148). Summers
Figure 12.24 billion Kgrams (1.1995 . 147. World PVC resin capacity .5 billion pounds) (1.6. America 4% E.
6 Others 5% Goodyear 1% Policyd 2% Esso 2% Primex 3% Westlake 4% Vista 7% Georgia Gulf 8% Borden 9% FPC 14%
Figure 13. North American PVC resin capacity . America 27%
Africa 2% Australia 1% Mid East 3% S. 147. 148).1995 . Source for both fig 12 & 13: CMAI (148). (4. Europe 24%
148). (1. Source: CMAI (148). South America.
. the Mideast. Japan. and Western Europe. with the growth accelerating (figure 14). with lots of room for growth in Africa. Mexico. and Eastern Europe (figure 15). World demand for PVC.
Figure 14. 147. the Far East.
25 BILLIONS KILOGRAMS 20 15 10 5 0 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997
Per capita demand for PVC is high in Canada. USA. Summers
World demand is 22 billion kilograms (49 billion pounds) in 1995.page 54 POLY(VINYL CHLORIDE) James W.
Figure 15. 147.page 55 POLY(VINYL CHLORIDE) James W. Source: CMAI (148). 148). partly because only about half the molecule is based on hydrocarbon raw material
. Per capita demand for PVC by region. (1.
Africa & Mideast Average Far East Mexico South America Eastern Europe World Western Europe Japan USA Canada 0 10 20 Pounds per capita 30 40
PVC resin price PVC resin prices tend to be more stable than other plastics’ prices.
Figure 16 compares PVC prices to other plastics’ prices. 120 ABS 100
80 Cents/lb. Source: CMAI (148). Summers
sources.page 56 POLY(VINYL CHLORIDE) James W. PS
HDPE PP PS PVC ABS
40 HDPE 20 PP PVC
0 1Q '94 2Q '94 3Q '94 4Q '94 1Q '95 2Q '95 3Q '95 4Q '95
. Figure 17 looks at PVC’s prices over several years.
Figure 16. PVC prices compared to other plastics’ prices (147. 148).
50 45 40 35 Cents/pound 30 25 20 15 10 5 0 1990 1991 1992 1993 1994 1995
SPECIFICATIONS AND STANDARDS
Numerous specifications and standards are used to define PVC resins and compounds. Chem Data. Inc.page 57 POLY(VINYL CHLORIDE) James W. PVC prices over several years ( 147. Summers
Figure 17. Table 8 summarizes a few of these standards.
. 149. ).
fittings PVC wire insulation PVC T.
. 3 inch thin wall PVC PSP sewer pipe and fittings PVC PSM sewer pipe and fittings PVC rigid building products compounds PVC potable water. THW. THHN wire insulation PVC telecommunications wire insulation jacket PVC NM jacket PVC AWM wire insulation PVC TC cable jacket
USES AND MARKETS
PVC is so versatile that it can be compounded for a wide range of properties and it is used in a wide variety of markets. 80. schedule 80 DWV pipe and fittings PVC Sewer pipe and fittings PVC tubing CPVC hot water distribution system PVC DWV. schedule 40.page 58 POLY(VINYL CHLORIDE) James W. THWN. one time use. Summers
Table 8. A list of all major uses is found in table 9. Standard ASTM D1755 ASTM D1784 ASTM D1785 ASTM D2287 ASTM D2464 ASTM D2466 ASTM D2467 ASTM D2665 ASTM D2729 ASTM D2740 ASTM D2846 ASTM D2949 ASTM D3033 ASTM D3034 ASTM D4216 NSF 14 UL 62 UL 83 UL 444 UL 719 UL 758 UL 1272 Description PVC resin cell classification PVC rigid compound cell classification PVC pipe. Specifications and standards for PVC resins and compounds. TW. schedule 40 PVC socket fittings. products is limited. Its use in short term. Most of the products are durable goods and have long lifetimes. 120 PVC non-rigid (plasticized) compound cell classification PVC THR fittings PVC socket fittings.
Pipe and fittings
Pipe and fittings are a major market for PVC.000 140.000 70.000 50.000 160.000 2.360.000 80.000 180. These applications are designed with PVC for long term satisfactory performance.000 240. Summers
Table 9.page 59 POLY(VINYL CHLORIDE) James W. These are a prime example of PVC as an engineering thermoplastic. The products are designed to meet appropriate ASTM standards.000 850. and vacuum sizing/cooling. twin screw extruders.000 60.000 640.1995 (1).070.000 390. Pipe manufacturing uses powder compounds. USA Markets .000 5. Because of the volume of products.
. The applications are highly optimized for efficient production at high rates and minimal costs.000 100. the process is highly developed. Metric tons Construction Flooring Pipe & Conduit Wire & Cable Siding Windows & Doors Extrusions Packaging Bottles Extrusions Calendering Custom Moldings Paste Processes Textiles & Coating Exports & Resale Other Total 120.
waste. PVC’s chemical response to weathering is well understood so that compounds and products can be designed for satisfactory performance outdoors. This absorption is affected by PVC’s previous thermal degradation during processing (150. & doors
PVC is accepted commercially as an excellent weathering material. particularly by ultraviolet light.
Weatherable siding. For this reason it is important to avoid thermal damage to PVC during processing. and at the same time. Plastic materials are damaged by the sun. The mechanism of degradation starts by absorbing the sun’s damaging ultraviolet light. windows. 151). CPVC is also used in automated fire-safety sprinkler systems.
Chlorinated PVC (CPVC) is used in higher temperature applications such as for hot water piping. Summers
Products include pressure pipe of various sizes and drain. and vent applications. with a proper choice of the type of titanium dioxide to control the rate of the oxidation and bleaching process.page 60 POLY(VINYL CHLORIDE) James W. The absorbed light breaks bonds and forms free radicals. Because of its superior creep resistance. With a proper level of titanium dioxide to protect the PVC by it absorption of ultraviolet light (152). oxidative bleaching (removal of yellowing). This leads to loss of hydrogen chloride and yellowing. and with a proper choice of other weather stable
a well designed PVC formulation can be very durable to the weather. Products include siding. Siding uses powder compounds. Because elastic swell is reduced at lower melt temperatures. soffits. and vacuum sizing/cooling. where the PVC grains are already broken down. For windows. may or may not use the powder compound/twin screw extruder/vacuum sizing approach. and vinyl protected wood windows. and door glazing applications and garage doors. Because of the volume of products. the process is highly developed and optimized.
As with pipe. die design is simpler. including the all-vinyl windows. and requires large investments to develop and operate the process. The products are designed to meet appropriate ASTM standards. windows. Either vacuum sizing or air sizing/cooling is possible. siding manufacturing is highly optimized for efficient production at high rates and minimal costs.page 61 POLY(VINYL CHLORIDE) James W. Cubed compound. because lower melt temperatures are typical.
Other products such as windows. twin screw extruders. this is a much more complex operation than for pipe. can be run faster and on simpler single screw extruders. Summers
ingredients. gutters & down spouts.
The compounds are optimized for the requirements. Some line speeds are 5000 feet/minute (60 mph). and cooling and sizing equipment that delivers the exact dimensions required. and is due to the billion molecule flow units. maintain. Cubed compound.page 62 POLY(VINYL CHLORIDE) James W.
Wire & cable
PVC has been used in wire & cable applications since World War II. die design is simpler and often is the same dimensions as the desired profile. Other plastics have higher die swell. can be run faster and on simple single screw extruders. Thus those plastics have much more difficulty in designing dies and in maintaining a process to hold dimensions. where the PVC grains are already broken down. These products are manufactured by cross-head extrusion. and operate extrusion dies. usually from pellet compounds on single screw extruders. Because elastic swell is reduced at lower melt temperatures. including low
. which increases at lower melt temperatures (153). Summers
Complex profiles require specialty manufacturing skills to build.
The low elastic swell is unique to PVC. when the Navy demanded lower combustibility materials in construction. because low melt temperatures are typical. Either vacuum sizing or air sizing/cooling is possible.
page 63 POLY(VINYL CHLORIDE) James W. electrical enclosures. weatherability. Summers
Pipe fittings require quite high tensile and creep resistance. high use temperature. These take advantage of PVC’s outstanding Underwriter Laboratories flammability ratings and easy molding into thin walled parts.
Plasticized compounds are injection molded into a variety of parts requiring elastomeric properties.
Injection molded products
Numerous housings. and cabinets are injection molded from rigid PVC. PVC has developed melt flow capabilities to the point where it competes with essentially any other flame retarded engineering thermoplastic and molds easier than most.
. especially low combustibility. and high resistance to cut-through. thus they are molded from compounds have less melt flow than for thin walled housings.
as well as all feedstocks. mixing or doing other tasks
Health [references (154 .158)]
There are no significant health hazards arising from exposure to polyvinyl chloride at ambient temperature. While the processing and use of PVC is not any more hazardous than that of other plastic materials. this section goes into potential concerns in some detail.S. a British study found a small decrease in breathing capacity for workers who smoked and were exposed to vinyl resin dust. These are available to anyone who wishes to review them. Summers
HEALTH AND SAFETY FACTORS (TOXICOLOGY)
The potential health and safety effects of PVC and all PVC additives. are fully detailed by each manufacturer in material safety data sheets (MSDS).page 64 POLY(VINYL CHLORIDE) James W. This decrease was about one-seventh of that caused by normal aging and about equal to that expected with a one-pack-a-day cigarette smoker.
Since routine inhalation of dust of any kind should be avoided. and must be provided to all plant workers. However. law. reduction of exposure to polyvinyl chloride dust may be accomplished through the utilization of care when dumping bags. which are required by U.
such decomposition would involve hydrogen chloride.. e. pain and inflammation of the respiratory tract. In the case of PVC compounds. can result in personnel exposure to decomposition or combustion products. and this irritation may extend to the skin and eyes of sensitive people.g.)
. The use of an approved dust respirator is recommended where adequate ventilation may be unavailable. This is also true for PVC and its additives. most polymers emit fumes and vapors that may be irritating to the respiratory tract.5 ppm.
Fortunately. (The odor of hydrogen chloride is detectable as low as 1 . Depending upon the severity of exposure. Hydrogen chloride will cause irritation of the respiratory tract. Summers
which can create dust. eyes and skin. through greatly elevated temperatures above normal operating temperatures. causing exposed personnel to be driven from the area which prohibits long term exposure. physiological response will be coughing. Processing emissions exposure can also be greatly reduced or eliminated by the use of properly designed and maintained exhaust ventilation.page 65 POLY(VINYL CHLORIDE) James W. the pungent odor of hydrogen chloride provides an excellent warning signal.
At processing temperatures.
Decomposition of plastics.
The minimum ignition energy for explosion is much higher than that of natural materials such as corn starch and flour and also exceeds those of other plastic
. This action serves as a flame quencher in the vapor phase. Summers
First aid for exposure to processing emissions or decomposition products is simply to remove the exposed individual from the area of exposure. As mentioned previously. hydrogen chloride is generated during combustion.ASTM D-1929. In general. Precautions should be taken similar to those for any other combustible materials. polyvinyl chloride is difficult to ignite. principally as a consequence of the action of the halogen content of the material.page 66 POLY(VINYL CHLORIDE) James W. e.
Fire and explosion
Polyvinyl chloride resin has a flash point of approximately 391oC (735oF) and a self-ignition temperature of approximately 454oC (850oF) . polyvinyl chloride burns with difficulty because a substantial amount of energy is required to break down the polymer into smaller fragments that will sustain combustion in the gas phase..g. Consequently. It is recommended that a physician examine those persons complaining of persisting irritation.
Polyvinyl chloride powder has a very low tendency to explode. Polyvinyl chloride will release less heat than many other combustible materials. Fires will tend to extinguish naturally in the absence of a substantial external source of heat or flame. wood or other plastics.
However. These polymers are chemically incompatible. as with any powder materials.
With respect to firefighting where polyvinyl chloride is involved. should dusting occur. water. ABC dry chemical or protein-type air foams should be used as extinguishing media. care should be taken in addressing ignition sources in working and handling areas. an SCBA should be worn during cleanup immediately after a fire as well as during the attack phase of firefighting operations. mixing could cause rapid decomposition and gas evolution. Carbon dioxide may be ineffective on larger fires due to lack of cooling capacity which may result in reignition. Summers
materials. The International Agency for Research on Cancer (IARC) shows inadequate evidence that polyvinyl chloride is carcinogenic in animals or humans and has an overall evaluation of 3 (not
Toxicology studies have shown polyvinyl chloride to be equivocally tumorigenic through oral and implant studies.page 67 POLY(VINYL CHLORIDE) James W. for an enclosed or poorly ventilated area. PVC should not be melt mixed with acetal polymers. Also insure walkways and floors are cleared of polyvinyl chloride dust to prevent slippery footing. In addition. Firefighters should utilize a selfcontained breathing apparatus (SCBA) in positive-pressure mode.
POLYMER with a reporting threshold of 500 lbs. Environmental Hazardous Substances (EHS) List as CHLOROETHYLENE. Summers
classifiable). polyvinyl chloride is listed through its monomer.J. homopolymer [CASRN: 9002-86-2].
Polyvinyl chloride is listed on the TSCA inventory and the Canadian Domestic Substances List (DSL) as ethene. The United States has no occupational exposure limits for polyvinyl chloride except as particulates not otherwise classified (PNOC). For PNOC's the American Conference of Governmental Industrial Hygienists (ACGIH) has a threshold limit value (TLV) of 10 mg/m3 for inhalable and 3 mg/m3 for respirable while the Occupational Safety and Health Act (OSHA) permissible exposure limits (PEL's) are 15 mg/m3 for total dust and 5 mg/m3 for the respirable fraction. Since polymers are not listed on the European Community Commercial Chemical Substances listing or EINECS. In the United States polyvinyl chloride is an EPA Hazardous Air Pollutant under the Clean Air Act Section 112 (40 CFR 61) and is covered under the New Jersey Community Right-to-Know Survey: N.page 68 POLY(VINYL CHLORIDE) James W. vinyl chloride [CASRN: 75-01-4].
all found in large quantities in sea water. 159-164)
The chlorides found in common salt water are an essential element in all body fluids.169). oceans. A large number of complex organic chlorides and organochlorines are naturally produced chemicals. plants.
. the material used to make PVC
Chlorine is the 20th most common element on Earth.15 percent of total body weight. It is essential to human life. which have revolutionized the treatment of human bacterial and fungal infections. widely present in nature. and occasionally finds its way to the earth's surface in its elemental state (165). it reacts with water vapor to form hydrochloric acid. found virtually everywhere: in rocks. Chlorine is also an essential element of naturally occurring anti-bacterial and anti-fungal agents such as chlortetracycline. and play many essential roles (166 . animals and human bodies. More usually. magnesium chloride and potassium chloride. chloramphenicol and griseofulvin. Free chlorine is produced geothermally within the earth. Hydrochloric acid reacts quickly with other elements and compounds. however.page 69 POLY(VINYL CHLORIDE) James W. forming stable compounds (usually chlorides) such as sodium chloride (common salt). and in this form. makes up about 0. Summers
ENVIRONMENTAL CONSIDERATIONS AND RECYCLING (ref.
PVC is the world's leading electrical material. Summers
Even more complex cyclic organochlorines (including dioxins and furans) are produced from burning wood and other vegetable matter. with over 500 million pounds used annually for wire and cable insulation and sheathing. Chlorine-based chemicals are everywhere. Given the fact that chlorine compounds are naturally produced in such vast quantities. banning production of chlorine to keep chlorine compounds out of the environment would be futile. In addition. and have been so since before the existence of man. Not only is chlorine essential to the chemical composition of PVC. and would deprive the world of hundreds of products critical to society's health and well-being. it provides a number of unique properties that give this versatile plastic a distinct advantage in product applications and the marketplace. electrical conduit. is one of the most energy efficient polymers.
Over 30% of the chlorine produced on a global basis goes to make PVC. recycling PVC is easier because the
. and so widely distributed in the natural world. and are natural by-products of forest fires (170. Both dioxins and furans have been found in lake sediments dating back to 1860 (172) and samples taken from ice cores in Greenland dating back to 1869 show definite "spikes" in chlorine content correlating with volcanic activity (173). boxes and components. Chlorine makes PVC far more environmentally acceptable than other materials that are totally dependent on petrochemical feedstocks. extremely costly. 171). It makes PVC inherently flame retardant. And the environment would be worse off. PVC is over 50% chlorine and as a result.page 70 POLY(VINYL CHLORIDE) James W.
that are not disposed of quickly. That's because most vinyl applications are long-term uses. In fact.5 million pounds of post-consumer vinyl were recycled in the U.S.
In landfills. Summers
chlorine in PVC acts as a marker. More than 3.500 communities accept vinyl products in their recycling programs. are extremely resistant to decomposition. Most of that consists of vinyl packaging. such as pipe and house siding. about 6. like all plastics.S.page 71 POLY(VINYL CHLORIDE) James W. An estimated additional 300 million pounds of vinyl post industrial scrap was diverted from landfills and recycled into second-generation products.
Vinyl is recycled by at least 170 recyclers in the U. less than one-half percent by weight is found in the municipal solid waste stream. high-technology landfills are often lined with thick-gauge
Vinyl Solid Waste and Recycling
Although vinyl is the world's second most widely used plastic. blister packaging and flexible film. landfilling and incineration (including waste-to-energy). In 1994. enabling automated equipment to sort PVC containers from other plastics in the waste stream (174). which is about 25 percent of all communities that recycle. Vinyl wastes are handled by all conventional disposal methods: recycling. and Canada. bottles. vinyl wastes.
commercial incinerator facilities throughout the world. Those tests revealed that the presence or absence
. found no relationship between the chlorine content of waste and dioxin emissions from combustion processes. involving the analysis of over 1. the scientific literature is clear that the operating conditions of combustors are the critical factor in dioxin generation (177). Summers
vinyl and use PVC pipe to handle liquid leachate and methane gas.700 test results from 155 large-scale. This work includes and confirms a number of other studies. a lifecycle assessment comparison of specific packages made from glass.
Incinerating PVC Wastes
A recent study sponsored by the American Society of Mechanical Engineers (ASME). Vinyl saves more than 34 million BTUs per 1.
Vinyl compares favorably to other packaging materials.page 72 POLY(VINYL CHLORIDE) James W. paperboard. In 1992.000 pounds manufactured compared to the highest energy-consuming plastic (176). most notably. Instead. and the lowest fossil fuel and raw material requirements of the plastics studied (175). the study stated. paper and selected plastics concluded that vinyl was the material with the lowest production energy and carbon dioxide emissions. the work conducted in 1987 by the New York Energy Research and Development Authority. to protect the environment.
Environmental Protection Agency make scrubbers mandatory on all incinerators so that they can neutralize a range of acid gases. power plants burning fossil fuels. which produce sulfur dioxide and nitrogen oxide.page 73 POLY(VINYL CHLORIDE) James W. Summers
of PVC had no effect on the amount of dioxin produced during the incineration process (178).S.
Incinerator scrubbing systems can remove about 99 percent of the hydrogen chloride generated by incinerating vinyl plastics and other chlorine-containing compounds and materials (179). concluded that removing vinyl from the waste stream would not eliminate the need either for air pollution control devices and monitoring equipment. along with automotive exhaust (182. New requirements from the U. which are produced by a variety of materials.02 percent of all acid rain can be traced to incineration of PVC (184). In fact.
Common misperceptions about vinyl
. A recent study. Since acid generated in incinerators comes from a variety of sources including such things as table salt and paper products. including sulfur dioxide and nitrogen oxide. Municipal incinerators are often targeted as a primary cause of acid rain. In Europe and Japan. scrubbers are necessary whether or not PVC is present in the waste feed (180). conducted by Midwest Research Institute and published by the ASME. nor would it influence the choice of incineration equipment (181). are actually the leading cause of acid rain. 183). studies show that only about 0.
Not true. with about 6. the University of Toledo identified nearly 100 uses for recycled vinyl. Of course. 207 million pounds available via recycling of bottles).5 million pounds of post-consumer vinyl (primarily bottles) currently being recycled. but now. Not true. Overall. When the Council for Solid Waste Solutions (now. A recent directory published by the Vinyl Institute lists nearly 50 companies that make commercial products out of recycled vinyl (185). it found that there were an estimated 1. the potential demand for recycled vinyl is estimated to be over twice the potential supply of all vinyl bottles produced in the US each year (494 million pounds needed vs. the American Plastics Council) conducted a nationwide survey in 1991. Summers
a) No one is recycling vinyl.100 municipal recycling programs in place or planned in the United States that include vinyl. industrial scrap vinyl has been recycled for years. b) There's no market for recycled vinyl. In 1989.page 74 POLY(VINYL CHLORIDE) James W.
. post-consumer vinyl recycling is growing. too.
Not true. different plastic materials cannot be mixed successfully in most recycled products applications. e) Vinyl gives off dioxin when it's incinerated. d) PET and HDPE packaging are listed as 1 and 2 in the SPI recycling coding system because they are the most recyclable. Except for commingled plastics applications. Rather. Not true. Thanks to the chlorine that is present in it. it was found that incinerator operating conditions (primarily temperature) were the key to controlling dioxin formation (168). found that the presence--or absence--of chlorine containing wastes in incinerators had no effect on the levels of dioxin produced. This is why it's so important to efficiently separate one plastic from another. Misleading.
. vinyl lends itself very well to automated sorting technology. A study conducted by ASME in 1995. German officials examined the issue of incinerating vinyl waste and decided there was no cause for concern. Most recently.page 75 POLY(VINYL CHLORIDE) James W. Summers
c) Vinyl is the problem in municipal recycling because it contaminates other resins. Contamination occurs whether or not vinyl is present. The numbers assigned to each plastic in the SPI coding system are purely arbitrary and do not reflect the material's recyclability. Other resins are just as much a contamination problem for vinyl.
g) European packagers. Most vinyl products do not contain heavy metals and vinyl is a small fraction in feed to incinerators. Some municipalities in Germany have restricted the use of certain vinyl products in municipally funded building projects. Re-formulation to replace heavy metals is in progress but some use will continue. and regulators have banned vinyl.page 76 POLY(VINYL CHLORIDE) James W. Industry is working to change those restrictions with several notable reversals. regulations should specify that incinerator residues (ash) be disposed of appropriately. There is only one ban on vinyl packaging in Europe. The current trend in Europe (led by the Germans) is to take a comprehensive look at waste
. a commercial ploy to block the sale of French mineral water in that country. In Great Britain.188). This is an evolving issue. Elsewhere in Europe. Summers
f) Vinyl should be banned from incinerators because it contains heavy metal additives. has chosen vinyl over other materials as the chain's most "environmentally friendly polymer. Marks & Spencer. vinyl packaging continues to be widely used. one of the leading retailers. Banning vinyl from incinerators will not eliminate this problem." In Switzerland. grocery stores. and that is on the use of vinyl bottled mineral water in Switzerland. Government studies on PVC in Belgium and The Netherlands concluded there should be no bias against the use of PVC (186 . Rather. Misleading. including Berlin and Bielefeld. retailer Migros has stated that its whole attitude toward vinyl will change when incinerator scrubber technology is fully employed. Not true. There is a voluntary agreement in Denmark by industry to substitute alternatives to vinyl packaging when feasible.
.page 77 POLY(VINYL CHLORIDE) James W. This involves all industries. lead to a worsening of the environmental situation. compared vinyl to a number of other packaging materials and found that vinyl consumed the least amount of energy. On those occasions when vinyl chloride monomer is detected in landfills. It resists chemical attack and degradation. these are especially a problem with other materials that readily burn. Overall.S. Because vinyl products contain chlorine. Like all plastics. carbon dioxide
. vinyl is an extremely stable landfill material. vinyl is unusually hazardous and damaging Not true. Inc. In fact. vinyl produces carbon monoxide. an independent consulting firm. Europe remains a larger consumer of vinyl packaging than the U. Not true. the Norwegian environmental group Bellona has concluded that "a generally reduced use of vinyl plastics will. When it does burn however. not just the vinyl industry. The real hazards in a fire are carbon monoxide and heat. A recent study conducted by Chem Systems. given today's circumstances." j) In a fire. Summers
reduction and make industry a partner in that process. used the lowest level of fossil fuels. Not true. it typically can be traced to the presence of other chemicals and solvents. they are inherently flame-retardant and resist ignition. i) Other plastics are more environmentally "friendly" than vinyl. h) Vinyl plastics decompose in landfills and give off vinyl chloride monomer. and is so resistant to the conditions present in landfills it is often used to make landfill liners. consumed the least amount of raw materials and produced the lowest levels of carbon dioxide of any of the plastics studied.
In those studies.000 ppm(193). the increased use of more fire-resistant materials. fire death rate is decreasing. However. when wood burns. research indicates that those levels are never reached or even approached in real fires. The U. Hydrogen chloride is an irritant gas that can be lethal at extremely high levels. Burning wool will produce hydrogen cyanide. the most hazardous is carbon monoxide. More recent studies indicate less of a potential for delayed effects on lung
. to 29 per million in the 1980s (by which time. virtually all burning materials produce carbon monoxide. All organic materials. dropping from a rate of 76 per million in the 1940s (when most construction and decorative products were made of "natural" materials). For instance. Even the simple act of barbecuing a steak or smoking a cigarette will produce dioxin (190). PVC had replaced natural materials in numerous applications) (192). deserves part of the credit for this improvement.page 78 POLY(VINYL CHLORIDE) James W. including benzene and acrolein (189). which is by far considered the greatest toxic hazard in fires because of the abundant levels produced and the low levels that cause death (191). Of these.S. This downward trend can be attributed in large part to improved building codes and the broader use of sprinkler systems and smoke detectors. release a lengthy list of chemical by-products. when burned. like PVC. test animals were able to survive exposures to hydrogen chloride reaching 10. Hydrogen chloride is produced when PVC burns. However. A series of tests for the Federal Aviation Administration studied this issue. as many as 175 different fire gases may be produced. Summers
and hydrogen chloride. More importantly.
Of course the previous authors of this review. hydrogen chloride levels rarely exceed 300 ppm.
I wish to thank The Geon Company for allowing me over the years to build a knowledge of PVC that makes this review possible. halogen-free compounds and found that neither type of material presented a clear-cut advantage in a fire.. a fact confirmed by the Boston Fire Department and Harvard University (195). made my job easier. and that the halogenated compounds sometimes outperformed the nonhalogenated products in terms of creating less corrosion (196). not one death has been linked to the presence of PVC. In a typical fire. and thanks to D’Lane Wisner and Fred Krause for helping with the environmental considerations and recycling. In hundreds of autopsies conducted on fire victims in the U. Summers
function than expected (194).page 79 POLY(VINYL CHLORIDE) James W.
.S. Bell Laboratories studied wire and cable compounds made of PVC or other halogen-based compounds vs. I wish to thank Lu Liu and Dick Roman for assistance in determining the size of this industry. John Davidson and the late Keith Gardner. Thanks to Mark Hross for his assistance on the section on health and safety.
6. M. 38 (1984). V. V. 2.. Bonnemayre. E. Rabinovitch.W. Vinyl Technol.Y. Rev. Summers
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ABSTRACT PVC has a large sales volume, second only to polyethylene. Its high chlorine content provides it with a very high level of combustion resistance for building products, electrical enclosures, and wire & cable insulation. PVC has a unique ability to be compounded with a wide variety of additives, making it possible to produce materials in a range from flexible elastomers (the first thermoplastic elastomers) to rigid compounds, materials that are weatherable such as for siding and windows, compounds that have stiff melts and little elastic recovery for outstanding dimensional control useful in profile extrusion, or low viscosity melts which compete effectively with ABS and PC/ABS in thin walled injection molding parts such as computer monitor housings.
Some of PVC’s properties are attributed to unique morphology. The polymer precipitates from its monomer and grows into primary particles, which are later the melt flow units. Fusion into larger structures and product strength are controlled by break-down of the grains into primary particles, by the choice of additives, by the amount of melting (temperature), and by the number of tie molecules (molecular weight).
The main type of polymerization is the suspension process, with significant polymerization made by the mass process, solution process, microsuspension, and emulsion process. In the suspension process, the polymerization takes place in droplets of monomer suspended in water.
The analysis from 155 large-scale.500 communities accept vinyl products in their recycling programs.S. Summers
From an environmental viewpoint. PVC is over 50% chlorine and as a result. is one of the most energy efficient polymers. commercial incinerator facilities. makes PVC inherently flame retardant. EPA make scrubbers mandatory on all incinerators and are necessary whether or not PVC is present in the waste feed. and dioxin emissions from combustion processes. Vinyl is recycled by at least 170 recyclers in the U.
.S. found no relationship between the chlorine content of waste nor the addition of PVC. enabling automated equipment to sort PVC containers from other plastics in the waste stream. and acts as a marker. New requirements from the U. and Canada and more than 3.page 97 POLY(VINYL CHLORIDE) James W.