Kirk-Othmer Encyclopedia of Chemical Technology.

Copyright

c John Wiley & Sons, Inc. All rights reserved.

POLY (VINYL FLUORIDE)

Vinyl fluoride can be polymerized into homopolymers and copolymers with the aid of a free-radical generating
catalyst (initiator), usually under high pressure. Du Pont first commercialized a poly(vinyl fluoride) (PVF) based
film in 1961 under the trade name Tedlar and is the only known supplier of this polymer. PVF homopolymers
and copolymers have excellent resistance to sunlight degradation, chemical attack, water absorption, and
solvent, and have a high solar energy transmittance rate. These properties have resulted in the utilization of
PVF film and coating in outdoor and indoor functional and decorative applications. These films have found use
where thermal stability, outdoor durbility, stain resistance, adherence, and release properties are required.

1. Monomer

Vinyl fluoride [75-02-5] (VF) (fluoroethene) is a colorless gas at ambient conditions. It was first prepared by
reaction of 1,1-difluoro-2-bromoethane [359-07-9] with zinc (1). Most approaches to vinyl fluoride synthesis
have employed reactions of acetylene [74-86-2] with hydrogen fluoride (HF) either directly (2–5) or utilizing
catalysts (3, 6–10). Other routes have involved ethylene [74-85-1] and HF (11), pyrolysis of 1,1-difluoroethane
[624-72-6] (12–15) and fluorochloroethanes (16–20), reaction of 1,1-difluoroethane with acetylene (21, 22), and
halogen exchange of vinyl chloride [75-01-4] with HF (23–25). Physical properties of VF are given in Table 1.

2. Polymerization

Vinyl fluoride undergoes free-radical polymerization. The first polymerization involved heating a saturated
solution of VF in toluene at 67◦ C under 600 MPa (87,000 psi) for 16 h (26). A wide variety of initiators and
polymerization conditions have been explored (27–29). Examples of bulk (30, 31) and solution (27, 30, 32,
33) polymerizations exist; however, aqueous suspension or emulsion methods are generally preferred (28, 34–
43). VF volatility dictates that moderately high pressures would be required. Photopolymerizations, usually
incorporating free-radical initiators, are also known (28, 30, 31, 37).
The course of VF polymerizations is dominated by the high energy, and hence high reactivity of the prop-
agating VF radical. The fluorine substituent provides little resonance stabilization, leading to a propagating
intermediate that is indiscriminant in its reactions. Monomer reversals, branching, and chain-transfer reac-
tions are common. The reactivity of the VF radical limits the choice of polymerization medium, surfactants,
initiators, or other additives and makes impurity control important. Species that can participate in chain trans-
fer or incorporate in the polymer can depress molecular weight or degrade the thermal stability characteristics
of the final polymer.
The combination of triisobutylborane [1116-39-8] and oxygen has been used to polymerize VF at reduced
temperature and pressure (44). Polymerization temperature was varied from 0 to 85◦ C with a corresponding
drop in melting point from ∼ 230◦ C (0◦ C polymerization) to ∼ 200◦ C (85◦ C polymerization). This dependance
1
2 POLY (VINYL FLUORIDE)

Table 1. Physical Properties of Vinyl Fluoride

Property Value
molecular weight 46.05
boiling point, ◦ C −72.2
freezing point, ◦ C −160.5
critical temperature, ◦ C 54.7
critical pressure, MPaa 5.1
critical density, g/cm3 0.320
liquid density at 21◦ C, g/cm3 0.636
vapor pressure at 21◦ C, MPaa 2.5
solubility in water at 80◦ C, g/100 g H2 O
at 3.4 MPaa 0.94
at 6.9 MPaa 1.54
a To convert MPa to atm, divide by 0.101.

of melting temperature, and degree of crystallinity, have been interpreted in terms of variations in the extent
of monomer reversals during polymerization (45). Copolymers of VF with vinylidene fluoride [75-38-7] and
tetrafluoroethylene [116-14-3] also have been prepared with this initiation system. VF tends toward alterna-
tion with tetrafluoroethylene and incorporates preferentially in copolymerization with vinylidene fluoride (see
Fluorine compounds, organic–polytetrafluoroethylene; poly(vinylidene fluoride)). More recently, interpolymers
of VF have been reported with tetrafluoroethylene and other highly fluorinated monomers such as hexafluoro-
propylene, perfluorobutylethylene, and perfluoroethylvinylether (46, 47). Polymerization reaction took place in
an aqueous medium using an initiator consisting of water-soluble organic azo compounds or salts of inorganic
peracids, examples of which include 2,2 -azobis(2-amidinopropane) dihydrochloride and ammonium persulfate.
Reaction conditions were relatively mild at temperatures of 60–100◦ C and pressures of 1–12 MPa in the absence
of any surfactant.
Copolymers of VF and a wide variety of other monomers have been prepared (6, 44, 45, 48–53). The high
energy of the propagating VF radical strongly influences the course of these polymerizations. VF incorporates
well with other monomers that do not produce stable free radicals, such as ethylene and vinyl acetate, but
is sparingly incorporated with more stable radicals such as acrylonitrile [107-13-1] and vinyl chloride. An
Alfrey-Price Q value of 0.010 ± 0.005 and an e value of 0.8 ± 0.2 have been determined (54). The low value of
Q is consistent with little resonance stability and the e value is suggestive of an electron-rich monomer.

3. Polymer Properties

Poly(vinyl fluoride) [24981-14-4] (PVF) is a semicrystalline polymer with a planar, zig-zag configuration (55).
The degree of crystallinity can vary significantly from 20–60% (56) and is thought to be primarily a function
of defect structures. Wide-line Nuclear magnetic resonance (nmr) and X-ray diffraction studies show the unit
cell to contain two monomer units and have the dimensions of a = 0.857 nm , b = 0.495 nm , and c = 0.252 nm
(57). Similarity to the phase I crystal form of poly(vinylidene fluoride) suggests an orthorhombic crystal (58).
The relationship of polymer structure to melting point and degree of crystallinity has been the subject of
a number of studies. Head-to-head regio irregularities in PVF are known (56, 59, 60) and the concentration
of such units has been suggested as the source of variations in melting point (45, 52, 61). Commercial PVF
contains ∼ 12% head-to-head linkages by 19 F- nmr and displays a peak melting point of ∼ 190◦ C (52, 53, 62,
63). Both nmr and infrared (ir) studies have shown PVF to be atactic (52, 56, 59, 60, 64–67) and, as such,
variations in stereoregularity are not thought to be a contributor to variations in melting point.
 POLY (VINYL FLUORIDE) 3

PVF with controlled amounts of head-to-head units varying from 0 to 30% have been prepared (52, 53) by
using a chlorine substituent to direct the course of polymerization of chlorofluoroethylenes and then reductively
dechlorinating the products with tributyltin hydride. This series of polymers shows melting point distributions
ranging from ∼ 220◦ C for purely head-to-tail polymer down to ∼ 160◦ C for polymer containing 30% head-to-
head linkages. This study, however, does not report the extent of branching in these polymers. Further work
has shown that the extent of branching has a pronounced effect upon melting temperature (62, 63). Change of
polymerization temperature from 90 to 40◦ C produces a change in branch frequency from 1.35 to 0.3%, while
the frequency of monomer reversals is nearly constant ( 12.5 ± 1% ). The peak melting point for this series
varies from 186◦ C (90◦ C polymerization) to 206◦ C (40◦ C polymerization).
PVF displays several transitions below the melting temperature. The measured transition temperatures
vary with the technique used for measurement. Tg (L) (lower) occurs at −15 to −20◦ C and is ascribed to be
relaxation free from restraint by crystallites. Tg (U) (upper) is in the 40–50◦ C range and is associated with
amorphous regions under restraint by crystallites (68). Another transition at −80◦ C has been ascribed to
short-chain amorphous relaxation and one at 150◦ C associated with premelting intracrystalline relaxation.
PVF has low solubility in all solvents below ∼ 100◦ C (66). Polymers with greater solubility have been
prepared using 0.1% 2-propanol polymerization modifier and were characterized in dimethylformamide (DMF)
solution containing 0.1 N LiBr. Mn ranged from 76,000 to 234,000 (osmometry), and Ms from 143,000 to 654,000
(sedimentation velocity). Sedimentation velocity molecular weights can be related to intrinsic viscosity using
the Mark–Houwink equation:

ηinh = K Ma

Using an a value of 0.80, which is typical of an extended polar polymer in good solvent, K is determined to be
6.52 × 10−5 (69).
The conformational characteristics of PVF are the subject of several studies (58, 70). The rotational
isomeric state (RIS) model has been used to calculate mean square end-to-end distance, dipole moments, and
conformational entropies. 13 C nmr chemical shifts are in agreement with these predictions (71). The stiffness
parameter (†) has been calculated (72) using the relationship between chain stiffness and cross-sectional
area (73). In comparison to polyethylene, PVF has greater chain stiffness that decreases melting entropy, ie,
(S)m = 8.58 J/(molK · ) [2.05 cal/(mol·K)] vs 10.0 J/(mol·K) [2.38 cal/(molK
· )].
A solubility parameter of 24.5 − 24.7 MPa1/2 [12.0 − 12.1 (cal/cm3 )1/2 ] has been calculated for PVF using
room temperature swelling data (74). The polymer lost solvent to evaporation more rapidly than free solvent
alone when exposed to air, which was ascribed to reestablishment of favorable dipole–dipole interactions within
the polymer. Infrared spectral shifts for poly(methyl methacrylate) in PVF have been interpreted as evidence
of favorable acid–base interactions involving the H from CHF units (75). This is consistent with the greater
absorption of pyridine than methyl acetate despite a closer solubility parameter match with methyl acetate.
PVF is more thermally stable than other vinyl halide polymers. High molecular weight PVF is reported
to degrade in an inert atmosphere, with concurrent HF loss and backbone cleavage occurring at ∼ 450◦ C (76,
77). In air, HF loss occurs at ∼ 350◦ C, followed by backbone cleavage ∼ 450◦ C.
More recent work reports the onset of thermal degradation at lower temperatures and provides a clearer
picture of the role of oxygen (78–80). In the presence of oxygen, backbone oxidation and subsequent cleav-
age reactions initiate decomposition. In the absence of oxygen, dehydrofluorination eventually occurs, but at
significantly higher temperatures.
PVF is transparent to radiation in the ultraviolet (uv), visible, and near-ir regions, transmitting 90% of
the radiation from 350 to 2500 nm. Radiation between 7000 and 12,000 nm is absorbed (81). Exposure to low
dose γ irradiation produces cross-links in PVF and actually increases tensile strength and etching resistance,
whereas the degree of crystallinity and melting point are reduced (82). PVF becomes embrittled upon exposure
4 POLY (VINYL FLUORIDE)

to electron beam radiation of 10 MGy (109 rad), but resists breakdown at lower doses. It retains its strength at
0.32 MGy ( 32 × 106 rad ) while polytetrafluoroethylene is degraded at 0.02 MGy ( 2 × 106 rad ) (83).

4. Fabrication and Processing

Commercial PVF is insoluble at room temperature because of the large number of hydrogen bonds and high
degree of crystallinity. Some latent solvents solvate PVF at temperatures > 100◦ C. PVF is converted to thin
films and coatings. Processing of PVF, eg, by melt extrusion, depends on latent solvation of PVF in highly polar
solvents and its subsequent coalescence. An example is plasticized melt extrusion of PVF into thin films (84).
Pigments, stabilizers, plasticizers, and other additives can be incorporated in the film by dispersing them with
the polymer in the latent solvent. The solvent is recovered by evaporation after extrusion. The extruded film
can be biaxially oriented to varying degrees.
PVF can be applied to substrates with solvent-based or water-borne dispersions, or by powder-coating
techniques. Viscosity modifiers are often needed to obtain a coatable dispersion. Dispersions can be applied
by spraying, reverse roll coating, dip coating, and centrifugal casting. Other methods include casting on a
continuous belt, extrusion into a hot liquid (85), and dipping a hot article into the dispersion (86).
Table 2 lists properties of PVF films. Various multilayer cast PVF films have been reported (87). Physical
and tensile properties of the film depend on the extent of its orientation (88).

Table 2. Properties of Poly(vinyl fluoride) Film

Property Value ASTMa test method
Physical and thermal properties
bursting strength, kPab 200–450c D774
coefficient of friction with metal 0.18–0.21 D1894-78
density, g/cm3 1.38–1.72 weighed samples
impact strength, kJ/md 43–90 D3420-80
refractive index, nD 1.46 D542; Abbe
refractometer, 30◦ C
tear strength, kJ/md
propagated 6–22 D1922-67
initial 129–196 D1004-66
tensile modulus, MPae 44–110 D882
ultimate elongation, % 115–250 D882
ultimate yield strength, MPae 33–41 D882
linear coefficient of expansion, cm/(cm·◦ C) 0.00005 air oven, 30 min
useful temperature range, ◦ C
continuous use −70 to +107
short cycle (1–2 h) 175
zero strength, ◦ C 260–300 hot bar
thermal conductivity (1◦ C/cm), W/(m·K)
−30◦ C 0.14
60◦ C 0.17
self-ignition temperature, ◦ C 390 D1929
solar energy transmittance, 359–2500 nm, % 90 E427-71
Permeability
moisture absorption, % 0.5 D570-81
moisture vapor transmission, f nmol/(m2 s) g
at 7.0 kPa,h 39.5◦ C 4.65–29.4 E96-58T
gas permeability, f nmol/(m·sGPa) i at
98 kPa,h 23◦ C D1434
carbon dioxide 22.4
helium 302
 POLY (VINYL FLUORIDE) 5

Table 2. Continued
Property Value ASTMa test method
hydrogen 117
nitrogen 0.5
oxygen 6.6
vapor transmission rate, j nmol/(m2 s) k at 23.5◦ C E96, modified
acetic acid 4.9
acetone 1570
benzene 13
carbon tetrachloride 3.9
ethyl acetate 13
hexane 10
waterl 22
Electrical propertiesm
corona endurance, h at 60 Hz, 40 V/µm 2.5–6.0 D2275
dielectric constant at 1 MHz, 23◦ C 6.2–7.7 D150-81
dielectric strength, D150-81
short term ac, kV/µm 0.08–0.13
short term dc, kV/µm 0.15–0.19
dissipation factor, % D150-81
1 MHz at 23◦ C 0.17–0.28
1 MHz at 100◦ C 0.09–0.21
10 kHz at 23◦ C 0.019–0.019
10 kHz at 100◦ C 0.21–0.067
volume resistivity for transparent film, Gm D257
23◦ C 2000–700
100◦ C 0.7–2
surface resistivity, Gm D257
23◦ C 60,000–20,000
100◦ C 7–20

a Unless otherwise noted.

b To convert kPa to psi, multiply by 0.145.
c Range dependent on composition and tensile modification.
d To convert kJ/m to
ft·lbf /in. , divide by 0.0534 (ASTM D256).
e To convert MPa to psi, multiply by 145.
f Measurements made on films of nominal 25 µm thickness.
g To convert
nmol/(m2 ·s) to g/(m2 ·d) , multiply by 1.94.
hTo convert kPa to mm Hg, multiply by 7.5.
i To convert
nmol/(m·s·GPa) to mL·mil/(m2 ·d·atm) , multiply by 7.725.
j At partial pressure of vapor at given temperature.
k To convert
nmol/(m2 ·s) to g/(m2 ·d) , multiply by 1.94 and by the density.
l At 39.5◦ C.
mRange of electrical properties is given; the first value refers to 54.8-µm transparent film, and the second value to 54.8-µm white

pigmented film.

Adherability of the film may be enhanced by its treatment with flame, electric discharge, boron trifluoride
gas, activated gas plasma, dichromate sulfuric acid, and a solution of alkali metal in liquid ammonia (89–92).
A coating of polyurethane, an alkyl polymethacrylate, or a chlorinated adhesive can be applied to PVF surfaces
to enhance adhesion (85, 93, 94).
6 POLY (VINYL FLUORIDE)

5. Economic Aspects

PVF is available from Du Pont both as transparent and pigmented films and as a resin under the trademark
Tedlar PVF film. Films are available in nonoriented and oriented grade in several tensile modifications and
thicknesses, with either adherable or nonadherable release-grade surfaces. Nonorieted films exhibit extensive
conformability to various shapes. PVF films are available in single layer and integrated multilayers where
the top layer of the latter is clear and the bottom layer may possess aesthetic effects such as color, metallic
appearance or pearlescenc. The prices in the year 2000 ranged from $30 to 70/kg. Prices for specially tailored
films were significantly higher.

6. Health and Environment

A number of studies and reviews of the toxicological effects of exposure to VF have been conducted (95–97). A
1995 report (98) by International Agency for Research on Cancer (IARC) has evaluated the preceding data for
VF and a classification of “probably carcinogenic to humans” was assigned to VF. In 1998, American Conference
of Government Industrial Hygienist (ACGIH) classified VF as an A2 carcinogen defined as “suspected human
carcinogen”. These classifications are based only on animal data since sufficient epidemiology data do not
exist. The oncogenic potential of VF has been studied in male and female rats and mice administered VF
via inhalation. Exposure concentrations ranged from 0 to 2500 ppm for 6 h/day, 5 days/week for up to 2 yr
(95). Under the conditions of this study, VF was found carcinogenic, similar to other monohaloethylenes, at
concentrations of 25 ppm or greater. Mice were more susceptible than rats to the carcinogenic effects of VF
and were found to metabolize VF more readily than rats or humans (99). A metabolite of VF is the suspected
carcinogenic species. VF is metabolized to the suspected carcinogenic intermediate at a rate approximately
one-fifth that of vinyl chloride (100–104).
VF is flammable in air between the limits of 2.6 and 22% by volume. Minimum ignition temperature for
VF and air mixtures is 400◦ C. A small amount, <0.2% , of terpenes is added to VF to prevent spontaneous
polymerization. The U.S. Department of Transportation has classified the inhibited VF as a flammable gas.
The self-ignition temperature of PVF film is 390◦ C. The limiting oxygen index (LOI) for PVF is 22.6%
(105), which can be raised to 30% in antimony oxide-modified film (106). Hydrogen fluoride and a mixture of
aromatic and aliphatic hydrocarbons (107) are generated from the thermal degradation of PVF. Toxicity studies,
ie, survival and time to incapacitation, of polymers, cellulosics (108, 109), and airplane interior materials (110)
expose mice to pyrolysis products and show PVF thermal degradation products to have relatively low toxicity.

7. Uses

The uses of PVF depend on its weatherability, strength over a wide range of temperatures, and inertness toward
a wide variety of chemicals, corrosives, and staining agents. It finds wide use as a protective or decorative
coating. It can be applied as a preformed film in a laminating step or from a dispersion in a coating step. It may
be transparent or pigmented in a variety of colors. PVF film is laminated to cellulosics, flexible vinyls, plastics,
rubbers, and resin-impregnated felt. These laminated products are applied to exterior wall panels for buildings
(111, 112), highway sound barriers (113), automobile trim, truck and trailer siding (114), vinyl awnings, backlit
signs (115), pipe covering (116), stain-resistant wall coverings, and aircraft cabin interiors (117, 118).
On metal or plastics, PVF surfaces serve as a primer coat for painting, eg, automobile parts, or where
improved adhesion is desired (119). Because of its moisture impermeability and wide operating temperature
range, PVF film is used to fabricate bags to contain glass fiber mats for insulating exterior airplane walls and
cargo space, and air conditioning ducts. PVF has long been used to construct bags for sampling gases (120).
 POLY (VINYL FLUORIDE) 7

Fiber-reinforced panels covered with PVF have been used for greenhouses. Transparent PVF film is
used as the cover for flat-plate solar collectors (121) and photovoltaic cells (qv) (122). White PVF pigmented
film is used as the bottom surface of photovoltaic cells. Nonadhering film is used as a release sheet in plastics
processing, particularly in high temperature pressing of epoxy resins for circuit boards (123–125) and aerospace
parts. Dispersions of PVF are coated on the exterior of steel hydraulic brake tubes and fuel lines for corrosion
protection.

BIBLIOGRAPHY

“Poly(vinyl fluoride)” under “Fluorine Compounds, Organic,” in ECT 2nd ed., Vol. 9, pp. 835–840, by L. E. Wolinski, in ECT
3rd ed., Vol. 11, pp. 57–64, by D. E. Brasure; “Poly(vinyl Fluoride” under “Fluorine Compounds, Organic,” in ECT 4th ed.,
Vol. 11 pp. 683–694, by S. Ebnesajjad, L. G. Snow, DuPont Company; “Fluorine-Containing Polymers, Poly (Vinyl Fluoride)”
in ECT (online), posting date: December 4, 2000, by S. Ebnesajjad, L. G. Snow, DuPont Company.

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10 POLY (VINYL FLUORIDE)

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