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Recent Advances in Fluoropolymers: Copolymers of Tetrafluoroethylene and

Related Fluorinated Molecules

Article · November 2003

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 Recent Advances in Fluoropolymers: Copolymers of
Tetrafluoroethylene and Related Fluorinated Molecules.

Giovanni Rojas
University of Florida
November 25th 2003

KEYWORDS: Tetrafluoroethylene, fluoropolymer, suspension, emulsion, Supercritical carbon dioxide.

Abstract: Tetrafluoroethylene copolymers have been prepared using regular or

perfluorinated solvents, aqueous medium, and surface modification by radiation and
supercritical carbon dioxide. The use of perfluorinated solvents is frequently avoided because
of environmental problems. Water polymerizations contemplate suspension, emulsion and
Cyclodextrines processes, although the use of surfactants (usually fluorinated) is required.
Surface modification of polymer films is a cleaner methodology but stereo regular polymers
are not guaranteed. The most promising method is carried out under supercritical CO2
conditions, solving the environmental problem of the use chlorofluoro compounds;
furthermore the industrial use of CO2 makes PTFE production much cheaper.

Contents

1 INTRODUCTION............................................................................................................................... 2
2 COPOLYMERIZATION OF TETRAFLUOROETHYLENE AND MONOMERS RELATED
EMPLOYING ORGANIC SOLVENTS..................................................................................................... 3
2.1 POLYMERIZATION INVOLVING REGULAR ORGANIC SOLVENTS...................................................... 4
2.2 POLYMERIZATION INVOLVING FLUORINATED AND PERFLUORINATED SOLVENTS ......................... 6
3 COPOLYMERIZATION OF TETRAFLUOROETHYLENE AND RELATED
FLUOROPOLYMERS UNDER AQUEOUS MEDIUM .......................................................................... 9
3.1 SUSPENSION PROCESS................................................................................................................... 9
3.2 EMULSION PROCESS ..................................................................................................................... 9
3.3 CYCLODEXTRINES IN POLYMER SYNTHESIS .................................................................................11
4 SURFACE MODIFICATION OF TETRAFLUOROETHYLENE AND RELATED
POLYMERS ................................................................................................................................................13
4.1 INCORPORATION OF METALLIC ATOMS INTO POLYTETRAFLUOROETHYLENE SURFACES ..............15
4.2 DEGRADATION MECHANISM OF TETRAFLUOROETHYLENE COPOLYMERS ....................................16
5 POLYMERIZATION IN SUPERCRITICAL CO2 ........................................................................17
6 CONCLUSION ..................................................................................................................................18
7 REFERENCES ...................................................................................................................................18
 2

1 Introduction

Teflon is one of the most important and representative fluoropolymers; it was synthesized
for first time in 1938 and commercialized in the 1970s by DuPont. It is synthesized using
radical polymerization and its process did not change much after those days. In essence it
is a polymer material that is prepared using tetrafluoroethylene (TFE) initiated by radical
agents under high temperatures and pressure. Its physical and chemical properties make
this material interesting and useful because it is resistant to high temperatures (300°C)
and it is not soluble in regular organic solvents and water; also it is not flammable or
adherent.

Teflon is frequently used in parts of artificial organs, heart valves and Fallopian tubes.
They are also used in plastic surgery to substitute parts of the nose, heart, and jaw. They
are also manufactured in plastic artificial sanguine arteries and tubes for drainage of
fluids from the brain and thorax, because it does not produce an immunologic reaction
when they are implanted in contact with the natural tissues. In 1982, it was used in
artificial heart for the first time to substitute the human heart in a permanent way or
during a long period of time. After that it has been used on several occasions, although
investigators have to solve certain technical and physiological problems. Teflon and
related polymers are also used in aerospace, aeronautics, engineering, optics, textile
finishing, lithography and microelectronics.

Fluorinated polymers have the inherent advantage of present high thermal stability, and
chemical inertness to acids, bases and organic solvents; also their dielectric constants and
dissipation factors are low, as well as low water absorptivity, excellent weatherability and
a good resistance to oxidation and aging, besides low flammabilities and very interesting
surface properties. However, fluoroplastics exhibit various drawbacks: homopolymers are
often crystalline, which is the reason for their high cost; also they present low solubility
in organic solvents, which cannot permit their full characterization by the conventional
NMR techniques. Furthermore, homopolymers and copolymers are cured with difficulty.
A solution to avoid these problems consists of performing a copolymerization of
fluorinated monomers with either hydrogenated or non-perfluorinated comonomers.

Many methodologies to obtain copolymers of TFE have been reported. Most of them
employ wet chemistry in regular organic solvents and more often chlorofluoro
compounds (CFC) with many environmental implications 1-9. Other methodologies that
reduce environment problems employ dispersion polymerization; water is used as solvent
but it has to be treated with surfactants that make possible the formation of micelles
where the propagation reaction is carried out 10-12. A third methodology to obtain
copolymers of TFE is just to modify the surface of the polytetrafluoroethylene using
plasma and light bombarding over the film; it is to activate the surface forming free
radicals on the film, further graft copolymerization can be performed via radical
copolymerization 13-21. The last method and the most friendly in terms of the environment
is using supercritical CO2; this methodology is very convenient and cheap because it does
not employ conventional organic solvents but it is restricted for radical polymerizations
because anionic chains react with the CO2 inactivating the propagation or incorporating
 3

ester moieties in the main backbone; although some examples of anionic polymerization
in scCO2 have been reported 22-24.

PTFE is insoluble in any solvent, so that ordinary methods using solvents cannot be
applied to determine the molecular weight. Instead, it is customary to estimate the
molecular weight of PTFE by measuring the specific gravity and the heat of
crystallization.

2 Copolymerization of tetrafluoroethylene and monomers related

employing organic solvents

Many fluorinated monomers have been synthesized. Among the most used, commercially
available olefins are tetrafluoroethylene (TFE), vinylidene fluoride (VDF),
chlorotrifluoroethylene (CTFE), hexafluoropropene (HFP), hexafluoroisobutylene
(HFIB), trifluoropropene (TFP), perfluoroalkylvinyl ethers (PAVE), methyl
trifluoroacrylate (MTFA), whereas less used are perfluorobutadiene, trifluorostyrene and
its derivatives, and bromotrifluoroethylene 8.

The copolymerization of fluorinated monomers with non-fluorinated ones has produced

many industrial products. Two of the most important are CTFE/ethylene (E) and TFE/E.
Those are commercialized by Ausimont and Dupont under the trademark HALAR1 and
TEFZEL1 respectively, while Allied patented CM1 composed by HFIB/VDF
comonomers. On the field of elastomers, the Asahi Glass Company commercializes
TFE/propene (P) copolymers under the trademark of AFLAS1 8.

Around the 1980s, some companies proposed coatings based on CTFE copolymers, for
example CTFE/vinyl ether copolymers (LUMIFLON1) from Asahi Glass, CTFE/2-allyl
oxyethanol/vinyl acetate copolymers (FLUOROBASE1) from Ausimont and a
tetrapolymer of VDF/CTFE/TFE/2-allyl oxyethanol from Elf Atochem. For the case of
the fluoroalkenes copolymers, the Solvay Company developed the Solef thermoplastics
which mainly contain PVDF and a small amount of HFP or CTFE. The Elf Atochem,
Kureha and Dyneon companies also commercialize flexible PVDF composed of
VDF/CTFE or VDF/HFP comonomers 8. In the case of fluorothermoplastic elastomers
(FTE), the Central Glass Company produces (VDF/CTFE)-g-VDF, which is a graft
copolymer with a Tg of 218°C. Daikin Company produces a block copolymer VDF-b-
(VDF/HFP). Ausimont prepares fluorothermoplastic elastomers from perfluoropolyether
under the trademark of Zdol1 8.

Polymerization can be performed in different solvents depending of the nature of the

fluoromonomer and comonomer. Two kind of reactions can be described, including
reactions on regular solvents such as acetonitrile, dimethyl formamide (DMF),
tetrahydrofurane (THF), etc. Reactions on fluorinated and perfluorinated solvents also
have been reported, because some fluoromonomers are not soluble in the regular organic
solvents; then CF2Cl2, trichlorfluorethane (CFCl2CF2Cl), perfluorooctyl bromide or
 4

Perflubron, n-C8F17Br, perfluoro-2-butyltetrahydrofuran (FX-80), perfluorotributylamine,

perfluorooctane and some perfluoropolyethers have been employed.

2.1 Polymerization involving regular organic solvents

Tetrafluoroethylene and related monomers can be homopolymerized using regular

organic solvents, via free radical polymerization. The reaction has to be initiated by the
formation of free radicals, which are usually obtained from thermal decomposition of
peroxides. The free radical formed attacks one molecule of the monomer and then a new
free radical is formed. A new monomer is attacked for the previous radical formed and
the propagation is carried out. The termination process can be reached when two
activated polymer chains react by disproportionation or radical chain transfer. The
mechanism of copolymerization involves the same steps but two or more monomers are
added to the reaction; then random copolymers are formed.

Tetrafluoroethylene and VDF have been copolymerized with different fluorinated

comonomers; typically the reaction is carried out in acetonitrile and initiated with t-butyl
peroxide. However, other authors have reported reactions initiated by diisopropyl
peroxydicarbonate (IPP), lauroyl peroxide (LPO), benzoyl peroxide (BPO), t-butyl
peroxyisobutyrate (PBIB), and azobisisobutyronitrile (AIBN). All these initiators have
shown good activity toward the polymerization.

One of the favorite comonomers used for copolymerization of TFE or VDF is

hexafluoropropene, because its simplicity in terms of the chemical structure; the resultant
polymer has a low dielectric constant, and low water absorptivity, and it shows potential
application in engineering and optics 9. (Fig. 1)

Figure 1. Copolymerization of VDF and hexafluoropropene (HFP)

Boutevin and Ameduri have synthesized a new copolymer using a ω-trifluorovinil

alcohol. Also the kinetics for the reaction was studied 2. (Fig. 2)

Figure 2. Copolymerization of VDF and 2,3,3-trifluoro prop-2-enol (FA1)

 5

Copolymerization of VDF with unsaturated-fluorinated esters has been studied by

Bauduin and Amerudi. Both reactions were performed in acetonitrile at 120°C 1-4. (Fig. 3
and 4)

Figure 3. Copolymerization of VDF and 4,5,5-trifluor-4-ene pentyl acetate (FAc)

Figure 4. Copolymerization of VDF and methyl 1,1-dihydro-4,7-dioxaperfluoro-5,8-dimethyl non-1-enoate

(MDP)

Different copolymers of the type VDF/CF2=CF-X-OH have been prepared, where X =

(CH2)m or (CF2)(CH2)m. Trifluorovinyl alcohols exhibited a lower reactivity while
copolymerization of VDF with the previous trifluorovinyl monomers was successfully
achieved 3. Ameduri and Boutevin have reported the copolymerization at 50°C of VDF
with CF2=C(CF3)-O-R 3. (Fig. 5)

CF3 (H3C)3COOC(CH3)3
Poly TFE/BPFP
F2C CF2 + F2C
0
R acetonitrile, 50 C

R = -OBz BPFP

R = -OAc APFP

Figure 5. Copolymerization of TFE and 2-benzoyloxypentafluoropropene (BPFP)

A series of great investigations about copolymerization of VDF with different fluorinated

comonomers using solvents such as acetonitrile, acetone, DMF, DMAc, and THF, has
been reported 1-4. The monomer reactivity ratios using the Tidwell and Mortimer method
for diverse comonomers have been reported.
 6

Table 1. Monomer Reactivity Ratios for Copolymerization of VDF (A) with Other Fluoromonomers (B)
and Ethylene

Assuming that rA < 1 and rB > 1, one can consider that the rate constants k can be
compared as follows: kAA < kAB and kBB > kBA, showing that both radicals Poly-VDF• and
Poly-comonomer• have a high tendency to react to the comonomer. Then, this table is
very useful, because it can be used to extrapolate the results to other monomers (A) and
predict reactivities with certain grade of confidence. An interesting conclusion of this
table is the more the double bond substituted by fluorinated atoms, the more reactive the
TFE in copolymerization.

2.2 Polymerization involving fluorinated and perfluorinated solvents

Most of the copolymers obtained by the reaction in regular organic solvents produce low
molecular weight, because regular solvents do not have the ability to solubilize large
molecules of perfluorinated polymers, and premature precipitation is observed. The use
of fluorinated or perfluorinated solvents produces a medium where the fluoropolymer is
more soluble and higher molecular weight can be reached. The solvents widely used for
copolymerization of fluoropolymers are CF2Cl2, trichlorfluorethane (CFCl2CF2Cl),
perfluorooctyl bromide or Perflubron, n-C8F17Br and perfluorooctane.

The polymerization using fluorinated solvents confers stability to the process; obtaining
polymers with higher molecular weight and permitting the copolymerization of species
nonpolymerizable under regular organic solvent conditions. Sianesi et al. have developed
 7

a new copolymer using TFE and oxygen via free radical polymerization 5, which under
regular organic solvent conditions is not possible, because oxygen is an inhibitor of the
propagation. A perfluorinated ether copolymer is obtained. The general structure for this
material is represented for the following formula: RFO(CF2CF2O)n(CF2O)m(O)pRF where
(O) represents a peroxide oxygen and RF is a CF3 or a C2F5 group. The proposed
mechanism based on the kinetic studies involves the formation of peroxide radicals that
react with the monomer, which can react with oxygen forming new peroxides. This new
peroxide can decompose forming oxygen and alkoxy radicals, and those propagate the
reaction forming a perfluorinated polyether 5. (Fig. 6)

Figure 6. Elementary Steps of the Reaction Model

Merkel et al. have performed studies about the gas sorption on copolymers of TFE with
2,2-Bis(trifluoromethyl)-4,5-difluoro-1,3-dioxole (Teflon AF). This fluorinated material
has shown permeability toward oxygen, which is comparable with PDMS rubbers; this is
very convenient in terms of biocompatibility and makes the material potentially useful in
biomedicine 6. The TFE / 2,2-Bis(trifluoromethyl)-4,5-difluoro-1,3-dioxole copolymer is
obtained by the copolymerization of their respective monomers into perfluorooctane; the
reaction is usually initiated by peroxides. (Fig. 7)

F F
F F
F F
(H3C)3COOC(CH3)3 CF2CF2
+ n
O O O O m
F F perfluorooctane

F3C CF3 F3C CF3

Figure 7. Synthesis of Teflon AF in perfluorooctane

 8

The monomer 2,2-Bis(trifluoromethyl)-4,5-difluoro-1,3-dioxole is particularly interesting

because it is an acetal, and they are usually employed as protective groups for ketones
and aldehydes. The advantage of their use as protectors is that they are hydrolyzed easily
under acidic conditions; but in this particular case the 2,2-Bis(trifluoromethyl)-4,5-
difluoro-1,3-dioxole monomer and the respective copolymer is resistant to the attack of
acids. This behavior is explained by the presence of the fluorine atoms which confer
stability to the acetal due the high electronegativity and electroattractive effect.

Another interesting material is the copolymer obtained from the reaction between TFE
and ethylene (ETFE) because it provides a melt-processable fluoropolymer with a unique
combination of excellent thermal, mechanical, chemical, and electrical properties. The
copolymer is crystalline with a nearly 1:1 alternating monomer sequence and its structure
has been characterized. The ETFE copolymer occupies a special position among
fluoropolymers as it contains alternating structural units of polyethylene and
polytetrafluoroethylene [–(CF2–CF2–CH2–CH2)n–] that confers on it a unique
combination of properties imparted from both fluorocarbon and hydrocarbon polymers 8.
For example, ETFE is less dense, tougher, stiffer and exhibits more high-tensile strength,
flexural modulus and creep resistance than the fully fluorinated polymer i.e.
polytetrafluoroethylene (PTFE), poly(tetrafluoroethylene-co-hexafluoropropylene) (FEP)
and poly(tetrafluoroethylene-co-perfluorovinyl ether) (PFA).

The copolymerization of ETFE has been performed under various initiators such as
diisopropyl peroxydicarbonate (IPP), lauroyl peroxide (LPO), benzoyl peroxide (BPO),
t-butyl peroxyisobutyrate (PBIB), and azobisisobutyronitrile (AIBN). All of these have
shown good yields toward the polymerization, although t-butyl peroxyisobutyrate at 65°C
is widely used 7. Reaction is usually carried out under trichlorotrifluoroethane
(CFCl2CF2Cl) (R113) because it is an inert solvent. However, trichlorofluoromethane
(CCl3F) (R11) probably acts as a chain transfer agent toward the polymerization. The
chain transfer reaction occurs through the extraction of the chlorine atom from solvent by
the propagating polymer radical, producing copolymers that contain a small amount of
chlorine (of the order of 103 ppm). Copolymers of the desired molecular weight can be
obtained by using a mixture of solvent, at a constant monomer relation 7. (Fig. 8)

Figure 8. Control of the molecular weight by addition of R11 to R113

 9

Many methodologies have been reported about copolymerization of ETFE and related
fluoropolymers under perfluorinated solvents and high pressures, although
copolymerizations that involve water as solvent are preferred, because of environmental
implications. It has been known since the 1940s and they will be discussed in the
following section.

3 Copolymerization of tetrafluoroethylene and related fluoropolymers

under aqueous medium

Copolymerization of TFE and related monomers are more often developed in aqueous
medium, because it avoids the use of fluorinated solvents that have been found friendlier
in terms of the environment; however the use of surfactants is required. The
copolymerization of TFE in aqueous medium can be carried out by two different
procedures, suspension and emulsion polymerization.

3.1 Suspension process

Suspension polymerizations are carried out when a small amount of or no dispersion

agent is employed with vigorous agitation to produce precipitation resin, commonly
referred to as “granular” resin. Highly fluorinated and perfluorinated dispersing agents
have been used to give a stable aqueous dispersion of small polymer particles, as well as
permitting a high rate of polymerization, avoiding premature precipitation of the
polymeric product and decreasing the contamination of the polymer product with
hydrocarbon-based residues 12. As a consequence of this, the rate of polymerization and
the shape of the polymer particles are strongly related to the concentration of surfactant
12
.

3.2 Emulsion process

Emulsion polymerization is developed with sufficient dispersing agent and mild

agitation, which produces small colloidal particles dispersed in the aqueous reaction
medium. Control of coagulant formation is important for the emulsion polymerization
process. Coagulation can be formed because the surfactant probably does not work
properly for the specific reaction, or because too much shear, or poor temperature control
12
. A stabilizer or anticoagulant has to be added to prevent coagulation during the
polymerization.

Generally, emulsion polymerization has been discussed on the basis of Harkins'

hypothesis and the Smith-Ewart theory, which assume that the particle generation occurs
with each entry of the dissolved free radical into an emulsifier micelle and continues until
the micelle population vanishes. But the accepted concepts of the mechanism of emulsion
polymerization have been questioned and new ideas have been proposed. A reevaluated
Smith-Ewart theory, particularly for particle generation, on the basis of many
 10

experimental results propos, that the particle generation is independent of the presence of
micelles; it occurs at each interaction of a dissolved free radical with a dissolved
monomer molecule and continues until the emulsifier is depleted to a level below which
new particles cannot achieve stability by adequate adsorption of emulsifier 11.

In the formation of particles of the PTFE dispersion it has been observed that the
polymerization of the PTFE dispersion passes through two distinct periods or phases. The
initial period of the reaction is a nucleation phase in which a given number of
polymerization sites or nuclei is established. Subsequently, there occurs a growth phase
in which the predominant action is the polymerization of TFE on established particles
with little or no formation of new particles. The transition from nucleation to the growth
stage occurs smoothly when the solid particle is between 4% and 10% in solution.
Particle number directly affects the reaction rate in emulsion polymerization and depends
on the mechanism of particle formation (micellar initiation, precipitation from the
aqueous phase, or polymerization in monomer droplets), as well as on coalescence
processes. Although the particle formation of the PTFE dispersion was known to be
dominated generally by the action of the surfactant, the exact mechanism of particle
formation remained unclear 11.

In the 1960s, tetrafluoroethylene was copolymerized with propylene (P) to give

fluoroelastomers with an alternating structure of copolymer chain, where the TFE
provides the hard phase while the soft phase is provided for the propylene. To improve
the mechanical properties crosslinking is required; this can be done bombarding the
material with hydrogen to generate free radicals that react among them forming the cured
material. Another alternative to produce crosslinking is incorporating side chains
functionalities which react binding all the polymer chains. TFE/P has been cured
incorporating small amounts of glycidyl vinyl ether (GVE). TFE/P/GVE copolymer has
been cured even at room temperature with tris(dimethylaminoethyl) phenol in the
presence of phenol accelerators or at 170°C by diamines 10. Another functionality that can
be incorporated to form crosslinked materials is the VDF which confers improved low
temperature properties, and it can be cured either with a peroxide radical trap system or
with dinucleophiles. Copolymers of TFE/alkyl vinyl ether with chloroalkyl vinyl ethers
as CSM have also been reported to be curable with diamines 10.

Figure 9. Copolymerization of TFE, P, and 4,5,5-trifluoro-4-penten-1-ol FA3

Different functionalities with potential for crosslinking can be obtained. Vinyl alcohols,
carboxylic acids, and generally various functionalized vinyl moieties can facilitate
crosslinking. (Fig. 9) Previous reaction is performed under ammonium
perfluorooctanoate as emulsifier and NaH2PO4/NaOH as buffer in order to maintain the
 11

pH between 8 and 9. The molecular weight was measured and compared with PMMA
standard; experiments at different monomer concentrations have reported molecular
weight around 6,000-35,000 g/mol 10.

3.3 Cyclodextrines in polymer synthesis

The particular chemical and physical characteristics of fluorinated monomers prohibit the
polymerization in water without addition of surfactants or cosolvents, but the addition of
surfactants does not solve the environmental problem at all, because most of the
surfactants employed to perform the reaction have to contain a certain number of fluorine
atoms. In terms of “green” chemistry, the reactions have to be developed only in water
without the intervention of environmental contaminants. This motivation has inspired the
use of molecules that can convert an insoluble molecule into a soluble one, avoiding the
use of surfactants 13. Cyclodextrines (CD) are able to enclose smaller molecules to form a
host-guest complex, which forms a hydrophobic interior where molecules are
encapsulated, and a hydrophilic exterior that is soluble in water (Fig. 10). Cyclodextrines
are produced by enzymatic conversion of starch. There are oligoamyloses consisting of
6(α), 7(β), 8(γ) and 9(δ) units of α-1,4-linked D-glucose.

Figure 10. Molecular structure of Cyclodextrines, 3D representation

 12

Water-insoluble molecules become water-soluble on treatment with aqueous solutions of

CDs without any chemical modification of the guest molecule, because there are no
covalent bonds formed between the host-guest interaction of the CD and the water-
insoluble molecule. The hydrophobic, mostly water-insoluble monomer is complexed by
the CD in water. This results in an increased monomer concentration in the aqueous
phase, where the polymerization takes place after initiation by a water-soluble initiator.
Upon polymerization, the water-insoluble polymer precipitates out, while the CD remains
in the aqueous phase and can be reused (Fig. 11) 13.

Figure 11. Schematic representation of the complexation of monomers with CD and polymerization in water

Storsberg and Ritter have homopolymerized various perfluorinated methacrylates (1, 2,

3) in presence of 1 mol of randomly methylated β-cyclodextrin (RAMEB) in aqueous
medium at 50°C using a water soluble azo initiator or a redox system conformed by
K2S2O8/NaHSO3 13. The corresponding polymers (4, 5, 6) have shown glass-transition
temperatures (Tg) of 69.5°C, 39°C and 71°C respectively. In addition they have been
copolymerized these monomers with styrene (7, 8, 9) where the Tg of 79.9°C, 60°C and
85°C were respectively reported.

Figure 12. Homopolymerization and copolymerization of perfluorinated methacrylates in presence of

RAMEB and water
 13

Additionally, the copolymer 12 (Fig. 13) was prepared in water in the presence of
RAMEB. After 2 hours at 65°C the reaction yielded 80%

Figure 13. Copolymerization of perfluorinated acrylate 10 with stearyl methacrylate 11 in the presence of
RAMEB under aqueous condition

4 Surface modification of tetrafluoroethylene and related polymers

Surface modification of polymers is a convenient and effective means to produce

polymers with improved physicochemical properties starting with inexpensive surfaces
such as TFE. Some physical properties such as wettability, adhesion, lubrication and
biocompatibility can be improved. Among the many techniques available, surface
modification via graft copolymerization appears to be one of the most versatile
techniques because it allows the molecular redesign of most polymer surfaces to impart
new and specific functionalities. The most widely used method for activating the PTFE
surface is the treatment with a reducing agent such as sodium naphthalene and t-
BuOK/benzoin/DMSO. Another method which only affects the surface is the ion
bombardment with x-ray and cold plasma 14-21. Surface modification via radiation
chemistry produces active films which are graft copolymerized with different
functionalities, producing new materials with varied physical and chemical properties,
producing non-regular polymers. Free radicals are produced randomly, contrary to the
incorporation of activated monomers in the polymerization which is structural controlled.
 14

Polyaniline (PANI) is one of the most widely studied conducting polymers. Normally the
coating process involves the physical coat of electronic devices with conductive or
polymer films. This method is not convenient because most of the coating does not
remain permanently on the surface. Polyaniline has potential in corrosion protection of
metals, light emitting devices, control of electromagnetic reactions (EMR) and the
dispersion of electrostatic charges. Kang et al. have reported the UV-induced graft
copolymerization of an aniline group-containing vinyl monomer, 4-vinylaniline (4-VAn),
on the plasma-pretreated PTFE substrate. The aniline groups of the grafted 4-VAn chains
on the PTFE surface are subsequently copolymerized with aniline via oxidative
polymerization. The covalently tethered aniline copolymers readily impart electrical
conductivity onto the surface of the highly insulating PTFE substrate 17. Kang et al. in a
series of articles have reported different methodologies with diverse chemistry to
incorporate new spacers into the grafting chain. Another method for the covalent
immobilization of the PANI involves surface modification of the Ar plasma-pretreated
PTFE film via UV-induced graft copolymerization with glycidyl methacrylate
(GMA).The GMA graft-copolymerized PTFE surface is then subjected to oxidative graft
copolymerization with aniline. Thermal curing of the epoxide functional groups of the
graft GMA chains with the amine groups of the PANI homopolymer readily resulted in
further covalent bonding of the PANI chains on the insulating PTFE substrate 18, 19.
Figure 14 shows an schematic representation of the activation and graft copolymerization
of TFE with argon plasma GMA and aniline.

Figure 14. Schematic representations of the surface modification processes and the surface structures of the
PTFE substrates with grafted GMA and aniline polymers.
 15

4.1 Incorporation of metallic atoms into polytetrafluoroethylene surfaces

Incorporation of metals into PTFE surface makes the resulting material ideal for
microelectronic applications. Modification of polymer surface by graft copolymerization
and incorporation of metals with specific functional monomers also improves the
adhesion properties 10.

Kang et al. have been copolymerized 1-vinylimidazole (VIDz) and glycidyl methacrylate
(GMA) into PTFE surfaces. The curing process by heat and evaporated copper promotes
the crosslink reaction in the graft layer.

Figure 15. Structures of 1-vinylimidazole (VIDz) and glycidyl methacrylate (GMA)

Many kinds of plastics can be contaminated or infected by microorganisms such as

bacteria if they are exposed to the atmosphere. One method of combating these
microorganisms is to develop polymer materials that have bactericidal activity. The
incorporation of metals such as CrIII, MnII, CuII, AgI and CdII has presented bactericidal
activity. Copolymers of polyacrylic acid (PAAc) with poly(tetrafluoroethylene-
perfluorovinyl ether) (PFA) have been prepared by El-Sawy and Sagheer via radiation-
induced graft polymerization 20. Complexes of CrIII, MnII, CuII, AgI and CdII with PFA-g-
PAAc were prepared, although only PFA-g-PAAc-CrIII (E. Coli; S. aureus) and PFA-g-
PAAc-CdII (E. Coli; B. anthrax; B. cereus) have presented bactericidal properties.

Figure 16. Polymer complexes formed by inter (I) and/or intramolecular (II) crosslinking in polymer
matrix
 16

4.2 Degradation Mechanism of tetrafluoroethylene copolymers

The Teflon AF or Cytop (trademarks from DuPont and Asahi Glass) contain dioxole;
depending of the desired mechanical properties such as rigidity at high temperatures,
different amounts of dioxole have to be incorporated. A possible mechanism for the
formation of acid functionalities, which involves initial cleavage of the bond between the
oxygen and the quaternary carbon has showed in the figure 17 16. The degradation
mechanism is the same mechanism proposed for the crosslink; two chain radicals react by
disproportionation forming the crosslinked material. Nasef et al. have developed studies
of degradation and crosslinking of ETFE films; the degree of decomposition Vs
crosslinking depends of the intensity and the time of radiation exposure 21. (Fig 17)

Figure 17. Mechanism for the formation of acid fluoride and acid end groups. The new chain ends are
formed from chain scission at the dioxole monomer (Left). Schematic representation of the mechanism of
electron irradiation induced reaction in ETFE films (Right).
 17

5 Polymerization in Supercritical CO2

Supercritical CO2 (scCO2) has the ability of dissolve fluorinated materials at accessible
pressures and temperatures, in contrast to regular organic solvents where the
perfluorinated polymers are completely insoluble. It has also been demonstrated to be an
excellent reaction medium for a number of polymerizations. The use of CO2 as reaction
medium has several advantages compared to conventional techniques. It is nontoxic and
inexpensive, especially compared to solution polymerization where fluorinated solvents
have to be used. The polymer can be synthesized and easily isolated in a dry and pure
form. Also no additional workup is necessary to remove the solvent or water which
eliminates the need for wastewater treatment. Another advantage inherent with its use is
that the free radical initiators have high efficiencies and acceptable decomposition
kinetics in CO2 and do not exhibit appreciable chain transfer. Moreover, TFE is made
safe to handle by forming a mixture of TFE and CO2 which is nonignitable. Resnick,
Kipp and DeSimone have obtained Teflon AF (Fig. 7) using Bis(perfluoro-2-N-
propoxypropionyl) peroxide as initiator and CO2 as solvent at temperatures below 35°C.
They found that the molecular weight was adjustable just changing the amount of
initiator. In addition, no difference between the commercial Teflon AF (DuPont) and
synthesized in scCO2 one has been found 24.

Under living anionic polymerization conditions CO2 terminates the anionic chain because
CO2 is susceptible to nucleophilic attack. It also reacts with anionic initiators or actively
propagating carbanions, making the chain unreactive toward the polymerization,
retarding or inhibiting the chain growth. It was found that the polymerization of
cyanoacrylates is virtually unaffected by the addition of oxygen, water and CO2. Only the
addition of strong acid (HCl) terminates the propagation 22. Kung et al. have reported
anionic composite formation in scCO2 of ethyl 2-cyanoacrylate over a surface of
poly(tetrafluoroethylene-co-hexafluoropropylene) (FEP). Pyridine and triphenyphosphine
were employed as initiator 22. The initiator is usually swollen into the surface sample and
the monomer (ethyl-2-cyannoacrylate) is incorporated. The polymerization produces a
surface modified polymer system (Fig. 18) where the composites are produced much
easier than previous methods. The use of scCO2 shows a new panorama in the chain
polymerization techniques to obtain modified surfaces for various applications.

Figure 18.Composte surface formation

 18

6 Conclusion

The chemistry of fluorinated polymers is very rich and many methodologies have been
employed to improve the mechanical and physical properties of the PTFE. Copolymers
have been prepared in order to produce new materials with more industrial applications.
Processes that involve regular or perfluorinated solvents, aqueous medium, and surface
modification by radiation and scCO2 have been reported to create TFE copolymers. The
most promising method is carried out under scCO2 conditions because it solves the
environmental problem of solvent use and CFCs. Furthermore, the industrial use of CO2
makes the PTFE production much cheaper.

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