Progress in Organic Coatings 53 (2005) 207–211

Fluorinated acrylic copolymers

Part I: Study of clear coatings
V.C. Malshe ∗ , Nivedita S. Sangaj
Paints and Polymer Division, University Institute of Chemical Technology,
N.M. Parekh Road, Matunga, Mumbai 400019, India

Received 22 November 2004; accepted 1 March 2005

Abstract

Fluorinated polymers find applications in various speciality coatings due to their low surface tension, non-wettability by water and oil,
non-adhesive nature and antifouling properties. However, synthesis and composition of such fluorinated polymers remains a proprietary of few
manufacturers and also requires expensive fluoro-intermediates. In this study we have adopted a simple method of synthesizing fluorinated
acrylic copolymers. Acrylic copolymers based on methyl methacrylate (MMA), butyl acrylate (BA), and functional monomer, 2-hydroxy
ethyl methacrylate (HEMA) were synthesized. The pendant OH functionality were partially esterified with tetrafluoro propanoic acid to
varying extent and cured with butylated melamine–formaldehyde resin. The fluorine content of the resins was in the range of 4–10%. The
clear coatings were studied for their optical, mechanical and protective properties. Incorporation of fluorine was found to extend the protective
ability of coatings against atmospheric corrosion. The properties were compared with their non-fluorinated analogs.
© 2005 Elsevier B.V. All rights reserved.

Keywords: Fluoropolymers; Hydrophobicity; Sorption; Atmospheric corrosion; Protective coatings

1. Introduction to its electrical conductive nature, ability to dissolve other

corrosive components in the atmosphere like O2 , SO2 , etc.,
Fluoropolymers are used in functional coating applica- and ionic species. Polymers act as barrier in the protective
tions due to their unique properties like low coefficient of coatings. However, polar groups like hydroxyl, ester, amide,
friction, low surface tension, oil and water repellency, non- etc., in conventional polymers result in molecular interaction
adhesive nature and antifouling properties along with the with moisture leading to increased surface condensed water.
added advantages like their outstanding thermal and chem- By minimizing such interactions, wetting of the surface can
ical stability in extreme conditions [1,2]. Because of their be reduced and protective life of the coatings can be extended.
small size, fluorine atoms can shield a fluorinated carbon Although most of the polymers have critical surface tension
atom without any steric stress. Fluorine is difficult to po- less than that of water (72 × 10−3 N/m) and hence are poorly
larize. This results in low intermolecular force and hence wetted by water, fluoropolymers are known to have very low
low surface tension of fluoropolymers [3]. This is especially critical surface tension due to the small bond polarization of
advantageous for their applications in surface coatings for C F bond [4]. Hence fluoropolymers can hinder water reach-
imparting corrosion protection properties. Oxygen and wa- ing the metallic surface in two ways: fluorinated polymers are
ter are two essential ingredients for initiating corrosion and not wetted by water and secondly the molecular absorption
water acts as an electrolyte in atmospheric corrosion. Liquid of water into these polymers is relatively small, about 15%
water especially is the most efficient corrosion medium due of the conventional films [5].
A number of polymers with perfluorinated parts in the
∗ Corresponding author. Tel.: +91 22 24145616x462; main chain or a side chain of acrylates [6], aromatic polyesters
fax: +91 22 24145614. [7] and polyurethanes [8] have been reported. The lowest
E-mail address: [email protected] (V.C. Malshe). surface tensions between 10 and 13 mN/m were found if

0300-9440/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.porgcoat.2005.03.003
208 V.C. Malshe, N.S. Sangaj / Progress in Organic Coatings 53 (2005) 207–211

semifluorinated side chains were attached to polymers [9]. Attempts are made worldwide to achieve hydrophobic
In these polymers the internal microphase separation of alkyl characteristic at the lowest possible fluorine content. In this
and perfluoroalkyl parts of the side chains causes the forma- study we have used a simple and non-hazardous approach of
tion of highly ordered surfaces with increased concentration introducing fluorine on the main chain. The resins are cured
of CF3 groups in the top layer. The attachment of fluorinated with butylated melamine–formaldehyde resin and tested for
side chain to polymeric backbones has been proven to com- their optical, mechanical and corrosion protective ability. No
bine the mechanical stability of polymers with the specific pigment has been used for assessment of anticorrosion prop-
surface properties of fluoro compounds. Constitutive law of erty, in order to accelerate the process.
wettability as proposed by Shafrin and Zisman [10] states that
in general the wettability of organic surfaces is determined
by the nature and packing of the surface atoms or exposed 2. Experimental work
groups of atoms of the solid and is otherwise independent
of the nature and arrangement of the underlying atoms and 2.1. Raw materials
molecules.
Number of polymers with perfluorinated parts in main and Fluorinated component, i.e. tetrafluoro propanoic acid
side chains have been developed and commercialized world- (TFPA) [756-09-2] was obtained by acidifying aqueous
wide. However the exact compositions of such commercial- sodium tetrafluoro propanate ([22898-01-7], M.P. 152 ◦ C),
ized products are strictly guarded. Incorporation of fluorine a chemical used as a herbicide, with sulfuric acid. Sodium
in the polymer requires expensive perfluoroalkyl compounds tetrafluoro propanate was obtained from M/s. Winner Impex
and the like. Synthesis of such fluorinated compounds re- (P) Ltd., Mumbai. TFPA was extracted with diethyl ether and
mains to be a proprietary of a few multinationals due to the separated by distillation. The product was a pale colored clear
high cost of corrosion resistant equipments involved in their liquid. The purity of the acid was determined by acid value
production. (B.P. was 133 ◦ C, Acid value of TFPA was found to be 380 mg
Both surface fluorination and bulk fluorination are used to of KOH per g compound. % purity was 98.9%). Acrylic
impart hydrophobicity. The former approach involves addi- monomers like methyl methacrylate (MMA), butyl acrylate
tion of fluoro-component to the composition and it is allowed (BA), 2-hydroxy ethyl methacrylate (HEMA) were obtained
to migrate to the surface. It is then cross-linked thus anchor- from the local suppliers. Azoisobutyronitrile (AIBN) and 2-
ing in the matrix. The latter approach is expensive, involving dodecyl mercaptan (DM) were used as a free radical initiator
addition of fluoropolymers like PTFE and the like, which also and a chain transfer agent, respectively. Propanoic acid and
limits the processiblity of the system [11]. Delucchi et al. [8] solvents like cyclohexanone, HPLC grade tetrahydrofuran,
studied the fluoropolyether coatings based on perfluoroether diethyl ether were procured from the local suppliers.
oligomeric diols cured with isocyanates. They concluded that
fluorine content is not always the dominating parameter since 2.2. Synthesis and characterization
other physical factors such as the cross-linking density, phase
separation phenomena and glass transition temperature may Acrylic copolymers were synthesized by solution poly-
play major roles. US navy has done good lot of work on merization technique using free radical initiator, AIBN (3%
fluorinated epoxy resins. Use of these fluoroepoxies was in- based on total monomer weight) and cyclohexanone as a sol-
tended in defense-related applications where performance is vent. Fifty percent solution of the monomer in cyclohexanone
foremost important rather than the cost; e.g., adhesive based was used for polymerization. In a three-necked round bot-
on fluoroepoxy for lap joints in aircraft can repel water and tom flask fitted with water condenser, thermometer pocket
hence prevent ingress of water into aircraft wings and thus and a Teflon stirrer, required quantity of acrylic monomers
can alleviate corrosion problems [12]. Various possibilities were charged along with the solvent, initiator and chain-
of incorporation of fluorine were explored right from synthe- terminating agent. The polymerization was carried out at
sis of fluorinated bisphenol [12,13] to reaction of fluorinated 75 ◦ C using water bath.
diol with epichlorohydrin [14] and to the use of fluorinated In the second stage, the required quantity of tetrafluoro
curing agents like anhydrides [12] in order to extend thermal propanoic acid (depending upon the desired extent of esteri-
performance of epoxies. fication) was added along with the esterification catalyst, p-
Deflorian et al. [15] have investigated the roles of bar- toluene sulphonic acid (PTSA) at 1% concentration based on
rier properties and metal-coating interface in the corrosion weight of acid and hydroxyl components. Esterification was
protection properties of fluoropolymers coatings. The perfor- carried out at 120 ◦ C using cyclohexanone as an azeotropic
mance was investigated by using EIS technique and peel-off solvent. The reaction was monitored by water of condensa-
adhesion test. Copolymers of tetrafluoroethylene, chlorotri- tion. Similarly the esterification was also carried out using
fluoroethylene, with vinyl ethers, hydroxy containing vinyl propanoic acid. The reaction time was around 2 h. The gen-
ethers and various polar monomers like acrylics were found eralized structure of the resins is represented in Fig. 1.
to give polymers soluble in organic solvents and that can be The products were analyzed for their hydroxyl value,
cross-linked with various cross-linking agents [11]. molecular weight and molecular weight distribution by gel
 V.C. Malshe, N.S. Sangaj / Progress in Organic Coatings 53 (2005) 207–211 209

Table 1
Composition of various acrylic copolymers
Resins Monomers Esterification OH valueb Mn Mw /Mn
MMA HEMA BA Acid % Mola
MHBT-24 50 20 30 TFPA 40 51.1 6536 2.00
MHBP-24 50 20 30 PA 40 50.3 6445 1.75
MHBT-26 50 20 30 TFPA 60 26.1 6625 1.95
MHBP-26 50 20 30 PA 60 43.8 6640 1.82
MHBT-275 50 20 30 TFPA 75 16.3 6691 1.82
MHBP-275 50 20 30 PA 75 21.3 5784 1.73
MHBT-34 50 30 20 TFPA 40 58.7 5746 1.93
MHBP-34 50 30 20 PA 40 69.5 6180 1.85
MHBT-36 50 30 20 TFPA 60 36.6 6670 1.98
MHBP-36 50 30 20 PA 60 45.7 6500 1.86
MHBT-375 50 30 20 TFPA 75 20.3 6666 1.98
MHBP-375 50 30 20 PA 75 33.9 6296 2.07
Solvent: cyclohexanone; AIBN: 3%; dodecyl mercaptan: 7.2%; temperature: 75 ◦ C (1st stage) and 120 ◦ C (2nd stage); TFPA: 2.2,3,3-tetrafluoro propanoic
acid; PA: propanoic acid.
a Based on mole of HEMA.
b mg of KOH per g resin.

permeation chromatography (GPC). For GPC, tetrahydrofu- 2.3. Testing of resins

ran was used as an elutant. Shodex® polystyrene (Polymer
Laboratories, UK) was used as a standard for calibrating the The resins were tested for their mechanical and optical
column. The column used was Hibar RT250-7 Lycrogel PS- properties as per ASTM standards [17]. For testing the prop-
400 (Merck-make) having L/D of 250 mm × 7 mm and par- erties of coatings like corrosion protection, scratch hardness
ticle size of 5 ␮m. Fluoride content of the resins was found and falling weight impact resistance, mild steel panels of
by the following method [16]. Known weight of the resin 15 cm × 7.5 cm were used. The panels were abraded with
was mixed with the excess anhydrous sodium carbonate and emery paper no. 60 followed by cleaning with the solvents xy-
heated at 800 ◦ C for 8 h in the furnace. On cooling the inciner- lene and acetone. The resins were cured with stoichiometric
ated product was dissolved in water and liquor ammonia was quantity of butylated melamine formaldehyde resin at 135 ◦ C
added to make the solution more basic and to avoid formation for 15 min. Since non-fluorinated resins showed non-wetting
of gel-like solution. The content was then heated to boiling behaviour, 0.1% (w/w) of commercial urethane-based wet-
for 15 min. The content was cooled and calcium chloride was ting agent W$D1070 (K-Tech India (P) Ltd., Thane) dis-
added to convert sodium fluoride to calcium fluoride. The so- solved in methyl ethyl ketone was mixed with the resin solu-
lution was filtered to separate the solid calcium fluoride. The tion for all the compositions before applying on the panels by
product was incinerated at 750 ◦ C in the furnace for 4 h and leveling technique. The solid content of the resin solution was
weighed after cooling. From the amount of calcium fluoride maintained at 30% by diluting with cyclohexanone. Other
formed fluorine content was calculated after correcting for properties like gloss, flexibility, cross-hatch adhesion, pencil
the solubility of calcium fluoride in aqueous solution (Solu- harness and solvent resistance were tested on aluminium pan-
bility of CaF2 in water is 16 mg/lit corresponding to 10 mg/lit els. All the fluorinated resins were dark colored as compared
as fluoride). The theoretical fluorine content was calculated to their non-fluorinated counterparts. Dry film thickness of
from the composition of the copolymer. the coatings (DFT) was measured by using magnetic DFT
Table 1 shows composition and properties of various meter on mild steel panel. Pencil hardness of the coatings
acrylic copolymers synthesized. Table 2 shows the fluorine was determined using standard pencils of hardness of 6B to
content of the resins. 5A. Impact resistance was measured by using falling weight

Table 2
Fluorine content of the resins
Resin % Fluorine content

Theoretical Experimental
MHBT-24 4.48 4.1
MHBT-26 6.28 6.1
MHBT-275 7.77 7.5
MHBT-34 6.16 6.1
MHBT-36 8.78 8.7
MHBT-375 10.59 10
Fig. 1. Molecular structure of fluorinated acrylic copolymers.
210 V.C. Malshe, N.S. Sangaj / Progress in Organic Coatings 53 (2005) 207–211

impact tester having a load of 1 kg. Flexibility of the coatings in the case of electrodeposited ED primers) and this is the
was tested on a conical mandrel of 38–3 mm diameter size main component with high diffusivity for oxygen and water.
and the panels were inspected for cracks or delamination af- Pigments being impervious in nature, extend the barrier prop-
ter bending. Adhesion was determined by using cross-hatch erties of the polymer by providing tortuous path to the diffus-
adhesion test. Specular gloss of the coatings was measured ing molecules. No pigments were therefore used. The panels
by using Gardner Glossometer at an angle of 45◦ . The sol- were checked for corrosion by visual inspection regularly.
vent resistance of the coatings was determined for methyl
ethyl ketone and xylene rubs and the panels were inspected
for loss of gloss or other impairment. For corrosion testing, 3. Results and discussion
the panels were exposed in humidity chamber, which was es-
sentially salt spray chamber except that the salt solution was The properties of all the clear coatings are given in
replaced by deionised water. Humidity inside the cabinet was Tables 3 and 4. It can be seen that the falling weight impact
84% RH at 30 ◦ C. In the present study the clear coats have and flexibility were not affected by introduction of fluorine.
been investigated on metal panels without any prior surface All the films showed good pencil hardness but some fluo-
treatments and hence the failure is much earlier compared rinated films showed less scratch hardness. Other properties
to the conventional coatings. In any protective coating, the like adhesion, gloss were more or less the same. The coatings
volume concentration of resin is 50% or more (up to 85% showed good gloss. MEK and xylene rub tests showed loss of

Table 3
Mechanical properties of coatings
Resins Properties

Film thickness Pencil hardness Flexibility (conical Scratch hardness Cross-hatch Impact resistance
(ASTM D1186-93) (ASTM D3363-74) mandrel) (ASTM (gm) (ASTM adhesiona (ASTM (ASTM D2794-84)
(␮m) D522-93a) D2197-98) D 3359-83)
Direct Indirect
(0.6 Kg m) (Kg m)
MHBT-24 75–100 2H Passes 700 Good Passes 0.55
MHBP-24 75–100 2H Passes 1100 Good Passes 0.55
MHBT-26100–150 2H Passes 700R Good Passes 0.55
MHBP-26100–150 2H Passes 1400R Good Passes 0.55
MHBT-27575–100 2H Passes 600R Good Passes 0.55
MHBP-27575–100 2H Passes 1000R Good Passes >0.60
MHBT-34100–150 2H Passes 500R Good Passes 0.55
MHBP-34100–150 2H Passes 1200R Good Passes 0.55
MHBT-36100–150 2H Passes 500R Good Passes 0.55
MHBP-36 75–100 2H Passes 1000 Good Passes 0.55
MHBT-37575–100 2H Passes 300R Good Passes >0.60
MHBP-37575–100 2H Passes 1100 Good Passes >0.60
R: failed in the reverse travel of the test panel.
a Good: the film was intact.

Table 4
Optical, chemical and protective properties of coatings
Resins Properties

Gloss @45◦ (ASTM D523-67) Solvent resistance (ASTM D5402-93) Corrosion testa (h)
Xylene rub test MEK rub test
MHBT-24 52 100 100 41
MHBP-24 59 100 100+ 21
MHBT-26 63 100 70 41
MHBP-26 50 100 100 21
MHBT-275 47 100 100 54
MHBP-275 56 100 100 21
MHBT-34 54 100 100 44
MHBP-34 58 100 100+ 21
MHBT-36 58 100 70 44
MHBP-36 58 100 100 21
MHBT-375 58 100 100 54
MHBP-375 45 100 100 21
a Exposed to deionised water in humidity chamber at 84% RH and 30 ◦ C.
 V.C. Malshe, N.S. Sangaj / Progress in Organic Coatings 53 (2005) 207–211 211

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Acknowledgements corrosion protection properties of fluoropolymers coatings, Br. Corr.
J. 32 (2) (1997) 145–149.
Authors thank Dr. S.S. Laddha of M/s. Winner Impex (P) [16] A.I. Vogel, Quantitative Inorganic Analysis, 3rd ed., Longman Group
Ltd., London, 1975, p. 570.
Ltd., Mumbai and K-Tech India (P) Ltd., for gifting sodium [17] ASTM standards: ASTM D 1957–86 Hydroxyl value of fatty oils and
tetrafluoropropionate and wetting agent, respectively. Au- acids; ASTM D1186-93 Test method for nondestructive measurement
thors are also grateful to Department of Science and Tech- of dry film thickness of nonmagnetic coatings applied to a ferrous
nology (DST), India and University of Grant commission base; ASTM D5402-93 Standard practice for assessing the solvent
(UGC), India for funds. resistance of organic coatings using solvent rubs; ASTM D523-67
Test method for measurement of gloss at 60◦ ; ASTM D3363-74
Standard test method for measurement of pencil hardness; ASTM
D552-93a Standard test methods for mandrel bend test of attached
References organic coatings; ASTM D 3359-83 Standard test method for mea-
surement of cross-hatch adhesion; ASTM D2794-84 Test method for
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