Progress in Organic Coatings 53 (2005) 207211

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 nd 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 uorinated polymers remains a proprietary of few manufacturers and also requires expensive uoro-intermediates. In this study we have adopted a simple method of synthesizing uorinated 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 esteried with tetrauoro propanoic acid to varying extent and cured with butylated melamineformaldehyde resin. The uorine content of the resins was in the range of 410%. The clear coatings were studied for their optical, mechanical and protective properties. Incorporation of uorine was found to extend the protective ability of coatings against atmospheric corrosion. The properties were compared with their non-uorinated analogs. 2005 Elsevier B.V. All rights reserved.
Keywords: Fluoropolymers; Hydrophobicity; Sorption; Atmospheric corrosion; Protective coatings

1. Introduction Fluoropolymers are used in functional coating applications due to their unique properties like low coefcient of friction, low surface tension, oil and water repellency, nonadhesive nature and antifouling properties along with the added advantages like their outstanding thermal and chemical stability in extreme conditions [1,2]. Because of their small size, uorine atoms can shield a uorinated carbon atom without any steric stress. Fluorine is difcult to polarize. This results in low intermolecular force and hence low surface tension of uoropolymers [3]. This is especially advantageous for their applications in surface coatings for imparting corrosion protection properties. Oxygen and water are two essential ingredients for initiating corrosion and water acts as an electrolyte in atmospheric corrosion. Liquid water especially is the most efcient corrosion medium due
Corresponding author. Tel.: +91 22 24145616x462; fax: +91 22 24145614. E-mail address: vcmalshe@rediffmail.com (V.C. Malshe).

to its electrical conductive nature, ability to dissolve other corrosive components in the atmosphere like O2 , SO2 , etc., and ionic species. Polymers act as barrier in the protective coatings. However, polar groups like hydroxyl, ester, amide, etc., in conventional polymers result in molecular interaction with moisture leading to increased surface condensed water. By minimizing such interactions, wetting of the surface can be reduced and protective life of the coatings can be extended. Although most of the polymers have critical surface tension less than that of water (72 103 N/m) and hence are poorly wetted by water, uoropolymers are known to have very low critical surface tension due to the small bond polarization of C F bond [4]. Hence uoropolymers can hinder water reaching the metallic surface in two ways: uorinated polymers are not wetted by water and secondly the molecular absorption of water into these polymers is relatively small, about 15% of the conventional lms [5]. A number of polymers with peruorinated parts in the main chain or a side chain of acrylates [6], aromatic polyesters [7] and polyurethanes [8] have been reported. The lowest 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

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semiuorinated side chains were attached to polymers [9]. In these polymers the internal microphase separation of alkyl and peruoroalkyl parts of the side chains causes the formation of highly ordered surfaces with increased concentration of CF3 groups in the top layer. The attachment of uorinated side chain to polymeric backbones has been proven to combine the mechanical stability of polymers with the specic surface properties of uoro compounds. Constitutive law of 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 groups of atoms of the solid and is otherwise independent of the nature and arrangement of the underlying atoms and molecules. Number of polymers with peruorinated parts in main and side chains have been developed and commercialized worldwide. However the exact compositions of such commercialized products are strictly guarded. Incorporation of uorine in the polymer requires expensive peruoroalkyl compounds and the like. Synthesis of such uorinated compounds remains to be a proprietary of a few multinationals due to the high cost of corrosion resistant equipments involved in their production. Both surface uorination and bulk uorination are used to impart hydrophobicity. The former approach involves addition of uoro-component to the composition and it is allowed to migrate to the surface. It is then cross-linked thus anchoring in the matrix. The latter approach is expensive, involving addition of uoropolymers like PTFE and the like, which also limits the processiblity of the system [11]. Delucchi et al. [8] studied the uoropolyether coatings based on peruoroether oligomeric diols cured with isocyanates. They concluded that uorine content is not always the dominating parameter since other physical factors such as the cross-linking density, phase separation phenomena and glass transition temperature may play major roles. US navy has done good lot of work on uorinated epoxy resins. Use of these uoroepoxies was intended in defense-related applications where performance is foremost important rather than the cost; e.g., adhesive based on uoroepoxy for lap joints in aircraft can repel water and hence prevent ingress of water into aircraft wings and thus can alleviate corrosion problems [12]. Various possibilities of incorporation of uorine were explored right from synthesis of uorinated bisphenol [12,13] to reaction of uorinated diol with epichlorohydrin [14] and to the use of uorinated curing agents like anhydrides [12] in order to extend thermal performance of epoxies. Deorian et al. [15] have investigated the roles of barrier properties and metal-coating interface in the corrosion protection properties of uoropolymers coatings. The performance was investigated by using EIS technique and peel-off adhesion test. Copolymers of tetrauoroethylene, chlorotriuoroethylene, with vinyl ethers, hydroxy containing vinyl ethers and various polar monomers like acrylics were found to give polymers soluble in organic solvents and that can be cross-linked with various cross-linking agents [11].

Attempts are made worldwide to achieve hydrophobic characteristic at the lowest possible uorine content. In this study we have used a simple and non-hazardous approach of introducing uorine on the main chain. The resins are cured with butylated melamineformaldehyde resin and tested for their optical, mechanical and corrosion protective ability. No pigment has been used for assessment of anticorrosion property, in order to accelerate the process.

2. Experimental work 2.1. Raw materials Fluorinated component, i.e. tetrauoro propanoic acid (TFPA) [756-09-2] was obtained by acidifying aqueous sodium tetrauoro propanate ([22898-01-7], M.P. 152 C), a chemical used as a herbicide, with sulfuric acid. Sodium tetrauoro propanate was obtained from M/s. Winner Impex (P) Ltd., Mumbai. TFPA was extracted with diethyl ether and separated by distillation. The product was a pale colored clear liquid. The purity of the acid was determined by acid value (B.P. was 133 C, Acid value of TFPA was found to be 380 mg of KOH per g compound. % purity was 98.9%). Acrylic monomers like methyl methacrylate (MMA), butyl acrylate (BA), 2-hydroxy ethyl methacrylate (HEMA) were obtained from the local suppliers. Azoisobutyronitrile (AIBN) and 2dodecyl mercaptan (DM) were used as a free radical initiator and a chain transfer agent, respectively. Propanoic acid and solvents like cyclohexanone, HPLC grade tetrahydrofuran, diethyl ether were procured from the local suppliers. 2.2. Synthesis and characterization Acrylic copolymers were synthesized by solution polymerization technique using free radical initiator, AIBN (3% based on total monomer weight) and cyclohexanone as a solvent. Fifty percent solution of the monomer in cyclohexanone was used for polymerization. In a three-necked round bottom ask tted with water condenser, thermometer pocket and a Teon stirrer, required quantity of acrylic monomers were charged along with the solvent, initiator and chainterminating agent. The polymerization was carried out at 75 C using water bath. In the second stage, the required quantity of tetrauoro propanoic acid (depending upon the desired extent of esterication) was added along with the esterication catalyst, ptoluene sulphonic acid (PTSA) at 1% concentration based on weight of acid and hydroxyl components. Esterication was carried out at 120 C using cyclohexanone as an azeotropic solvent. The reaction was monitored by water of condensation. Similarly the esterication was also carried out using propanoic acid. The reaction time was around 2 h. The generalized structure of the resins is represented in Fig. 1. The products were analyzed for their hydroxyl value, molecular weight and molecular weight distribution by gel

V.C. Malshe, N.S. Sangaj / Progress in Organic Coatings 53 (2005) 207211 Table 1 Composition of various acrylic copolymers Resins Monomers MMA MHBT-24 MHBP-24 MHBT-26 MHBP-26 MHBT-275 MHBP-275 MHBT-34 MHBP-34 MHBT-36 MHBP-36 MHBT-375 MHBP-375 50 50 50 50 50 50 50 50 50 50 50 50 HEMA 20 20 20 20 20 20 30 30 30 30 30 30 BA 30 30 30 30 30 30 20 20 20 20 20 20 Esterication Acid TFPA PA TFPA PA TFPA PA TFPA PA TFPA PA TFPA PA % 40 40 60 60 75 75 40 40 60 60 75 75 Mola 51.1 50.3 26.1 43.8 16.3 21.3 58.7 69.5 36.6 45.7 20.3 33.9 6536 6445 6625 6640 6691 5784 5746 6180 6670 6500 6666 6296 OH valueb Mn

209

Mw /Mn

2.00 1.75 1.95 1.82 1.82 1.73 1.93 1.85 1.98 1.86 1.98 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-tetrauoro propanoic acid; PA: propanoic acid. a Based on mole of HEMA. b mg of KOH per g resin.

permeation chromatography (GPC). For GPC, tetrahydrofuran was used as an elutant. Shodex polystyrene (Polymer Laboratories, UK) was used as a standard for calibrating the column. The column used was Hibar RT250-7 Lycrogel PS400 (Merck-make) having L/D of 250 mm 7 mm and particle size of 5 m. Fluoride content of the resins was found by the following method [16]. Known weight of the resin was mixed with the excess anhydrous sodium carbonate and heated at 800 C for 8 h in the furnace. On cooling the incinerated product was dissolved in water and liquor ammonia was added to make the solution more basic and to avoid formation of gel-like solution. The content was then heated to boiling for 15 min. The content was cooled and calcium chloride was added to convert sodium uoride to calcium uoride. The solution was ltered to separate the solid calcium uoride. The product was incinerated at 750 C in the furnace for 4 h and weighed after cooling. From the amount of calcium uoride formed uorine content was calculated after correcting for the solubility of calcium uoride in aqueous solution (Solubility of CaF2 in water is 16 mg/lit corresponding to 10 mg/lit as uoride). The theoretical uorine content was calculated from the composition of the copolymer. Table 1 shows composition and properties of various acrylic copolymers synthesized. Table 2 shows the uorine content of the resins.

2.3. Testing of resins The resins were tested for their mechanical and optical properties as per ASTM standards [17]. For testing the properties of coatings like corrosion protection, scratch hardness and falling weight impact resistance, mild steel panels of 15 cm 7.5 cm were used. The panels were abraded with emery paper no. 60 followed by cleaning with the solvents xylene and acetone. The resins were cured with stoichiometric quantity of butylated melamine formaldehyde resin at 135 C for 15 min. Since non-uorinated resins showed non-wetting behaviour, 0.1% (w/w) of commercial urethane-based wetting agent W$D1070 (K-Tech India (P) Ltd., Thane) dissolved in methyl ethyl ketone was mixed with the resin solution for all the compositions before applying on the panels by leveling technique. The solid content of the resin solution was maintained at 30% by diluting with cyclohexanone. Other properties like gloss, exibility, cross-hatch adhesion, pencil harness and solvent resistance were tested on aluminium panels. All the uorinated resins were dark colored as compared to their non-uorinated counterparts. Dry lm thickness of the coatings (DFT) was measured by using magnetic DFT meter on mild steel panel. Pencil hardness of the coatings was determined using standard pencils of hardness of 6B to 5A. Impact resistance was measured by using falling weight
Table 2 Fluorine content of the resins Resin % Fluorine content Theoretical MHBT-24 MHBT-26 MHBT-275 MHBT-34 MHBT-36 MHBT-375 4.48 6.28 7.77 6.16 8.78 10.59 Experimental 4.1 6.1 7.5 6.1 8.7 10

Fig. 1. Molecular structure of uorinated acrylic copolymers.

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impact tester having a load of 1 kg. Flexibility of the coatings was tested on a conical mandrel of 383 mm diameter size and the panels were inspected for cracks or delamination after bending. Adhesion was determined by using cross-hatch adhesion test. Specular gloss of the coatings was measured by using Gardner Glossometer at an angle of 45 . The solvent 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, the panels were exposed in humidity chamber, which was essentially salt spray chamber except that the salt solution was replaced by deionised water. Humidity inside the cabinet was 84% RH at 30 C. In the present study the clear coats have been investigated on metal panels without any prior surface treatments and hence the failure is much earlier compared to the conventional coatings. In any protective coating, the volume concentration of resin is 50% or more (up to 85%
Table 3 Mechanical properties of coatings Resins Properties Film thickness (ASTM D1186-93) ( m) Pencil hardness (ASTM D3363-74) Flexibility (conical mandrel) (ASTM D522-93a)

in the case of electrodeposited ED primers) and this is the main component with high diffusivity for oxygen and water. Pigments being impervious in nature, extend the barrier properties of the polymer by providing tortuous path to the diffusing molecules. No pigments were therefore used. The panels were checked for corrosion by visual inspection regularly.

3. Results and discussion The properties of all the clear coatings are given in Tables 3 and 4. It can be seen that the falling weight impact and exibility were not affected by introduction of uorine. All the lms showed good pencil hardness but some uorinated lms showed less scratch hardness. Other properties like adhesion, gloss were more or less the same. The coatings showed good gloss. MEK and xylene rub tests showed loss of

Scratch hardness (gm) (ASTM D2197-98)

Cross-hatch adhesiona (ASTM D 3359-83)

Impact resistance (ASTM D2794-84) Direct (0.6 Kg m) Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Indirect (Kg m) 0.55 0.55 0.55 0.55 0.55 >0.60 0.55 0.55 0.55 0.55 >0.60 >0.60

MHBT-24 75100 MHBP-24 75100 MHBT-26100150 MHBP-26100150 MHBT-27575100 MHBP-27575100 MHBT-34100150 MHBP-34100150 MHBT-36100150 MHBP-36 75100 MHBT-37575100 MHBP-37575100

2H 2H 2H 2H 2H 2H 2H 2H 2H 2H 2H 2H

Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes

700 1100 700R 1400R 600R 1000R 500R 1200R 500R 1000 300R 1100

Good Good Good Good Good Good Good Good Good Good Good Good

R: failed in the reverse travel of the test panel. a Good: the lm was intact. Table 4 Optical, chemical and protective properties of coatings Resins Properties Gloss @45 (ASTM D523-67) Solvent resistance (ASTM D5402-93) Xylene rub test MHBT-24 MHBP-24 MHBT-26 MHBP-26 MHBT-275 MHBP-275 MHBT-34 MHBP-34 MHBT-36 MHBP-36 MHBT-375 MHBP-375
a

Corrosion testa (h)

MEK rub test 100 100+ 70 100 100 100 100 100+ 70 100 100 100 41 21 41 21 54 21 44 21 44 21 54 21

52 59 63 50 47 56 54 58 58 58 58 45

100 100 100 100 100 100 100 100 100 100 100 100

Exposed to deionised water in humidity chamber at 84% RH and 30 C.

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gloss for both types of resins. However, the most noticeable difference was observed in case of their corrosion protective ability. Fluorinated lms showed better corrosion protection against corrosion than their non-uorinated analogs. Addition of uorine in a range 410% showed improvement of the protective properties signicantly. Air-drying alkyl coatings cured on these uorinated coatings could be peeled off from the surface thus making them suitable in anti-grafti paints. Amount of crosslinking agent used (510%) in this study was much less than that is used in conventional coatings, which is 2030% of the binder. So the mechanical properties of the coatings can be still improved. These uorinated binders can be used as a base coat, which can restrict the moisture from reaching the metal surface leading to a longer life of the coatings.

4. Conclusion An easy and low cost procedure of introducing uorine atoms in acrylic polymers was adopted to prepare uorinated polymers. Introduction of uorine in the range of 410% was found to enhance corrosion protection ability of coatings. This technique can be extended to any other resin systems involving esterication reaction by suitably increasing the polyol content. Polyesters for powder coatings, polyester polyols for polyurethanes can be expected to produce products with improved performance.

Acknowledgements Authors thank Dr. S.S. Laddha of M/s. Winner Impex (P) Ltd., Mumbai and K-Tech India (P) Ltd., for gifting sodium tetrauoropropionate and wetting agent, respectively. Authors are also grateful to Department of Science and Technology (DST), India and University of Grant commission (UGC), India for funds. References
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