Printer Friendly

Synthesis and evaluation of tetra(2,7-octadienyl) titanate as a reactive diluent for air-drying alkyd paints.

[C] ACA and OCCA 2010

Abstract Environmental regulations are forcing the reformulation of many decorative and protective coatings systems. In particular, air-drying solventborne alkyd paints need to meet increasingly stringent emission limits and often must be reformulated with suitable exempt solvents or reactive diluents to achieve volatile organic compound (VOC) reduction. In the research summarized in this article, a new reactive diluent, tetra(2,7-ocladienyl) titanate, was synthesized and evaluated in alkyd formulations for VOC reduction and property enhancement. A soy-based long-oil alkyd resin; a soy-based high-solids, long-oil alkyd resin; and a linseed-based, high-solids long-oil alkyd resin were evaluated in combination with the new reactive diluent at weight percentages ranging from 10% to 50%. Characterization included measuring viscosity, film dry times, and film performance of the reactive diluent formulations in comparison to neat alkyd resins used as control. The tetra(2,7-octadienyl) titanate formulations consistently exhibited reduced viscosities and dry times as a function of concentration. The resulting films were harder and more thoroughly cured than the control systems.

Keywords Alkyd, Reactive diluent, Tetra(2,7-octadienyl) titanale, Air drying

Introduction

Solvents in the coatings industry have been flagged as causes for air pollution and ozone layer depletion. This has resulted in environmental legislation for the limitation of allowable volatile organic compounds (VOCs) in air-drying commercial coatings. (1-3) In response, high-solid alkyd coatings have been developed for decorative markets with performance properties similar to those of conventional paints. (4) High-solid formulations employ lower molecular weight resins for viscosity reduction; however, this results in reduced drying performance. (5) In alkyds, increasing the oil length in the system generally results in reduced DP of the polymer and increased plasticization, resulting in reduced resin viscosity. However, the shorter primary polyester chain length leads to reduced hydrogen bonding and poor mechanical properties. (4) As an alternate route, the solvent can be partially replaced by a reactive diluent, thus retaining the resin molecular weight and increasing the solids content of the formulation. (4), (6-9) Reactive diluents function as a solvent during coating processing and application, but are not considered VOCs as they are converted into an integral part of the film during the curing/drying process. (6), (7)

In many cases, reactive diluents used in the formulation of high-solid coatings have resulted in reduced performance. For example, fatty acid esters were reported to possess lower dilution efficiency than while spirit and added extra sensitivity to wrinkling. (8-10) Acryloyl functional oligomers reportedly cause instabilities during storage and butadiene-based oligomers lead to early embrittlement during aging and weathering. (11) It is reported that allyl ethers exhibit emission of toxic fragments during drying. (12) Properties for an ideal reactive diluent include low intrinsic viscosity, good compatibility with alkyd resins, no evaporation during drying, and accelerated dry time. At the same time, the reactive diluent should not cause detrimental effects in film properties or reduce [T.sub.g]. Oxidatively curing reactive diluents react similarly to air-drying alkyds. (13-17) The crosslinking mechanism involves hydrogen abstraction from allylic methylene groups by oxygen in the presence of metal catalysts, yielding a resonance-stabilized radical which further reacts with oxygen to form a hydroperoxide. (18-24) The resulting hydroperoxide is degraded by metal catalysts into radicals and reacts with the double bonds in the resin to produce chemical crosslinking. (7) For this reason, a suitable reactive diluent for air-drying alkyd paints should possess an allylic methylene group as a reactive site for efficient oxidative curing. (6) The functional groups within the reactive diluent have major effects on its reactivity. For example, methylene sites in allylic alcohol esters have been found to be less reactive than those in allylic alcohol ethers. (6) In addition, successful reactive diluents should possess a large number of reactive sites while maintaining low viscosity. The central assembly unit approach, which involves connection of more than one reactive site to one center, has been utilized to achieve these properties. (6) Using this approach, a range of reactive diluents with varying numbers of arms have been synthesized and evaluated for their potential as reactive diluents for air-drying, high-solids alkyd formulations. (25-30)

A new reactive diluent, tetra(2,7-octadienyl) titanate, is proposed for air-drying, high-solid alkyd paints. Tetra(2,7-octadienyl) titanate was synthesized through ether exchange reaction between tetraethyl titanate and 2,7-octadienol. Characterization included proton nuclear magnetic resonance spectroscopy ([.sup.1]H-NMR), carbon nuclear magnetic resonance spectroscopy ([.sup.13]C-NMR), and Fourier transform infrared spectroscopy (FTIR). The resulting reactive diluent was evaluated in three alkyds, soy-based long-oil alkyd (70% solids) (Alkyd 1), soy-based long-oil, high-solid alkyd resins (92% solids) (Alkyd 2), and linseed-based long-oil, high-solid alkyd (100% solids) (Alkyd 3). Formulations were performed, both with and without metal driers, to determine reactive diluent influence on the alkyd resin system in terms of viscosity, dry time, and film properties. Properties are compared to those of controls formulated with tert-butyl acetate, a typical solvent used in low VOC formulations.

Material and methods

Materials

All reagents were used without further purification unless otherwise mentioned. Titanium(IV) ethoxide was purchased from Sigma Chemical Co. (technical grade). 2,7-Octadienol was purchased from TCI America (95%) and distilled over calcium hydride before use. Samples of Beckosol [R] 10-060 (soy-based, long-oil alkyd resin) and Beckosol 10-539 (high-solid, long-oil alkyd resin) were provided by Reichhold. Cook Composites and Polymers provided a sample of ChemPol [R] 801-2164 (linseed-based, 100% solid alkyd). tert-Butyl acetate (TBA) (99%) was donated by Ashland Inc. Zirconium (24%), calcium (5%), and cobalt (12%) metal driers were donated by OMG Americas, Inc. Sodium hydroxide, sulfuric acid, methyl ethyl ketone (MEK), and ethanol were purchased from Fisher Scientific.

Instruments

A Varian 200 MHz NMR equipped with a standard 5 mm [.sup.1]H/[.sup.13]C probe was utilized to identify the structure of tetra(2,7-octadienyl) titanate. Samples were prepared at 5 wt% in deuterated chloroform ([CDC1.sub.3]) containing 0.03 vol% tetramethylsilane (TMS) as an internal standard. [.sup.1]H NMR spectra of reactive diluent samples were obtained from 256 scans with a relaxation delay of 1 s and a pulse angle of 45 degrees. Viscosity measurements were performed at 25[degrees]C using a Brookfield CAP 2000+L viscometer (cone and plate rotational viscometer) equipped with a spindle #3. A Mettler-Toledo ReactIR [TM] 4000 Fourier transform infrared spectrometer (RT-FTIR) was utilized to monitor the reactive diluent synthesis.

Synthesis of tetra(2,7-octadienyl) titanate

In a typical process to form an allylic titanate, an allylic alcohol is reacted with titanium tetravalent salt, where the suitable ligands are selected from alkoxides. In general, alkoxides can be easily exchanged with an allylic alcohol under suitable reaction conditions. (6) Preferably, the initial ligand is removed from the reaction system as free alcohol, which drives the exchange reaction to completion. (6) For this purpose, titanium(IV) ethoxide was chosen as the titanium tetravalent salt, where ethoxide ligands were substituted with 2,7-octadienol under an inert and dry atmosphere.

Prior to synthesis, 2,7-octadienol was vacuum distilled over CaH. Titanium(IV) ethoxide (1 mol) was mixed with distilled 2,7-octadienol (4.1 mol) under inert atmosphere. The reaction medium was adjusted to 80[degrees]C for 2 h and then to 100[degrees]C for 6 h. Evolved ethanol was captured via distillation during the reaction. The temperature was then increased to 130[degrees]C for 2 h. Completion of the reaction was accomplished by maintaining the mixture at reduced pressure (20 mbar) for 4 h at 100[degrees]C. The resulting product was pale yellow in color and characterized using [.sup.1]H, [.sup.13]C NMR, and RT-FTIR. A yield of 90% was calculated based on the molar production of distilled ethanol before vacuum application.

The structure was confirmed through [.sup.1]H NMR (Fig. 7, Appendix) and [.sup.13]C NMR (Fig. 8, Appendix) analyses. Proton NMR signals are assigned as -[OCH.sub.2] a (4.8 ppm), double bond proton b (5.6 ppm), double bond proton c (5.7 ppm), double bond proton g (5.8 ppm), double bond proton h (5.0 ppm), double bond proton i (4.9 ppm), multiplet -[CH.sub.2] protons d (2.0 ppm), multiplet -[CH.sub.2] protons e (1.5 ppm), and multiplet -[CH.sub.2] protons f (2.1 ppm). The integration value (7) of proton resonances appearing between 6.0 and 4.6 ppm matches the number of protons which correspond to a, b, c, g, h, and i (7 protons). The integration value of proton resonances appearing between 2.2 and 1.2 ppm matches the number of protons corresponding to d, e, and f units (6 protons). The good match of integration values with the number of protons in each unit indicates near-complete conversion for the reaction.

The [.sup.13]C NMR spectrum signals are assigned as double bond carbon g (139 ppm), double bond carbons h (114 ppm), double bond carbon b (132 ppm), double bond carbon c (131 ppm), -[CH.sub.2] carbon next to oxygen a (34 ppm), -[CH.sub.2] carbon d (29 ppm), -[CH.sub.2] carbon f (32 ppm), and -[CH.sub.2] carbon e (27 ppm).

Alkyds' formulation

The three alkyds were diluted with reactive diluent at weight percentages of 10%, 20%, 30%, 40%, and 50%. Metal driers were added at levels varying from 0% to 2% (Table 1). A typical commercial metal drier package was employed in these formulations for comparison purposes. In addition, tert-butyl acetate was incorporated at weight percentages of 10%, 20%, and 30%.
Table 1: Alkyd types and metal driers weight percent in formulations

Alkyd    Oil type  Percent solid (%)  Cobalt (%)  Calcium  Zirconium
                                                  (%)      (%)

Alkyd 1  Soya                  69-71        0.20     0.45       0.25

Alkyd 2  Soya                  88-92        0.70        -       1.10

Alkyd 3  Linseed                 100        0.03     0.20       0.50


Dry time measurements

Alkyds (with and without metal driers) diluted with both reactive diluent and tert-butyl acetate were drawn on Q-panels at 6 mils wet film thickness. Set-to-touch dry times were evaluated via ASTM D 1040-95 at ambient temperature.

Film properties' measurements

A preliminary scanning study using pencil hardness as the criteria was conducted to determine the optimum reactive diluent--alkyd concentration. Two Q-panels for each alkyd solution (with and without metal driers) were drawn at 6 mils wet film thickness. One of the panels was heat dried at 100[degrees]C for 1 h. The other panel of each set was air dried. The panels were visually observed, and pencil hardness tests (ASTM D 3363-00) were performed after 10 days. It was noted that pencil hardness increases with concentration of the reactive diluent, and that heat drying and addition of metal driers resulted in improved pencil hardness (Table 2). Based on these results, heat-dried 30% reactive diluent--alkyd systems with metal driers were selected for further evaluation.
Table 2: Pencil hardness test on alkyd reactive diluent mixture
(after 10 days)

Alkyd         5%   10%  15%  30%  Control
AD M Alkyd 1  HB   HB   HB   H    7B
AD N Alkyd 1  HB   HB   B    B    Tacky
HD M Alkyd 1  H    H    H    H    7B
HD N Alkyd 1  HB   B    B    B    <9B
AD M Alkyd 2  F    H    H    H    8B
AD N Alkyd 2  B    9B   3B   HB   Tacky
HD M Alkyd 2  H    H    H    H    8B
HD N Alkyd 2  B    B    B    B    Tacky
AD M Alkyd 3  <9B  2B   HB   HB   <9B
AD N Alkyd 3  2B   B    B    B    3B
HD M Alkyd 3  <9B  HB   HB   H    <9B
HD N Alkyd 3  HB   HB   HB   HB   <9B

HD = heat dried; AD = air dried; M = with metal drier;
N = neat (without metal drier)


The formulations containing 30% reactive diluents and 0-2% metal driers were prepared. Films were drawn at 6 mils wet film thickness on Q-panels for each of the 17 samples (3 control neat alkyd samples plus 14 formulations). Panels were then heat dried for 1 h at 100[degrees]C and air dried for 10 days before testing. This drying procedure was employed to comply with the ASTM test protocol (ASTM D 1040-95) for standardized equilibration time prior to testing. The formulations were tested as follows:

* Pencil hardness (ASTM D 3363-00)

* Mandrel bend (ASTM D 522-93a)

* Impact resistance (ASTM D 2794-93)

* Adhesion (ASTM D 3359-02)

* Chemical resistance (ASTM D 1308-02)

* Solvent cure test (PCI-8) (31)

Results and discussion

Synthesis of tetra(2, 7-octadienyl) titanate

Tetra(2, 7-octadienyl) titanate was synthesized as shown in Fig. 1. Conversion was calculated based on the ethanol distilled from the reaction vessel. The resulting product was pale yellow with a 90% yield. The removal of residual solvent from the reaction medium was accomplished through vacuum distillation. Ethanol-2, 7-octadienol mixture was collected during the vacuum process until the termination of the reaction. The reaction conversion was also qualitatively monitored via Real Time-FTIR (Fig. 2). The absorbance between 3100 and 3600 [cm.sup.-1], attributed to the -OH stretching of 2, 7-octadienol, decreased sharply over 12 h. The presence of unreacted 2, 7-octadienol was confirmed after the 12-h reaction via FTIR; no evidence of residual alcohol was observed via [.sup.1]H and [.sup.13]C NMR.

[FIGURE 1 OMITTED]

[FIGURE 2 OMITTED]

Viscosity of reactive diluent-alkyd formulations

The viscosity of the reactive diluent--alkyd mixtures, with and without metal driers, was evaluated using cone and plate viscometry. The first group of formulations was prepared from Alkyd 1 and Alkyd 2 in the presence of metal catalyst at weight percentages of 10%, 20%, and 30% reactive diluent. Figure 3 shows the viscosity change of the formulations as a function of shear rate. The 10% formulation exhibits shear thinning behavior as a function of shear rate while 20% and 30% formulations exhibit more Newtonian viscosity behavior. In general, viscosity decreases with increasing titanate concentration, particularly at low shear rates. Figure 4 shows viscosity behavior of formulations diluted with TBA at the same percentages. Similar trends were observed, but substantially larger decreases in viscosity were obtained, as TBA is a much lower viscosity additive than the reactive diluent. In order to achieve similar reductions in viscosity as those achieved with TBA, approximately double the wt% loading of titanate is required.

[FIGURE 3 OMITTED]

[FIGURE 4 OMITTED]

The second group of formulations was prepared from Alkyd 1, Alkyd 2, and Alkyd 3 resins without metal driers at weight percentages 0%, 10%, 20%, 25%, 30%, 35%, 40%, and 50% tetra(2,7-octadienyl) titanate. Figure 5 depicts the viscosity change of these formulations as a function of shear rate. Similar trends are observed in the non-metal drier containing formulations, with a general decrease in viscosity as a function of increasing titanate loading. Low loading levels exhibited shear thinning behavior while higher loadings resulted in Newtonian viscosity. Tetra(2, 7-octadienyl) titanate behaves as an effective viscosity reducer; however, higher concentrations are required to achieve viscosity behavior similar to that achieved with TBA.

[FIGURE 5 OMITTED]

Drying performance of reactive diluent--alkyd formulations

The dry time results for tetra(2,7-octadienyl) titanate--alkyds (Alkyd 1 and Alkyd 2) and TBA--alkyds (Alkyd 1 and Alkyd 2) formulations (10%, 20%, 30%, and 50%) including metal driers are provided in Table 3. In all the cases, tetra(2,7-octadienyl) titanate formulations exhibited significantly reduced dry times in comparison to the TBA formulations. Most notably, extremely low set-to-touch times were observed for 30% and 50% reactive diluent formulations for both alkyds, demonstrating the ultra-fast curing properties of the titanate as a reactive diluent. While TBA proves to be a more effective viscosity modifier, its formulations show substantially longer dry limes than those diluted with the reactive titanate.
Table 3: Set-to-touch dry times of alkyds blended with metal driers

RD%  Alkyd 1/      Alkyd 2/      Alkyd 1/ TBA (b)  Alkyd 2/ TBA
     Titanate (a)  Titanate (a)  (min)             (b) (min)
     (min)         (min)

10             97           207               410           306

20             48            63               390           201

30              9            15               360           139

50              8             9                 -             -

(a) Alkyds diluted with tetra(2,7-octadienyl) titanate

(b) Alkyds diluted with tertbutyl acetate


Drying properties of tetra(2, 7-octadienyl) titanate--alkyds (Alkyd 1, Alkyd 2, and Alkyd 3) were also studied in formulations containing no metal driers (Table 4). As in the metal drier-containing formulations, dry times decrease dramatically with increasing reactive diluent concentration. The metal driers appear to have little effect on the dry times of the reactive diluent formulations, as the differences in measured set-to-dry times are within the expected experimental error of the measurement (i.e., comparison of the first two columns of Tables 3 and 4). Linseed oil-based alkyd mixtures (Alkyd 3) showed longer dry times than soy-based alkyd mixtures. In spite of the longer dry time for the linseed oil alkyds, the systems with reactive diluents dried to set-to-touch levels at a much faster rate than the technical data sheet values for the neat linseed oil Alkyd 3 (5-6 h).
Table 4: Set-to-touch dry time of alkyds diluted with tetra
(2,7-octadienyl) titanate, without metal driers

RD%  Alkyd 1 (min)  Alkyd 2 (min)  Alkyd 3 (min)

10             115            180              -
20              53             60              -
30               8             12            135
40               7              8             53
50               6              6             40


The extremely low dry times exhibited by tetra(2, 7-octadienyl) titanate-containing formulations result from the high reactivity and functionality of the reactive diluent. Drying proceeds through the oxidative crosslinking mechanism described in "Introduction." In the design of this reactive diluent, titanium was chosen as the central transition metal atom for its high electronegativity, which increases the reactivity of the allylic methylene groups, and its tetravalent character, which enables an increase in the number of reactive sites without excessive increase in the viscosity of the formulation. Figure 6 shows the structure of tetra(2,7-octadienyl) titanate with identification of the reactive sites. The molecule includes four allylic ether groups (a), with methylene hydrogens which serve as good initiation sites, (6), (32) four allylic olefin groups (b) which are polymerizable groups, and four terminal olefin groups (c) which provide additional reactivity. (6) This reactive diluent also possesses eight additional allylic methylene groups, providing further initiation sites to increase rates of crosslinking. Moreover, the central titanium atom may act as metal drier, providing self-catalytic properties to the reactive diluent. Tetra(2, 7-octadienyl) titanate also can undergo both homopolymerization and copolymerization with the alkyd resins through its polymerizable olefin sites (b).

[FIGURE 6 OMITTED]

Mechanical properties of air-cured tetra(2, 7-octadienyl) titanate--alkyd films

Physical property results are shown in Table 5. Note that although metal driers showed little effect on the dry times for reactive diluent formulations, they showed increased pencil hardnesses (Table 2), and so they were included in the formulations used for mechanical property testing. Addition of reactive diluents with the metal driers resulted in films with improved pencil hardness compared to the controls. All films passed the mandrel bend test indicating good flexibility. Impact resistance properties, however, decreased for reactive diluent-based films as compared to the controls. All films were relatively soft, based on the pencil hardness tests, and all films displayed increased hardness with reactive diluent. Adhesion was poor in both reactive diluent and control films, and this could be a contributing factor to the low impact values. Solvent cure tests showed that the extent of cure, i.e., crosslink density vs time, is improved in all reactive diluent-alkyd mixtures relative to controls. These results validate that the reactive diluent plays a role in increasing chemical crosslinking between alkyds and is incorporated throughout the polymer network of the dried alkyd films.
Table 5: Mechanical properties of films of 30% reactive diluent
(RD)-metal driers (MD)-alkyd mixture

Test                   Alkyd 1   Alkyd 2       Alkyd 3

Pencil     RD + MD +   B         2B            B
Hardness   Alkyd

           Neat Alkyd  4B        <6B           <6B

Mandrel    RD + MD +   Pass      Pass          Pass
Bend Test  Alkyd

           Neat Alkyd  Pass      Pass          Pass

Impact     Direct      80 in-lb  60 in-lb      140 in-lb

           Neat Alkyd  > 160     80 in-lb      >160 in-lb
                       in-lb

           Reverse     80 in-lb  50 in-lb      120 in-lb

           Neat Alkyd  >160      60 in-lb      140 in-lb
                       in-lb

Solvent    RD + MD +   64        109 (partial  156 (cure coating)
Cure       Alkyd       (partial  cure)
                       cure)

           Neat Alkyd  26        48            53

Adhesion   RD + MD +   0B        0B            1B
           Alkyd

           Neat Alkyd  1B        0B            0B


Chemical resistance of air-cured tetra(2,7-octadienyl) titanate-alkyd films

The chemical resistance values of the ambient-cured reactive diluent-alkyds are exhibited in Table 6. All reactive diluent-alkyds and controls were affected by exposure to basic solution. The reactive diluent film from Alkyd 1 and its control were not affected by exposure to acidic solution, while other formulations showed greater effects. Only the Alkyd 2 film was affected by ethyl alcohol. In general, the reactive diluent formulations exhibited chemical resistance similar to that of the standards. Although water resistance was not evaluated in this study, titanium alkoxides are known to be water sensitive. They are susceptible to degradation to the point of formation of insoluble hydrated titanium dioxide ([TiO.sub.2]) and four equivalents of 2,7-octadienol solvent. Formation of [TiO.sub.2] results in increased cure rates, comparable to those observed with commercial metal driers. (32)
Table 6: Chemical resistance of films of 30% reactive diluent--metal
driers--alkyds

Solvent                 Alkyd 1         Alkyd 2        Alkyd 3

2N NaOH                 Film dissolved  Film           Film
                                        dissolved      disintegrated

Neat Alkyd              Film dissolved  Yellow         Film
                                        discoloration  dissolved

2N [H.sub.2][SO.sub.4]  No effect       Slightly       Dark
                                        lighter        discoloration

Neat Alkyd              No effect       No effect      Dark
                                                       discoloration

[C.sub.2][H.sub.5]OH    No effect       Slight         No effect
                                        discoloration

Neat Alkyd              Slight bottle   No effect      No effect
                        ring


Conclusions

Herein, we report the synthesis of a new reactive diluent, tetra(2,7-octadienyl) titanate, which was characterized via [.sup.1]H NMR, [.sup.13]C NMR, and FTIR. The resulting alkyd-reactive diluent formulations exhibited low viscosities and extremely low dry times in comparison to neat alkyd resins. Their films yielded superior hardness and ultra-fast oxidative curing. The results indicate the potential utility of this compound to achieve lower VOC formulations with equivalent performance properties.

Acknowledgments The authors gratefully acknowledge the support of Noetic Technologies, Inc. This study was also partially supported by the RET program of the National Science Foundation under Award Number EEC-0602032.

Appendix

See Figs. 7 and 8.

[FIGURE 7 OMITTED]

[FIGURE 8 OMITTED]

References

(1.) Zabel, KH, "Characteristics of Air-Drying High-Solid Alkyd Paints." Polym. Paint Colour J., 178 526-529 (1988)

(2.) Proposal for a Council Directive on Limiting the Content of Volatile Organic Compounds in Decorative and Architectural Pints and in Cleaning Agents, Fillers, Primers, and Paints, Used in the Vehicle Refinishing Industry, CEPE, May 1996

(3.) Proposal for a Council Directive on Limiting the Content of Volatile Organic Compounds Owing to the Use of Organic Solvents in Certain Industrial Activities. EC OJ, C99 26.3.1997, p. 32

(4.) Lindeboom, J, "Air-Drying High Solids Alkyd Pants [Paints] for Decorative Coatings." Prog. Org. Coat., 34 147-151 (1998)

(5.) Holmberg, K, High Solid Alkyd Resins, p. 25. Marcel Dekker, New York (1987)

(6.) Zabel, KH, Klaasen, RP, Muizebelt, WJ, Gracey, BP, Hallett, C, Brooks, CD, "Design and Incorporation of Reactive Diluents for Air-Drying High Solids Alkyd Paints." Prog. Org. Coat., 35 255-264 (1999)

(7.) Muizebelt, WJ, Hubert, JC, Nielen, MWF, Klaasen, RP, Zabel, KH, "Crosslink Mechanisms of High-Solids Alkyd Resins in the Presence of Reactive Diluents." Prog. Org. Coat., 40 121-130(2000)

(8.) Muturi, P. Wang. D, Dirlikov, S, "Epoxidized Vegetable Oils as Reactive Diluents, II, Comparison of Vernonia, Epoxidized Soybean, and Linseed Oils." Prog. Org. Coat., 25 85-94 (1994)

(9.) Stenberg, C, Swensson, M. Wallstrom, E, Johanssson, M, "Drying of Linseed Oil Wood Coatings Using Reactive Diluents." Surf. Coat. Int. Part B: Coat. Trans., 88 119-126 (2005)

(10.) Samuelsson, J, Sundell, PE, Johansson, M, "Synthesis and Polymerization of a Radiation Curable Hyperbranched Resin Based on Epoxy Functional Fatty Acids," Prog. Org. Coal., 50 193-198 (2004)

(11.) Dhein, R, Eimers, E, Renter, K, Ruf, G, "Forschungsbericht T85-005: Neue Oxidative Vernetzende Lacksystemen Mit Hohem Festkorpergehalt." Bundes-ministerium fur Forschung and Technologie, January 1985.

(12.) Toivonen, H, "Block Resistant Gloss Emulsion Paint Based on Air-Drying Amino Resin," J. Oil Colour Chemists' Assoc., 8 213-217 (1984)

(13.) Markey, KS, Fatty Acids. Part 2, p. 1399. Interscience Publishers Inc., New York (1961)

(14.) Jones. FN (ed.), "Alkyd Resins." In: Ullman Encyclopedia of Industrial Chemistry, Vol. A1, p. 409. VCH Wiley, Verlag GmBH (1985)

(15.) Frankel, EN, Lipid Oxidation. The Oily Press Ltd., Dundee, Scotland (1998)

(16.) Frankel, EN, Neff, WE, Rohwedder, WK. Khambay, BPS, Garwood, RF. Weedon, BCL, "Analysis of Autoxidized Fats by Gas Chromatography--Mass Spectrometry; III. Methyl Linolenate." Lipids, 12 1055-1061 (1977)

(17.) Muizebelt, WJ, Hubert, JC, Venderbosch, RAM, "Mechanistic Study of Drying of Alkyds Resins Using Ethyl Linoleate as a Model Substance." Prog. Org. Coat., 24 263-279 (1994)

(18.) Hartshorn, JH, "Time-Lapse Infrared Spectroscopic Investigation of Alkyd and Lindeed Oil Cure." J. Coat. Technol., 54 53-61 (1982)

(19.) Salazar-Rojas, EM, Urban, MW, "Curing of Non-Pigmented Alkyd Coalings Detected by In Situ Photoacoustic Fourier Transform Infrared Spectroscopy (PAFT-IR)." Prog. Org. Coat., 16 371-386 (1989)

(20.) Hubert, JC, Venderbosch, RAM, Muizebelt, WJ, Klassen, RP, Zabel, KH, "Mechanistic Study of Drying of Alkyd Resins using (Z,Z)- and (E.E)-3.6-Nonadiene as Mosel Substances." Prog. Org. Coat., 31 331-340 (1997)

(21.) Porter. NA, Weber, BA, Weenen, H, Khan, JA, "Autoxidation of Polyunsaturated Lipids. Factors Controlling the Stereochemistry of Product Hydroperoxides." J. Am. Chem. Soc., 102 5597-5601 (1980)

(22.) Porter, NA, Lehman, LS, Weber, BA, Smith, KJ, "Unified Mechanism for Polyunsaturated Fatty Acid Auxidation. Competition of Peroxy Radical Hydrogen Atom Abstraction. Beta-Scission, and Crystallization." J. Am. Chem. Soc., 103 6447-6455 (1981)

(23.) Porter, NA, Wujek, DG, "Autoxidation of Polyunsaturated Fatty Acids, an Expanded Mechanistic Study." J. Am. Chem. Soc., 106 2626-2629 (1984)

(24.) Muizebelt, WJ, Hubert, JC, Venderbosch, RAM, Lansbergen, AJH, Klaasen, RP, Zabel, KH, "Aluminum Compound as Additional Crosslinkers for Air-Drying High Solids Alkyd Paints." J. Coat. Technol., 70 53-59 (1998)

(25.) Enomoto, S. Nishida, HTS, Wada, H, Mukaida, Y, Yanaka, M, "Study of Reactive Diluent for Air-Drying Alkyd Paint." J. Appl. Polym. Sci., 22 253-265 (1978)

(26.) Milligan, CL, Ward, RJ, Martin, RA, "Hexadienol and Hexadienal Derivatives. Useful as Reactive Diluents in Drying Oil Coatings." US Patent 3,529,389, 1970

(27.) Johnson. NW, "Allyl Ether-Esters as Reactive Diluents for Coating Compositions." GB Patent 2,190,672, 25, 1987

(28.) Hofland, A, "Reactive Diluent for Paint Compositions." EP Patent 0,357,128, A1, 1989

(29.) Hoehlein, P. Meixner, J. Pedain, J, "Use of Octadienyl Ethers as Reactive Diluents." EP Patent 0,546,417 A1, 1993

(30.) Yamauchi, T, Sato, Y, Koizumi, K, "Alkyd Resin using Mono- and Dioctadienyl Esters of Good Hardness. Water and Alkali Resistance." JP Patent 47045838, 1972

(31.) The Powder Coating Institute, Powder Coating The Complete Finisher's Handbook. 3rd edn., p. 425. Alexandria. VA (2004)

(32.) Gracey, BP, Hatlett, C., "Reactive Diluents, Preparation and Use in Paints." US Patent 20070004825 A1, 2007

A. H. Alidedeoglu, K. Davis. R. Robertson,

C. Smith, J. W. Rawlins, S. E. Morgan ([??])

School of Polymers and High Performance Materials, The University of Southern Mississippi, 118 College Drive, Box 10076, Hattiesburg, MS 39406-0001, USA

e-mail: sarah.morgan@usm.edu

DOI 10.1007/s11998-010-9276-z
COPYRIGHT 2011 American Coatings Association, Inc.
No portion of this article can be reproduced without the express written permission from the copyright holder.
Copyright 2011 Gale, Cengage Learning. All rights reserved.

Article Details
Printer friendly Cite/link Email Feedback
Author:Alidedeoglu, Alp H.; Davis, Kevin; Robertson, Rhonda; Smith, Crystal; Rawlins, James W.; Morgan, Sar
Publication:JCT Research
Date:Jan 1, 2011
Words:4491
Previous Article:Theoretical prediction on double-layer coating in wet-on-wet optical fiber coating process.
Next Article:Preparation of transparent ultrahydrophobic silica film by sol--gel process.
Topics:

Terms of use | Copyright © 2017 Farlex, Inc. | Feedback | For webmasters