Resin intermediates and specialty acids for high performance coatings

Transcription

1 Resin intermediates and specialty acids for high performance coatings Suggested starting point formulations

2 Enabling alkyd resins in coatings for more than 60 years Alkyd resins continue to be one of the most widely used binder systems for preparing high performance coatings for the global market. They are utilized in a large variety of applications as a result of their exceptional formulating versatility, low cost, and ease of application. This versatility originates from the large number of components that can be used for subsequent preparation, including glycols, diacids, fatty acids, naturally derived oils, and the like. Interest in alkyds is experiencing a renaissance mainly due to the sustainability benefits derived from the use of natural oils for resin preparation. The natural oil in alkyds can range range from 5% 85% depending on the type and the specific application of the coating. However, global government regulations are encouraging coatings producers to lower organic solvent levels. This has driven more interest in high-solids alkyds, emulsified alkyds, water soluble/reducible systems, and water-dispersible types. Since the 1950s, has participated in the global alkyd market through product offerings such as NPG glycol, CHDM glycol, and TMPD glycol. These glycols allow formulators to dial in specific properties such as hydrolytic stability, chemical resistance, and low VOC levels. Additionally, offers other components for making high quality alkyd resins such as isophthalic acid, benzoic acid, and a host of refined fatty acids such as Pamolyn 200 linoleic acid. This technical tip highlights the versatility of resin design provided by these components and subsequent performance properties.

3 RAW MATERIAL SUPPLIERS Product 3M Novec Fluorosurfactant FC-4432 BYK -301 additive Fascat 4201 catalyst Fascat 4102 catalyst Fascat 4100 catalyst Ti-Pure R-900 pigment Ti-Pure R-960 pigment CHDM-D90 TMPD glycol Pamolyn 200 NPG glycol n-butanol Isophthalic acid EB solvent MPK (methyl n-propyl ketone) MAK (methyl n-amyl ketone) Exkin 2 antiskinning agent Trimellitic anhydride Liosec HC Cobalt drier, 6% Liosec HC Manganese drier, 6% Pentaerythritol tech-eu Trimethylolpropane Palomar Blue 15:1 ACTIV-8 Drier Accelerator Company 3M Company Altana Arkema Arkema Arkema DuPont Company DuPont Company Elementis Flint Hills Resources Miracema-Nuodex Miracema-Nuodex Perstorp Perstorp Sun Chemical Vanderbilt Minerals

4 Table 1 shows three air-drying alkyd starting point resin formulations. Resin WA-17-2T is a two-stage waterreducible resin based on TMPD glycol, isophthalic acid, and Pamolyn 200. Pentaerithitol and TMA serve as branching agents for the formulation. Resin WA-17-6C is also a two-stage water-reducible type based on CHDM-D90 glycol, isophthalic acid, benzoic acid, and Pamolyn 200. Pentaerithitol and TMA are the branching agents used in this formulation as well. Resin HA-9-1N is a three-stage resin synthesis for a high-solids, solvent-based coating. It contains NPG glycol, isophthalic acid, and Pamolyn 200 in combination with trimethylolpropane (TMP) and trimellitic anhydride (TMA) to impart polymer branching. It should be noted the three resins highlighted differ by glycol type and brancher package. Synthesis of these resins is accomplished by using typical polyesterification equipment as found in publication N-345.

5 Table 1 Alkyd resin compositions RESIN COMPOSITION Component Formulation WA-17-2T Formulation WA-17-6C Formulation HA-9-1N 1st Stage Pamolyn TMPD CHDM D Trimethylolpropane Pentaerythritol Benzoic acid Isophthalic acid nd Stage NPG Isophthalic acid Trimellitic anhydride rd Stage Trimellitic anhydride Reactor charge, g Thero. H 2 AN, g Resin yield, g Catalyst 6.4 g Fascat g Fascat g Fascat 4102 Processing parametersᵃ 1st Stage processing temperature, C st Stage acid number 20 <10 <5 2nd Stage processing temperature, C nd Stage acid number <10 3rd Stage processing temperature, C rd Stage acid number Resin properties Acid number Hydroxyl number Gardner viscosity Z 6 Z 8 Z 4 Z 5 Z Z 2 Gardner color Nonvolatiles, % Solvent EB solvent EB solvent/n-butanol (1/1) MPK (methyl n-propyl ketone) ᵃReaction mixtures cooled to 170 C before addition of new components at each stage and subsequent processing.

6 Enamel compositions from the resin cited in Table 1 are depicted in Table 2 along with formulation constants. Formulations WA-17-2T and WA-17-6C utilize ammonium hydroxide as the neutralizing agent to afford water-reducibility. Preparation of the enamels employs a simple Cowles dispersing blade for preparing the pigment grind followed by a letdown. Note all three example formulations use a cobalt drier for surface cure and manganese as a through drier. A zirconium through drier could possibly be used as well but has not been investigated with these resin systems. The enamel compositions prepared from the alkyd resins provide highly desirable film properties such as good gloss, dry times, and hardness. Table 3 highlights the drying properties and subsequent film properties for the enamel compositions. Table 2 Alkyd enamel compositions ENAMEL COMPOSITION Component Formulation WA-17-2T Formulation WA-17-6C Formulation HA-9-1N Grind Alkyd resin (75% NV) TiO 2 R-900 pigment TiO 2 R-960 pigment Palomar Blue 15: Ammonium hydroxide, 28% EB solvent n-butanol Toluene Methyl n-amyl ketone (MAK) ACTIV-8 drier accelerator BYK -301 additive Exkin 2 antiskinning agent Novec FC4432 flow additive Liosec HC Cobalt drier, 6% Liosec HC Manganese drier, 6% Letdown Water Total formulation, wt% Formulation properties Nonvolatiles, % Pigment/binder, wt% 45/55 56/44 45/55 Water/organics, wt% 82/18 84/16 NA Viscosity, #4 Ford Cup, sec ph NA

7 Table 3 Dry times and dry film properties DRY TIMES AND PROPERTIES Component Formulation WA-17-2T Formulation WA-17-6C Formulation HA-9-1N Dry time properties Set to touch, min Tack free, min One-hour water spot after 6 hours Slight effect Full recovery Slight effect Full recovery - Film properties after 7-day cure Dry film thickness, mils Pencil hardness B-HB HB 3B Impact resistance, in.-lb Direct Reverse 4 < Gloss Gloss Salt spray resistance, 100 hours mm creepage No creepage No loss of gloss h Note: Limited accelerated weathering evaluations for the above formulations have been conducted with acceptable results. However, long-term sun exposure has not been conducted. It is the responsibility of the customer to validate the weathering performance in their geographical location to account for environmental effects. This technical tip reviewed three base alkyd resin formulations, production protocol, enamel composition, and subsequent film properties. Each system has merits derived from the monomers selected for use. All three utilized Pamolyn 200 linoleic acid. This material has been used for years as the main drying component in alkyd formulations that require exceptional curing and physical properties. Glycol selection also plays an important role. Resin WA-17-2T utilizes TMPD glycol, a glycol known for good hydrolytic stability in waterborne systems whereas WA-17-6C contains CHDM glycol which is known to toughen cured films. The remaining solventbased formulation based on NPG glycol offers the broadest properties of the three.

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