March 2016 - Chemical Dynamics, LLC: Paint & Coatings Consultants

Basics of Alkyd Resin Technology

Mastering the fundamentals of Alkyd Resin Technology

Although alkyds are no longer the largest volume resin type used in coatings, they still play a significant role in the coatings industry, not only because of their versatility, but also because they employ a significant amount of renewable material.

The term alkyd is derived from alcohol and acid.

Alkyds are prepared from the condensation reaction between polyols, dibasic acids and fatty acids. The fatty acid portion is derived from vegetable matter and thus is a renewable resource. Key performance features of alkyds include their ability to offer improved surface wetting (from the bio-based fatty acid portion of substrates and pigments) and lower cost (also primarily from the fatty acid portion). The most widely used polyols include glycerol, pentaerythritol and trimethyol propane whereas the most widely used dibasic acids are phthalic anhydride and isophthalic acid.

Naturally-occurring oils are in the form of triglcerides. Triglycerides are triesters of glycerol and fatty acids. Triglycerides can be drying oils, but many are not. The reactivity of drying oils with oxygen results in 1,4 –dienes. The naturally-occurring oils are comprised of mixtures of mixed triglycerides with different fatty acids as part of the glyceride molecules.

Some of these glyceride molecules are comprised of a higher percentage of fatty acids with a greater amount of non-conjugated unsaturation with diallylic methylene groups and result in improved drying capability. For example, linoleic acid has one active diallylic group (-CH=CH – CH2 – CH=CH -), whereas linolenic has two active methylene groups. Also, to increase drying speed, alkyds can be modified with vinyl toluene or styrene to increase the Tg and thus reduce the time required to reach a given hardness. If the amount of oil in an alkyd is over 60%, it is called a long oil alkyd. If it’s between 40 and 60%, it’s known as a medium oil alkyd, and those with less than 40 are considered short oil alkyds. The formula for calculating the percent oil length based on the amount of fatty acid is as follows:

Alkyd 2

In addition to the amount of oil as well as the selection of the alcohol and acid functional components, the type of oil has a profound effect on the dry time and performance.

Fatty acids are further categorized into drying, semidrying and non-drying. Non-conjugated oils are considered drying oils if their drying index, as calculated as follows, is more than 70. The higher the amount ofLinolenic and Linoleic content, the higher the drying index: Alkyd 3

Although drying speed is improved as the % linolenic increases, the rate of yellowing for exterior white coatings is also greater. Accordingly, alkyds using safflower and sunflower oils which provide improved resistance to yellowing as a result of their lower linolenic content.

Alkyd 4 Alkyd 5

In addition to classifying alkyds by their oil length and the type of fatty acid present, alkyds are also classified into oxidizing and non-oxidizing categories. Oxidizing alkyds crosslink through a complex multistage auto-oxidation mechanism, whereas Non-oxidizing alkyds do not crosslink and are thus thermoplastic unless their available hydroxyl groups are crosslinked with an aminoplast (heat cured) or isocyanate crosslinker (ambient cured).

To read the rest of the article, written by Chemical Dynamics’ President, Ron Lewarchik, click over to UL Prospector here.

UV-LED Curable Coatings Offer a High-Speed Light Curing Process

Posted on by chemical dynamics

UV-LED Curable Coatings offer a high-speed light curing process with a number of advantages over more conventional cure processes. Multiple advantages include High speed, lower energy requirements, little or no VOC, less production space, less dirt collection, high quality finish, rapid processing as well as instant on-off with some UV light technologies also expedite production and energy savings. UV Curable paint finishes have existed since the 1960’s and are based on polymerization reactions including free radical and cation-initiated chain-growth polymerization. As the majority of coatings for UV cure coating utilize free radical polymerization (>90% of market), this article will focus primarily on free radical polymerization initiated by a photoinitiator (Fig. 1):

The types of unsaturation used in UV/EB cure coatings are provided in Table I, with by far the largest type being acrylate.

Table I – Type of Unsaturation used in UV/EB Cure

Photoinitiator

considerations primarily include two different characteristics of the photoinitiator’s absorption curve. First, is the maximum wavelength (Lambda Max) of light that is absorbed by the PI and second, the strength of this absorption (molar extinction coefficient). Photoinitiators developed for curing pigmented films normally have higher molar extinction coefficients at longer wavelengths between 300 nm to 450 nm than those for curing clear formulations. To maximize cure and efficiency, the PI’s absorbance must match the light output of the lamp as different lamps have different spectral outputs (see Table I). Longer wave- length light is also essential to enhance cure in thicker coatings. Newer PI’s have also enabled the formulation of pigmented coatings in addition to that of clear coatings. The general cure considerations influenced by color, PVC, pigment particle size and film thickness are summarized in Fig. 2:

Figure 2 – UV Cure Considerations. Image: Ciba – Geigy literature

There are two main types of free radical photoinitiators, Type I and Type II. Type I photoinitiators undergo cleavage upon irradiation to form two free radicals. Normally only one of these free radicals is reactive and thus initiates polymerization. 1-hydroxy-cyclohexylphenyl-ketone is a widely used Type I PI. Type II photoinitiators form an excited state upon irradiation, and abstract an atom or electron from a donor molecule (synergist). The donor molecule in turn initiates polymerization. An example of a widely used Type II photoinitiator is benzophenone. Tertiaryamines are typically used as synergists as they react with benzophenone, and also retard the inhibition of polymerization by oxygen. Acrylated tertiary amine compounds are used when odor and extractables are of concern. Oxygen can also inhibit cure especially in thin films; to counteract oxygen inhibition, coatings can use amine synergists, be cured under a nitrogen atmosphere, employ the addition of wax, high initiator concentration, more intense UV Light, and/or surface active initiators.

To read the rest of the article, written by Chemical Dynamics’ President, Ron Lewarchik, click over to UL Prospector here.