Chemistry of Dimer Acid Production from Fatty Acids and the Structure–Property Relationships of Polyamides Made from These Dimer Acids
<p>Structure of clays, showing charge and sheet separation differences for the non-swelling kaolinite on the left, the swelling smectite on the right and the exfoliated clay on the bottom left. SiO represents silicon oxide layer; AlO represents aluminum oxide layer: SiMO is the silicon oxide layer where some of the silicon atoms are replaced by lower valent metals creating a negative charge on the lattice; AlMO is the silicon oxide layer where some of the aluminum atoms are replaced by lower valent metals creating a negative charge on the lattice. Minus signs show negative charge on the lattices, M<sup>+</sup> show counter balancing cations which can be mono-, di- or trivalent, and FA represents the adsorbed fatty acids.</p> "> Figure 2
<p>Schematic of the FA dimerization process and separation of products with the thicker bordered boxes representing commercial fatty acid products; often the hydrogenation step is skipped to yield a partially unsaturated and less expensive isostearic acid.</p> "> Figure 3
<p>Likely structures of typical hydrogenated and esterified dimer molecules from the polymerization of unsaturated FA. Due to isomerization and minor FA monomers, the chain lengths and location of unsaturation of the attached chains vary, with the m/e from mass spectroscopy indicting the molecular weight. Reprinted with permission from McMahon and Crowell [<a href="#B38-polymers-15-03345" class="html-bibr">38</a>].</p> "> Figure 4
<p>Desired composition of the oligomer is a dimer fatty acid (R<sub>1</sub>) with each end reacted with an ethylenediamine, that is then capped with a stearic acid. Figure taken from US patent 5,194,638 [<a href="#B45-polymers-15-03345" class="html-bibr">45</a>].</p> "> Figure 5
<p>Structure for ester-terminated amides using a dimer core for gel structure and terminal ester groups for compatibility with non-polar components. Image taken from [<a href="#B47-polymers-15-03345" class="html-bibr">47</a>], with n being the number of repeat units of the oligomer, R<sup>2</sup> being the 34 carbons of the dimer, R<sup>3</sup> being short chain primary diamines and R<sup>1</sup> being hydrocarbon groups with long chains.</p> "> Figure 6
<p>Typical type of cationic reactions to make linear and monocyclic dimers. These are only representative structures as the cationic reactions are generally not positional specific reactions due to isomerization of the unsaturated fatty acids, which in themselves have olefinic bonds at different locations.</p> "> Figure 7
<p>Left image (<b>A</b>) is of piperazine with only secondary amines. Right (<b>B</b>) is an image of 1,2-diaminopropane (DAP) with one hindered and one less hindered amine.</p> ">
Abstract
:1. Introduction
2. Fatty Acid Dimer Synthesis and Properties
2.1. Clay Structure and Property
2.2. Dimerization Products and Structures
2.3. Dimerization Mechanism
3. Dimer-Based Polyamides
Polyamide Composition and Properties
4. Conclusions
Funding
Institutional Review Board Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Structure/FA Feed | Linoleic | TOFA | Oleic/Eladic |
---|---|---|---|
Linear (non-cyclic) | 5 | 15 a | 40 a |
Monocyclic- aromatic | 25 | 20 | 5 |
Monocyclic- nonaromatic | 30 | 50 a | 50 a |
Polycyclic | 40 | 15 a | 5 a |
Polymer | Monomers | Melting Point, °C | Softening Point, °C |
---|---|---|---|
Nylon 6 | Caprolactam | 210–220 | |
Nylon 6,6 | Adipic acid, Heamethylene diamine | 245–265 | |
Nylon 6,12 | Dodecanoic acid, Heamethylene diamine | 215–220 | |
Polyamide | Dimer acid, Ethylene diamine | 100 | |
Polyamide | Dimer acid, Heamethylene diamine | 53–59 | |
Polyamide | Dimer acid, Dimer diamine | Liquid |
Dimer Acid, % of Total Acids | Sebacic Acid, % of Total Acids | Polyamide Softening Point, °C | Tensile Strength, MPa | Elongation, % |
---|---|---|---|---|
100 | 0 | 100 | 1600 | 500 |
95 | 5 | 135 | 1750 | 400 |
90 | 10 | 165 | 2100 | 350 |
85 | 15 | 200 | 3300 | 300 |
Polyamide Adhesive Prepared from | ||||
---|---|---|---|---|
Physical Properties | 1,2-Diaminopropane Example 1 | Ethylenediamine Example 2 | 1,3-Diaminopropane Example 3 | 2-Methyl=1,5—Pentanediamine Example 4 |
Softening Point, °C | 111 | 158 | 94 | 98 |
Viscosity at 190 °C, Pa-s | 9.8 | 8.5 | 9.5 | 5.4 |
Tensile strength, MPa | 2.48 | 3.61 | 0.52 | 0.09 |
Elongation, % | 556 | 402 | >2000 | >800 |
Modulus, Pa | 2335 | 12,690 | * | * |
Open time | 50 s | 10 s | >24 h | >24 h |
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Frihart, C.R. Chemistry of Dimer Acid Production from Fatty Acids and the Structure–Property Relationships of Polyamides Made from These Dimer Acids. Polymers 2023, 15, 3345. https://doi.org/10.3390/polym15163345
Frihart CR. Chemistry of Dimer Acid Production from Fatty Acids and the Structure–Property Relationships of Polyamides Made from These Dimer Acids. Polymers. 2023; 15(16):3345. https://doi.org/10.3390/polym15163345
Chicago/Turabian StyleFrihart, Charles R. 2023. "Chemistry of Dimer Acid Production from Fatty Acids and the Structure–Property Relationships of Polyamides Made from These Dimer Acids" Polymers 15, no. 16: 3345. https://doi.org/10.3390/polym15163345