Bio-Based Epoxy Polymers, Blends, and Composites. Группа авторов
Чтение книги онлайн.
Читать онлайн книгу Bio-Based Epoxy Polymers, Blends, and Composites - Группа авторов страница 12
![Bio-Based Epoxy Polymers, Blends, and Composites - Группа авторов Bio-Based Epoxy Polymers, Blends, and Composites - Группа авторов](/cover_pre859870.jpg)
Fatty acid | Vegetable oil, content of individual acids (wt%) | |||||
---|---|---|---|---|---|---|
Soybean | Rapeseed | Linseed | Sunflower | Castor | Palm | |
Palmitic | 12 | 4 | 5 | 6 | 1.5 | 39 |
Stearic | 4 | 2 | 4 | 4 | 0.5 | 5 |
Oleic | 24 | 56 | 22 | 42 | 5 | 45 |
Linoleic | 53 | 26 | 17 | 47 | 4 | 9 |
Linolenic | 7 | 10 | 52 | 1 | 0.5 | — |
Castor | — | — | — | — | 87.5 | — |
Other | — | 2 | — | — | — | 2 |
Functionality | 4.6 | 3.8 | 6.6 | 4.6 | 2.8 | 1.8 |
The functionality of oils (understood as the content of unsaturated bonds) primarily determines the cross‐linking density of oil‐based chemosetting polymers or polymers obtained by free radical polymerization as well as oil‐modified polymeric materials. In turn, the final polymer properties such as mechanical strength, thermal stability, and chemical resistance strongly depend on the cross‐linking density. The elasticity of the polymers with the addition of vegetable oil or based on them depends on the length of the alkyl chains in the oil molecule derived from fatty acids.
Vegetable oils can be easily and efficiently converted into epoxy derivatives by oxidizing unsaturated bonds present in fatty acid residues. Several methods of double bond oxidation in triglyceride molecules are known and commonly used [3]: the method based on the Prilezhaev reaction, the radical oxidation, the Wacker‐type oxidation, dihydroxylation of oils and fats, and enzyme–catalyst oxidation. The Prilezhaev reaction is the most often used method for natural oil epoxidation, commonly applied in the industry. In this method, the process of epoxidation of natural fatty acids and triglycerols is carried out in the system consisting of hydrogen peroxide, an aliphatic carboxylic acid, and an acidic catalyst. The organic peracid formed in situ by the reaction of acid with hydrogen peroxide is the real oxidizing agent in this method (Figure 1.2).
Carboxylic acids with one to seven carbon atoms are the most commonly used (in practice, mainly acetic acid). Inorganic or organic acids and their salts, as well as acidic esters, can be used as catalysts; however, sulfuric and phosphoric acid are the most often used in industrial practice. A promising method is oxidation in the presence of enzymes [4], heteropolyacids [5], and even ion exchange resins [6] as catalysts. The most commonly used oxidizing agent is hydrogen peroxide in the form of solution with a concentration of 35–90% (usually 50%). Epoxidation of plant oils in ionic liquids, as well as in supercritical carbon dioxide, is also described [7].
The earliest epoxidized esters of higher fatty acids have found wide applications as both plasticizers and stabilizers for thermoplastics, mostly poly(vinyl chloride), poly(vinylidene chloride), their copolymers, and poly(vinyl acetate) and chlorinated rubber [8, 9]. Epoxidized fatty acids containing oleic acid are used as a valuable intermediate in the production of lubricants and textile oils [10, 11]. It seems that epoxidized vegetable oils could also be used as hydraulic liquids [12]. However, primarily, they can also act as reactive diluents of bisphenol‐based epoxy resins [13], which are usually highly viscous. They have oxirane groups, although less reactive because of their central location in triglyceride chains (compared to terminal glycidyl groups), but also capable of reacting with polyamines or carboxylic anhydrides. By building into the structure of the cured resin in the process of co‐cross‐linking with it, they affect its final properties – improving flexibility and impact strength. In this way, embedded triglycerides not only facilitate the processing of resins with high intrinsic viscosity but also allow limiting their typical disadvantages (high brittleness, low impact strength, and flexibility) resulting from the rigid structure they owe because of the structure of bisphenols [14].
Figure 1.2 The reaction of triglyceride epoxidation with organic peracids.
However, the first, logically implied possibility of use of epoxidized vegetable oils is their application as stand‐alone materials: the networks cross‐linked with bifunctional compounds such as dicarboxylic acids or aliphatic and aromatic diamines, which are typically used as hardeners for the epoxy resins. Because of the content of more than one epoxy group in the molecule, epoxidized triglycerides may, according to the generally accepted definition, be treated as epoxy resins. However, curing of, e.g. epoxidized soybean oil [15] or vernonia oil (natural epoxidized oil mainly obtained from plant Vernonia galamensis), dicarboxylic acids [16] resulted in obtaining only soft elastomers. Materials with higher mechanical strength are synthesized by reacting epoxidized oils first with polyhydric alcohols (e.g. resorcinol) and phenols or bisphenols and then cross‐linking the obtained modified oil with partially reacted epoxidized rings [17]. Finally, curing by photopolymerization or polymerization with latent initiators allows to obtain from modified vegetable oils, without the addition of the bisphenol‐based or cycloaliphatic resins, coating materials with satisfactory mechanical properties. It was found [18] that the properties of hardened vegetable oils also depend on the type of used thermal latent initiator. The properties of epoxidized castor oil cross‐linked with N‐benzylpyrazine (BPH) and N‐benzylquinoxaline (BQH) were studied (Figure 1.3).
It was found that materials characterized by a higher glass transition temperature, a higher value of the coefficient of thermal expansion, and greater thermal stability are obtained using BPH as a photoinitiator. Nevertheless, the composition cross‐linked with BQH is characterized by better mechanical properties. Most likely, the better final properties result from the higher cross‐linking density of cured with BPH composition. Anhydrides of various carboxylic acids are used to cure epoxidized linseed oil [19], and cross‐linking