Artificial urushi

The reason why synthesis of natural urushiols involves multistep, tedious procedures is that the reactive unsaturated group cannot be directly introduced on the catechol moiety protection and deprotection of the catechol moiety are 

Cardanol, a main component obtained by thermal treatment of cashew nut shell liquid (CNSL), is a phenol derivative having mainly the meta substituent of a C15 unsaturated hydrocarbon chain with one to three double bonds as the major. Since CNSL is nearly one-third of the total nut weight, a great amount of CNSL is obtained as byproducts from mechanical processes for the edible use of the cashew kernel. Only a small part of cardanol obtained in the production of cashew kernel is used in industrial fields, though it has various potential industrial utilizations such as resins, friction-lining materials, and surface coatings. Therefore, development of new applications for cardanol is very attractive. 

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A new crosslinkable polymer was synthesized by the SBP-catalyzed polymerization of cardanol. When HRP was used as catalyst for the cardanol polymerization, the reaction took place in the presence of a redox mediator (phe-nothiazine derivative) to give the polymer. Fe-salen efficiently catalyzed the polymerization of cardanol in organic solvents (Scheme 29). " The polymerization proceeded in 1,4-dioxane to give the soluble polymer with molecular weight of several thousands in good yields. The curing of the polymer took place in the presence of cobalt naphthenate catalyst at room temperature or thermal treatment (150°C for 30 min) to form yellowish transparent films ( artificial urushi ... 

Figure 1. Dynamic viscoelasticity of artificial urushi from urushiol analogue having a linolenic acid group.

Fig. 16. Laccase-catalyzed curing of urushiol analogues to artificial urushi. ...

Kobayashi S, Ikeda R, Oyabu H et al (2(X)0) Artificial Urushi design, synthesis, and enzymatic curing of new urushiol analogues. Chem Lett 29 1214—1215... 

In the previous chapter Synthesis of Phenol Polymers Using Peroxidases , the enzymatic oxidative polymerization of monophenolic derivatives is described. This chapter deals with the enzymatic synthesis and properties of polymers from polyphenols, compounds having more than two hydroxyl groups on the aromatic ring(s). In particular, cured phenolic polymers (artificial urushi) and flavonoid polymers are examined from the standpoint of the enzymatic synthesis of functional materials. 

Fig. 3 Dynamic viscoelasticity of (A) artificial urushi from an urushiol analogue having linolenic acid moiety in the presence of AP and (B) natural urushi...

This review gives an overview of enzymatic synthesis and the properties of polymers derived from polyphenols. Catechol derivatives were enzymatically oxidized to form polymers. Urushiol analogues were designed and cured by laccase catalyst to produce artificial urushi of good elasticity. 

The urushi lacquer has been used for more than 5000 years in China " and it is known as a highly durable material. Polymerization of urushiol, the major component of the lacquer, involves laccase-catalyzed dimerization and aerobic oxidative polymerization, " and the drying process takes a very long time. Several studies on shortening of this time have been carried out UV curing " " and hybridizing with other reactive polymers or monomers. " " Cardanol has a similar structure to urushiol, and the enzymatic oxidative polymerization of cardanol were reported by three research groups. " The development of the polymerization process leads to artificial urushi . 

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