Bisphenols and high-performance resins from terpenes
View Patent ↗The invention describes a high yield process that utilizes selective catalysts for the conversion of abundant, naturally occurring terpenes into bisphenols, and their derivative bis(cyanate)esters, resins, and polymers. High performance, low-cost composite materials with low moisture uptake and high glass transition temperatures suitable for aerospace applications can be prepared from these renewable starting materials.
1. A para-substituted bisphenolic compound having the formula:
where R and R′ are independently H, an alkyl group of up to about 10 carbon atoms, an aromatic group, an alkyl aromatic group, fluorine, fluorinated alkane, chlorine, or chlorinated alkane;
where R″ is H, CN, a glycidyl group, or a phthalonitrile group; and,
where R′″ is an alkyl of 1 to 20 carbons.
2. The compound of claim 1 having the formula:
3. The compound of claim 1 having the formula:
4. The compound of claim 1 having the formula:
5. A process for converting terpene feedstock to para-substituted bisphenolic compounds having the formula
where R and R′ are independently H, an alkyl group of up to about 10 carbon atoms, an aromatic group, an alkyl aromatic group, fluorine, fluorinated alkane, chlorine, or chlorinated alkane;
where R″ is H, CN, a glycidyl group, or a phthalonitrile group; and,
where R′″ is an alkyl of 1 to 20 carbons, comprising:
converting a monocyclic terpene to a phenol;
wherein said phenol has the formula:
where R′″ is an alkyl of 1 to 20 carbons
and,
reacting said phenol with an aldehyde or ketone to generate said para-substituted bisphenolic compound,
wherein said aldehyde or ketone has the formula:
where R and R′ are independently H, an alkyl group of up to about 10 carbon atoms, an aromatic group, an alkyl aromatic group, fluorine, fluorinated alkane, chlorine, or chlorinated alkane.
6. The process of claim 5 comprising:
oxidizing said monocyclic terpene to generate an alpha,beta-enone;
isomerizing said enone to a phenol;
wherein said phenol has the formula:
where R′″ is an alkyl of 1 to 20 carbons
and,
reacting said phenol with an aldehyde or ketone to generate said para-substituted bisphenolic compound,
wherein said aldehyde or ketone has the formula:
where R and R′ are independently H, an alkyl group of up to about 10 carbon atoms, an aromatic group, an alkyl aromatic group, fluorine, fluorinated alkane, chlorine, or chlorinated alkane.
7. The process of claim 5 comprising
oxidizing the monocyclic terpene to generate a 1,2-epoxide;
isomerizing the 1,2-epoxide to a ketone;
oxidizing the ketone to a phenol;
and,
wherein said phenol has the formula:
where R′″ is an alkyl of 1 to 20 carbons
and,
reacting said phenol with an aldehyde or ketone to generate said para-substituted bisphenolic compound,
wherein said aldehyde or ketone has the formula:
where R and R′ are independently H, an alkyl group of up to about 10 carbon atoms, an aromatic group, an alkyl aromatic group, fluorine, fluorinated alkane, chlorine, or chlorinated alkane.
8. The process of claim 5 wherein said monocyclic terpene is dipentene.
9. The process of claim 5 wherein said enone is carvone.
10. The process of claim 5 wherein said phenol is carvacrol.
11. The process of claim 5 wherein said aldehyde or ketone is selected from formaldehyde, paraformaldehyde, 1,3,5-trioxane, acetaldehyde, propionaldehyde, butyraldehyde iso-butyraldehyde, acetone, 2-butanone, 3-pentanone, 2-pentanone, or vanillin.
12. The process of claim 5 having a para-substituted bisphenolic compounds yield of greater than 50 percent by weight.
13. The process of claim 5 further comprising reacting said para-substituted bisphenolic compounds with a base and a cyanogen halide or cyanogen pseudohalide to produce a bis(cyanate) ester.
14. A polymer derived from the bisphenolic compounds of claim 1 .
15. The polymer of claim 14 said polymer having a water uptake of less than about 1%.
16. The polymer of claim 14 said polymer comprising thermoset resins.
17. The polymer of claim 14 , said polymer comprising thermoplastics.
18. The polymer of claim 14 , said polymer comprising cyanate esters, epoxies, phthalonitriles, and benzoxazines, polycarbonates, polysulfones, polyesters, polyesterstyrenes, alkylphenolics, and polyalylates.
19. The polymer of claim 14 , said polymer having a Tg greater than about 204° C.
20. The polymer of claim 14 , said polymer having a Tg of about 224° C.