Furan based compositions and methods of making thereof
Disclosed herein are processes for the preparation of compounds of formula (I) from one or more bio-derived reactants, and their use as base oils: (R 1 -A) b -(CH x ) a (CHR 2 ) m —(C(R 4 R 5 )) n —(CHR 3 ) o —(CH y ) c -(A-R 1′ ) d (I) wherein a and c are independently 0 or 1, b and d are independently 1 or 2, x and y are independently 1 or 2, dependent upon the values of a-d, m and o are independently 0 or 1, n is an integer of 0-6, and each A is independently an unsaturated furan ring, a partially saturated furan ring, a saturated furan ring, or —(CH 2 ) 4 —. Also, R 1 , R 1′ , R 2 , R 3 , R 4 and R 5 are independently selected from the group consisting of H and alkyl groups having 1 to 18 carbon atoms, with a proviso that at least one of R 2 , R 3 , R 4 , and R 5 is not hydrogen, and the total carbon content of the compound of formula (I) is in the range of 20-62.
1 . A compound selected from one of the following:
(i) a condensed furan compound selected from the group consisting of 5,5-(ethane-11-dlyl)bis(2-pentylfuran), 5,5′-(dodecane-1,1-diyl)bis(2-methylfuran), 5,5′-(dodecane-1,1-diyl)bis(2-ethylfuran), 5,5′-(hexane-1,1-diyl)bis(2-pentylfuran), 5,5′-(dodecane-1,1-diyl)bis(2-propylfuran), 5,5′-(octane-1,1-diyl)bis(2-pentylfuran), 5,5′-(2-ethylhexane-1,1-diyl)bis(2-pentylfuran), 5,5′-(dodecane-1,1-diyl)bis(2-butylfuran), 5,5′-(decane-1,1-diyl)bis(2-pentylfuran), 5,5′-(2-ethylhexane-1,1-diyl)bis(2-hexylfuran), 5,5′-(dodecane-1,1-diyl)bis(2-pentylfuran), 5,5′-(2-ethylhexane-1,1-diyl)bis(2-heptylfuran), 5,5′-(dodecane-1,1-diyl)bis(2-hexylfuran), 5,5′-(dodecane-1,1-diyl)bis(2-heptylfuran), 5,5′,5″-(butane-1,1,3-triyl)tris(2-pentylfuran), 5,5′-(undecane-2,2-diyl)bis(2-pentylfuran), and 1,1,6,6-tetrakis(5-methylfuran-2-yl) hexane,
(ii) a condensed saturated furan compound selected from the group consisting of 5,5′-(dodecane-1,1-diyl)bis(2-pentyltetrahydrofuran), 5,5′-(dodecane-1,1-diyl)bis(2-butylltetrahydrofuran), 5,5′-(dodecane-1,1-diyl)bis(2-propyltetrahydrofuran), 5,5′-(dodecane-1,1-diyl)bis(2-ethyltetrahydrofuran), 5,5′-(dodecane-1,1-diyl)bis(2-methyltetrahydrofuran), 5,5′-(dodecane-1,1-diyl)bis(2-heptyltetrahydrofuran), 5,5′-(2-ethylhexane-1,1-diyl)bis(2-pentyltetrahydrofuran), 5,5′-(ethane-1,1-diyl)bis(2-pentyltetrahydrofuran), 5,5′-(2-ethylhexane-1,1-diyl)bis(2-heptyltetrahydrofuran), 5,5′-(2-ethylhexane-1,1-diyl)bis(2-hexyltetrahydrofuran), 5,5′-(octane-1,1-diyl)bis(2-pentyltetrahydrofuran), 5,5′-(decane-1,1-diyl)bis(2-pentyltetrahydrofuran), 5,5′-(hexane-1,1-diyl)bis(2-pentyltetrahydrofuran), and 1-((2S)-5-methyltetrahydrofuran-2-yl)-1,6,6-tris(5-methyltetrahydrofuran-2-yl) hexane, or
(iii) a condensed furan alkane compound selected from the group consisting of 6-pentylheptadecane, 10-pentylnonadecane, 8-heptylnonadecane, 10-heptylnonadecane, 10-(heptan-3-yl) nonadecane, 10-nonylnonadecane, 11-(heptan-3-yl) henicosane, 10-nonylhenicosane, 12-(heptan-3-yl)tricosane, 12-undecyltricosane, 10-methyl-12-nonylhenicosane, and 10-methyl-10-nonylnonadecane,
wherein the compound has a bio-based content in the range of 20 to 100%, according to ASTM-D6866.
2 . A compound selected from one of the following:
(i) a condensed furan compound selected from the group consisting of 5,5-(ethane-11-dlyl)bis(2-pentylfuran), 5,5′-(dodecane-1,1-diyl)bis(2-methylfuran), 5,5′-(dodecane-1,1-diyl)bis(2-ethylfuran), 5,5′-(hexane-1,1-diyl)bis(2-pentylfuran), 5,5′-(dodecane-1,1-diyl)bis(2-propylfuran), 5,5′-(octane-1,1-diyl)bis(2-pentylfuran), 5,5′-(2-ethylhexane-1,1-diyl)bis(2-pentylfuran), 5,5′-(dodecane-1,1-diyl)bis(2-butylfuran), 5,5′-(decane-1,1-diyl)bis(2-pentylfuran), 5,5′-(2-ethylhexane-1,1-diyl)bis(2-hexylfuran), 5,5′-(dodecane-1,1-diyl)bis(2-pentylfuran), 5,5′-(2-ethylhexane-1,1-diyl)bis(2-heptylfuran), 5,5′-(dodecane-1,1-diyl)bis(2-hexylfuran), 5,5′-(dodecane-1,1-diyl)bis(2-heptylfuran), 5,5′,5″-(butane-1,1,3-triyl)tris(2-pentylfuran), 5,5′-(undecane-2,2-diyl)bis(2-pentylfuran), and 1,1,6,6-tetrakis(5-methylfuran-2-yl) hexane,
(ii) a condensed saturated furan compound selected from the group consisting of 5,5′-(dodecane-1,1-diyl)bis(2-pentyltetrahydrofuran), 5,5′-(dodecane-1,1-diyl)bis(2-butylltetrahydrofuran), 5,5′-(dodecane-1,1-diyl)bis(2-propyltetrahydrofuran), 5,5′-(dodecane-1,1-diyl)bis(2-ethyltetrahydrofuran), 5,5′-(dodecane-1,1-diyl)bis(2-methyltetrahydrofuran), 5,5′-(dodecane-1,1-diyl)bis(2-heptyltetrahydrofuran), 5,5′-(2-ethylhexane-1,1-diyl)bis(2-pentyltetrahydrofuran), 5,5′-(ethane-1,1-diyl)bis(2-pentyltetrahydrofuran), 5,5′-(2-ethylhexane-1,1-diyl)bis(2-heptyltetrahydrofuran), 5,5′-(2-ethylhexane-1,1-diyl)bis(2-hexyltetrahydrofuran), 5,5′-(octane-1,1-diyl)bis(2-pentyltetrahydrofuran), 5,5′-(decane-1,1-diyl)bis(2-pentyltetrahydrofuran), 5,5′-(hexane-1,1-diyl)bis(2-pentyltetrahydrofuran), and 1-((2S)-5-methyltetrahydrofuran-2-yl)-1,6,6-tris(5-methyltetrahydrofuran-2-yl) hexane, or
(iii) a condensed furan alkane compound selected from the group consisting of 6-pentylheptadecane, 10-pentylnonadecane, 8-heptylnonadecane, 10-heptylnonadecane, 10-(heptan-3-yl) nonadecane, 10-nonylnonadecane, 11-(heptan-3-yl) henicosane, 10-nonylhenicosane, 12-(heptan-3-yl)tricosane, 12-undecyltricosane, 10-methyl-12-nonylhenicosane, and 10-methyl-10-nonylnonadecane, wherein the compound has a bio-based content in the range of 20 to 100%, according to ASTM-D6866.
3 . A personal care composition comprising:
a. a base oil comprising one or more compounds according to claim 1 ;
b. an effective amount of one or more additives selected from the group consisting of pigment, fragrance, emulsifier, wetting agent, thickener, emollient, rheology modifier, viscosity modifier, gelling agent, antiperspirant agent, deodorant active, fatty acid salt, film former, anti-oxidant, humectant, opacifier, monohydric alcohol, polyhydric alcohol, fatty alcohol, preservative, pH modifier, a moisturizer, skin conditioner, stabilizing agent, proteins, skin lightening agents, topical exfoliants, antioxidants, retinoids, refractive index enhancer, photo-stability enhancer, SPF improver, UV blocker, and water.
4 . The personal care composition of claim 3 , further comprising an active ingredient selected from the group consisting of antibiotic, antiseptic, antifungal, corticosteroid, and anti-acne agent.
5 . A pharmaceutical composition comprising:
a. a base oil comprising one or more compounds according to claim 1 ;
b. an effective amount of one or more pharmaceutically active ingredients; and
C. optionally, one or more pharmaceutically acceptable excipients.
6 . A grease comprising a base oil comprising one or more compounds according to claim 1 .
7 . A lubricant composition comprising:
a. 30-99% by weight of a base oil comprising one or more compounds according to claim 1 ; and
b. an effective amount of one or more lubricant additives.
8 . The lubricant composition according to claim 7 , wherein at least one of the one or more compounds has a furan ring or a tetrahydrofuran ring.
9 . The lubricant composition according to claim 7 , further comprising one or more co-base oils selected from the group consisting of API Group I base oil, Group II base oil, Group III base oil, Group IV base oil, Group V base oil, gas-to-liquid base oil, and combinations thereof.
10 . A method of making the compound according to claim 1 :
wherein the method comprises the steps of:
a) providing a first component comprising one or more of a 2-alkylfuran and a second component comprising one or more of:
i) an aldehyde,
ii) a dialdehyde,
iii) an enal, or
iv) a ketone,
wherein at least one of the first component and the second component is bio-derived from a renewable source,
wherein the first component and the second component are selected from one of the following combinations:
First Component
Second Component
2-pentylfuran
acetaldehyde
2-methylfuran, 2-ethylfuran,
lauraldehyde
2-propylfuran, 2-butylfuran,
2-pentylfuran, 2-hexylfuran,
2-heptylfuran,
2-pentylfuran
hexanal, octanal, decanal
2-pentylfuran, 2-hexylfuran,
2-ethylhexanal
2-heptylfuran
2-methylfuran
hexanedial
2-pentylfuran
crotonaldehyde
2-pentylfuran
2-undecanone
b) condensing the first component with the second component in the presence of an acidic catalyst to form the condensed furan compound;
c) optionally hydrogenating the condensed furan compound in the presence of a hydrogenation catalyst to obtain the condensed saturated furan compound; and
d) optionally hydrodeoxygenating the condensed furan compound or the condensed saturated furan compound in the presence of a hydrodeoxygenation catalyst and hydrogen to obtain the condensed furan alkane compound.
11 . The method according to claim 10 , wherein the step of providing an aldehyde comprises at least one of dehydrogenating one or more biomass derived alcohols and selective hydrogenation of one or more fatty acids from one or more natural oils or waste cooking oils.
12 . The method according to claim 10 , wherein the step of condensing the first component with the second component comprises carrying out the condensing in the presence of at least one thiol selected from the group consisting of ethanethiol, propanethiol, butanethiol and combinations thereof.
13 . The method according to claim 10 , wherein the acidic catalyst comprises at least one acidic catalyst selected from the group consisting of liquid acids and solid acids.
14 . The method according to claim 10 , wherein step c) is performed in the presence of a hydrogenation catalyst and the hydrogenation catalyst is a metal base catalyst selected from palladium catalysts supported on carbon or acidic materials and nickel based catalysts.
15 . The method according to claim 10 , wherein the step d) is performed in the presence of a hydrodeoxygenation catalyst and the hydrodeoxygenation catalyst is a solid acid supported metal based catalyst or a physical mixture of a metal based catalyst.
16 . The method according to claim 15 , wherein the hydrodeoxygenation catalyst is a solid acid supported metal based catalyst selected from Ni/ZSM-5, Pd/ZSM-5, Pd/BEA, or a physical mixture of a metal based catalyst with a solid acid and a supported metal-metal oxide catalyst.
17 . The method according to claim 14 , wherein the palladium catalysts are selected from the group consisting of Pd/C, Pd/SiO 2 and Pd/Al 2 O 3 , and the nickel based catalysts comprise Raney Ni.
18 . The method according to claim 15 , wherein the metal based catalyst includes Pd/C, Pd/SiO 2 or Pt/C, with a solid acid.
19 . The method according to claim 16 , wherein the solid acid includes Pd/C+ZSM-5, Pd/C+BEA, Pt/C+BEA, and the supported metal-metal oxide catalyst includes Ir-ReO x /SiO 2 , Ir—MoO x /SiO 2 or 1 M 2 MO/SiO 2 , wherein 1 M=Ir, Ru, Ni, Co, Pd, Pt, or Rh and 2 M=Re, Mo, W, Nb, Mn, V, Ce, Cr, Zn, Co, Y, or Al.