Engineering Green Lubricants II: Thermal Transition and Flow Properties of Vegetable Oil- Derived Diesters

Transcription

1 Engineering Green Lubricants II: Thermal Transition and Flow Properties of Vegetable Oil- Derived Diesters Latchmi Raghunanan and Suresh S. Narine. * Trent Centre for Biomaterials Research, Departments of Physics & Astronomy and Chemistry, Trent University, 1600 West Bank Drive, Peterborough, ON, Canada K9L 0G2 * Corresponding Author: Fax: ; Tel: ; sureshnarine@trentu.ca Total number of pages: 11 Table S.1: Nomenclature and structural characterization of the linear diesters synthesized in this work.. Scheme S.1: Synthesis of symmetric diesters from fatty acids and diols.... Scheme S.2: Showing the two-stage syntheses of asymmetric diesters Figure S.1: DSC cooling (3 C/min) thermograms of the linear aliphatic diesters. Figure S.2: DSC heating (3 C/min) thermograms of linear aliphatic diesters Figure S.3: (a) WAXD plots for and diesters obtained at 0 C and -25 C, respectively using a cooling rate of 1 C/min. (b) DSC cooling profiles of and obtained using the same thermal protocol as was used for determination of the WAXD profiles... Figure S.4: Shear rate versus shear stress plots of representative diester series measured at 40 C (a) 10-n-10 and (b) 22-n-22 diesters..... Figure S.5: Temperature-Viscosity profiles of representative diester series (a) 10-n-10; and (b) 22-n S2 S7 S7 S8 S8 S9 S10 S11 S1

2 Table S.1: Nomenclature and structural characterization of the linear diesters synthesized in this work. Compound IUPAC Name Structure Characterization Symmetric unsaturated diesters: ethane-1,2-diyl bis(dec-9- IR (ATR): 1735 (C=O) cm -1 ; 1 H-NMR in CDCl 3 δ (ppm): (12, m, C-CH 2 -), (4, m, H 2 C=CCCH 2 -), (4, m, O=CCCH 2 -), (4, q, H 2 C=CCH 2 -), (4, t, O=CCH 2 -), 4.26 (4, s, O-CH 2 -), (4, qd, -HC=CH 2 ), (2, m, H 2 C=CH-). MS (ESI): calculated for C 22 H 38 O 4 367, found m/z 390 ([M + Na] + ) propane-1,3-diyl bis(dec butane-1,4-diyl bis(dec hexane-1,6-diyl bis(dec- 9- IR (ATR): 1735 (C=O) cm -1 ; 1 H-NMR in CDCl 3 δ (ppm): (12, m, C-CH 2 -), (4, m, H 2 C=CCCH 2 -), (4, m, O=CCCH 2 -), (2, quin, O-CCH 2 -), (4, q, H 2 C=CCH 2 -), (4, t, O=CCH 2 -), (4, t, O-CH 2 -), (4, qd, -HC=CH 2 ), (2, m, H 2 C=CH-). MS (ESI): calculated for C 23 H 40 O 4 381, found m/z 404 ([M + Na] + ) ; Colourless oil (6.4 g, 90 %); IR (ATR): 1735 (C=O) cm -1 ; 1 H-NMR in CDCl 3 δ (ppm): (12, m, C-CH 2 -), (4, quin, H 2 C=CCCH 2 -), (4, quin, O=CCCH 2 -), (4, m, O-CCH 2 -), (4, q, H 2 C=CCH 2 -), (4, t, O=CCH 2 -), (4, m, O-CH 2 -), (4, qd, - HC=CH 2 ), (2, m, H 2 C=CH-). MS (ESI): calculated for C 24 H 42 O 4 395, found m/z 418 ([M + Na] + ) ; Colourless oil (7.7 g, 90 %); IR (ATR): 1735 (C=O) cm -1 ; 1 H-NMR in CDCl 3 δ (ppm): (12, m, C-CH 2 -), (8, m, H 2 C=CCCH 2 -, O-CCCH 2 -), (8, m, - H 2 CCO(C=O)CCH 2 -), (4, q, H 2 C=CCH 2 -), (4, t, O=CCH 2 -), (4, t, O-CH 2 -), (4, qd, -HC=CH 2 ), (2, m, H 2 C=CH-). MS (ESI): calculated for C 26 H 46 O 4 423, found m/z 446 ([M + Na] + ) ethane-1,2-diyl di IR (ATR): 1742 (C=O) cm -1 ; 1 H-NMR in CDCl 3 δ (ppm): (4, m, -CH=CH-), 4.24 (4, s, O-CH 2 -), (4, t, O=CCH 2 -), (8, m, C=CCH 2 -), (4, m, O=CCCH 2 -), (40, m, C-CH 2 -), (6, t, C-CH 3 ). MS (ESI): calculated for C 38 H 70 O 4 590, found m/z 608 ([M + NH 4 ] + ) propane-1,3-diyl di IR (ATR): 1739 (C=O) cm -1 ; 1 H-NMR in CDCl 3 δ (ppm): (4, m, -CH=CH-), (4, t, O-CH 2 -), (4, m, O=CCH 2 -), (8H, m, -CH=CCH 2 -), (2H, m, O- CCH 2 -), (4H, m, O=CCCH 2 -), (40, m, C-CH 2 -), (6, t, C-CH 3 ). MS (ESI): calculated for C 39 H 72 O 4 604, found m/z 622 ([M + NH 4 ] + ) butane-1,4-diyl di IR (ATR): 1738 (C=O) cm -1 ; 1 H-NMR in CDCl 3 δ (ppm): 5.32 (4, m, -CH=CH-), 4.07 (4, t, O-CH 2 -), (4, t, O=CCH 2 -), (8, m, -CH=CCH 2 -), (4, m, O-CCH 2 -), (4, m, O=CCCH 2 -), (40, m, C-CH 2 -), (6, t, C-CH 3 ). MS (ESI): calculated for C 40 H 74 O 4 618, found m/z 636 ([M + NH 4 ] + ). S2

3 hexane-1,6-diyl di IR (ATR): 1737 (C=O) cm -1 ; 1 H-NMR in CDCl 3 δ (ppm): (4, m, -CH=CH-), (4, t, O-CH 2 -), (4, t, O=CCH 2 - ), (8, m, -CH=CCH 2 -), (8, m, O-CCH 2 -, O=CCCH 2 -), (44, m, C-CH 2 -), (6, t, C-CH 3 ). MS (ESI): calculated for C 42 H 78 O 4 646, found m/z 664 ([M + NH 4 ] + ) nonane-1,9-diyl di IR (ATR): 1737 (C=O) cm -1 ; 1 H-NMR in CDCl 3 δ (ppm): (4, m, -CH=CH-), (4, t, O-CH 2 -), (4, t, O=CCH 2 - ), (8, m, -CH=CCH 2 -), (8, m, O-CCH 2 -, O=CCCH 2 -), (50, m, C-CH 2 -), (6, t, C-CH 3 ). MS (ES): calculated for C 45 H 84 O 4 688, found m/z 706 ([M + NH 4 ] + ) decane-1,10-diyl di IR (ATR): 1737 (C=O) cm -1 ; 1 H-NMR in CDCl 3 δ (ppm): (4, m, -CH=CH-), (4, t, O-CH 2 -), (4, t, O=CCH 2 - ), (8, m, -CH=CCH 2 -), (8, m, O-CCH 2 -, O=CCCH 2 -), (52, m, C-CH 2 -), (6, t, C-CH 3 ). MS (ESI): calculated for C 46 H 86 O 4 702, found m/z 720 ([M + NH 4 ] + ) propane-1,3-diyl (13Z,13'Z)-bis(docos butane-1,4-diyl (13Z,13'Z)-bis(docos hexane-1,6-diyl (13Z,13'Z)-bis(docos nonane-1,9-diyl (13Z,13'Z)-bis(docos decane-1,10-diyl (13Z,13'Z)-bis(docos-13- Asymmetric unsaturated diesters: (dec-9-enoyloxy)propyl IR (ATR): 1721 (C=O) cm -1 ; 1 H-NMR in CDCl 3 δ (ppm): (6, m, C-CH 3 ), (56, m, C-CH 2 -), (4, m, O=CCCH 2 -), (2, m, O-CCH 2 -), (8, m, - CH=CCH 2 -), 2.29 (4, t, O=CCH 2 -), 4.14 (4, t, O-CH 2 -), 5.34 (4, t, - CH=CH-). MS (ESI): calculated for C 47 H 88 O 4 717, found m/z 740 ([M + Na] + ). IR (ATR): 1723 (C=O) cm -1 ; 1 H-NMR in CDCl 3 δ (ppm): (6, m, C-CH 3 ), (56, m, C-CH 2 -), (4, m, O=CCCH 2 -), (4, m, O-CCH 2 -), (8, m, - CH=CCH 2 -), 2.29 (4, t, O=CCH 2 -), (4, m, O-CH 2 -), (4, m, -CH=CH-). MS (ESI): calculated for C 48 H 90 O 4 731, found m/z 754 ([M + Na] + ). IR (ATR): 1725 (C=O) cm -1 ; 1 H-NMR in CDCl 3 δ (ppm): (6, m, C-CH 3 ), (56, m, C-CH 2 -), 1.38 (4, dt, O-CCCH 2 -), (8, m, O=CCCH 2 -, O-CCH 2 -), (8, m, - CH=CCH 2 -), 2.28 (4, t, O=CCH 2 -), 4.05 (4, t, O-CH 2 -), 5.34 (4, t, - CH=CH-). MS (ESI): calculated for C 50 H 94 O 4 759, found m/z 782 ([M + Na] + ). IR (ATR): 1725 (C=O) cm -1 ; 1 H-NMR in CDCl 3 δ (ppm): (6, m, C-CH 3 ), (66, m, C-CH 2 -), 1.61 (8, quin, O=CCCH 2 -, O-CCH 2 -), (8, m, -CH=CCH 2 -), 2.28 (4, t, O=CCH 2 -), 4.05 (4, t, O-CH 2 -), (4, m, -CH=CH-). MS (ESI): calculated for C 53 H 100 O 4 801, found m/z 802 ([M + H] + ). IR (ATR): 1724 (C=O) cm -1 ; 1 H-NMR in CDCl 3 δ (ppm): (6, m, C-CH 3 ), (68, m, C-CH 2 -), 1.60 (8, quin, O=CCCH 2 -, O-CCH 2 -), (8, m, -CH=CCH 2 -), 2.27 (4, t, O=CCH 2 -), 4.04 (4, t, O-CH 2 -), (4, m, -CH=CH-). MS (ESI): calculated for C 54 H 102 O 4 815, found m/z 838 ([M + Na] + ). IR (ATR): 1738 (C=O) cm -1 ; 1 H-NMR in CDCl 3 δ (ppm): (1, m, CH 2 =CH-), (2, m, -CH=CH-), (2, qd, - S3

4 CH=CH 2 ), (4, t, O-CH 2 -), (4, t, O=CCH 2 -), (6H, m, -CH=CCH 2 -), (2H, m, O-CCH 2 -), (4H, m, O=CCCH 2 -), (28, m, C-CH 2 -), (3, t, C- CH 3 ). MS (ESI): calculated for C 31 H 56 O 4 493, found m/z 511 ([M + NH 4 ] + ) (dec-9-enoyloxy)butyl (dec-9-enoyloxy)hexyl (dec-9-enoyloxy)nonyl (oleoyloxy)propyl (Z)- docos-13-enoate (oleoyloxy)butyl (Z)- docos-13-enoate (oleoyloxy)hexyl (Z)- docos-13-enoate (oleoyloxy)nonyl (Z)- docos-13-enoate (oleoyloxy)decyl (Z)- docos-13-enoate IR (ATR): 1735 (C=O) cm -1 ; 1 H-NMR in CDCl 3 δ (ppm): (1, m, CH 2 =CH-), (2, m, -CH=CH-), (2, qd, - CH=CH 2 ), (4, t, O-CH 2 -), (4, t, O=CCH 2 -), (6H, m, -CH=CCH 2 -), (4H, m, O-CCH 2 -), (4H, m, O=CCCH 2 -), (28, m, C-CH 2 -), (3, t, C- CH 3 ). MS (ESI): calculated for C 32 H 58 O 4 507, found m/z 525 ([M + NH 4 ] + ). IR (ATR): 1735 (C=O) cm -1 ; 1 H-NMR in CDCl 3 δ (ppm): (1, m, CH 2 =CH-), (2, m, -CH=CH-), (2, qd, - CH=CH 2 ), (4, t, O-CH 2 -), (4, t, O=CCH 2 -), (6H, m, -CH=CCH 2 -), (8H, m, O-CCH 2 -, O=CCCH 2 - ), (4H, m, O-CCCH 2 -), (28, m, C-CH 2 -), (3, t, C-CH 3 ). MS (ESI): calculated for C 34 H 62 O 4 535, found m/z 553 ([M + NH 4 ] + ). IR (ATR): 1735 (C=O) cm -1 ; 1 H-NMR in CDCl 3 δ (ppm): (1, m, CH 2 =CH-), (2, m, -CH=CH-), (2, qd, - CH=CH 2 -), (4, t, O-CH 2 -), (4, t, O=CCH 2 -), (6H, m, -CH=CCH 2 -), (8H, m, O-CCH 2 -, O=CCCH 2 -), (38, m, C-CH 2 -), (3, t, C-CH 3 ). MS (ES): calculated for C 37 H 68 O 4 577, found m/z 578 ([M + H] + ). IR (ATR): 1738 (C=O) cm -1 ; 1 H-NMR in CDCl 3 δ (ppm): (6, m, C-CH 3 ), (48, m, C-CH 2 -), (4, m, O=CCCH 2 -), (2, m, O-CCH 2 -), (8, m, - CH=CCH 2 -), (4, t, O=CCH 2 -), (4, m, O-CH 2 -), (4, m, -CH=CH-). IR (ATR): 1738 (C=O) cm -1 ; 1 H-NMR in CDCl 3 δ (ppm): (6, m, C-CH 3 ), (48, m, C-CH 2 -), (4, m, O=CCCH 2 -), (4, m, O-CCH 2 -), (8, m, - CH=CCH 2 -), (4, t, O=CCH 2 -), (4, m, O-CH 2 -), (4, m, -CH=CH-). MS (ESI): calculated for C 44 H 82 O 4 675, found m/z 693 ([M + NH 4 ] + ). IR (ATR): 1737 (C=O) cm -1 ; 1 H-NMR in CDCl 3 δ (ppm): (6, t, C-CH 3 ), (48, m, C-CH 2 -), (4, m, O-CCCH 2 - ), (8, m, O=CCCH 2 -, O-CCH 2 -), (8, m, - CH=CCH 2 -), (4, t, O=CCH 2 -), (4, t, O-CH 2 -), (4, m, -CH=CH-). MS (ESI): calculated for C 46 H 86 O 4 703, found m/z 726 ([M + Na] + ). 1 H-NMR in CDCl 3 δ (ppm): (6, m, C-CH 3 ), (58, m, C-CH 2 ), (8, quin, O=CCCH 2 -, O-CCH 2 -), (8, m, -CH=CCH 2 -), (4, t, O=CCH 2 -), (4, t, O-CH 2 -), (4, m, -CH=CH-). IR (ATR): 1728 (C=O) cm -1 ; 1 H-NMR in CDCl 3 δ (ppm): (6, m, C-CH 3 ), (60, m, C-CH 2 -), (8, m, S4

5 O=CCCH 2 -, O-CCH 2 -), (8, m, C=CCH 2 -), (4, t, O=CCH 2 -), (4, t, O-CH 2 -), (4, m, -CH=CH-). MS (ESI): calculated for C 50 H 94 O 4 759, found m/z 782 ([M + Na] + ). Asymmetric saturated-unsaturated diesters: (palmitoyloxy)propyl (palmitoyloxy)butyl (palmitoyloxy)hexyl (palmitoyloxy)decyl (palmitoyloxy)propyl (Z)-docos-13-enoate (palmitoyloxy)butyl (Z)-docos-13-enoate (palmitoyloxy)hexyl (Z)-docos-13-enoate (palmitoyloxy)nonyl (Z)-docos-13-enoate IR (ATR): 1717 (C=O) cm -1 ; 1 H-NMR in CDCl 3 δ (ppm): (6, m, C-CH 3 ), (44, m, C-CH 2 -), (4, m, O=CCCH 2 -), (2, m, O-CCH 2 -), (4, m, C=CCH 2 - ), (4, t, O=CCH 2 -), (4, t, O-CH 2 -), (2, m, -CH=CH-). MS (ESI): calculated for C 37 H 70 O 4 579, found m/z 602 ([M + Na] + ). IR (ATR): 1725 (C=O) cm -1 ; 1 H-NMR in CDCl 3 δ (ppm): (6, m, C-CH 3 ), (44, m, C-CH 2 -), (4, m, O=CCCH 2 -), (4, m, O-CCH 2 -), (4, m, - CH=CCH 2 -), (4, t, O=CCH 2 -), (4, t, O-CH 2 -), (2, m, -CH=CH-). MS (ESI): calculated for C 38 H 72 O 4 593, found m/z 616 ([M + Na] + ). IR (ATR): 1727 (C=O) cm -1 ; 1 H-NMR in CDCl 3 δ (ppm): (6, m, C-CH 3 ), (44, m, C-CH 2 -), (4, m, O- CCCH 2 -), (8, m, O=CCCH 2 -, O-CCH 2 -), (4, m, - CH=CCH 2 -), (4, t, O=CCH 2 -), (4, t, O-CH 2 -), (2, m, -CH=CH-). MS (ESI): calculated for C 40 H 76 O 4 621, found m/z 644 ([M + Na] + ). IR (ATR): 1729 (C=O) cm -1 ; 1 H-NMR in CDCl 3 δ (ppm): (6, m, C-CH 3 ), (56, m, C-CH 2 -), (8, m, O=CCCH 2 -, O-CCH 2 -), (4, m, -CH=CCH 2 -), (4, t, O=CCH 2 -), (4, t, O-CH 2 -), (2, m, -CH=CH-). MS (ESI): calculated for C 44 H 84 O 4 677, found m/z 700 ([M + Na] + ). IR (ATR): 1725 (C=O) cm -1 ; 1 H-NMR in CDCl 3 δ (ppm): (6, t, C-CH 3 ), (52, m, C-CH 2 -), (4, m, O=CCCH 2 -), (2, m, O-CCH 2 -), (4, m, - CH=CCH 2 -), (4, t, O=CCH 2 -), (4, t, O-CH 2 -), (2, m, -CH=CH-). MS (ESI): calculated for C 41 H 78 O 4 635, found m/z 658 ([M + Na] + ). IR (ATR): 1726 (C=O) cm -1 ; 1 H-NMR in CDCl 3 δ (ppm): (6, t, C-CH 3 ), (52, m, C-CH 2 -), (4, m, O=CCCH 2 -), (4, m, O-CCH 2 -), (4, m, - CH=CCH 2 -), (4, t, O=CCH 2 -), 4.09 (4, m, O-CH 2 -), (2, m, -CH=CH-). MS (ESI): calculated for C 42 H 80 O 4 649, found m/z 672 ([M + Na] + ). IR (ATR): 1725 (C=O) cm -1 ; 1 H-NMR in CDCl 3 δ (ppm): (6, t, C-CH 3 ), (52, m, C-CH 2 -), (4, m, O-CCCH 2 - ), (8, m, O=CCCH 2 -, O-CCH 2 -), (4, m, - CH=CCH 2 -), (4, t, O=CCH 2 -), (4, m, O-CH 2 -), (2, m, -CH=CH-). MS (ESI): calculated for C 44 H 84 O 4 677, found m/z 700 ([M + Na] + ). IR (ATR): 1735 (C=O) cm -1 ; 1 H-NMR in CDCl 3 δ (ppm): (6, t, C-CH 3 ), (62, m, C-CH 2 -), (8, m, O-CCH 2 -, S5

6 O=CCCH 2 -), (4, m, -CH=CCH 2 -), (4, t, O=CCH 2 -), (4, m, O-CH 2 -), (2, m, -CH=CH-). MS (ESI): calculated for C 47 H 90 O 4 719, found m/z 720 ([M + H] + ) (palmitoyloxy)decyl (Z)-docos-13-enoate IR (ATR): 1728 (C=O) cm -1 ; 1 H-NMR in CDCl 3 δ (ppm): (6, t, C-CH 3 ), (64, m, C-CH 2 ), (8, m, O-CCH 2 -, O=CCCH 2 -), (4, m, -CH=CCH 2 -), (4, t, O=CCH 2 -), (4, m, O-CH 2 -), (2, m, -CH=CH-). MS (ESI): calculated for C 48 H 92 O 4 733, found m/z 734 ([M + H] + ). S6

7 Scheme S.1: Synthesis of symmetric diesters from fatty acids and diols. Scheme S.2: Showing the two-stage syntheses of asymmetric diesters. Given in brackets are the reaction conditions and products when fatty acid chlorides are used instead of fatty acids. S7

8 (a) 10-n-10 (b) 10-n-18 (c) 16-n-18 (d) 16-n-22 (e) 18-n-22 (f) 22-n-22 Heat Flow (W/g; exo up) P 1 P 1 P 1 P T P 1 P T P 1 n= Temperature ( o C) Figure S.1: DSC cooling (3 C/min) thermograms obtained for the linear aliphatic diesters. P 1, and P T are the lead, main, and tail peak events, respectively. (a) 10-n-10 (b) 10-n-18 (c) 16-n-18 (d) 16-n-22 (e) 18-n-22 (f) 22-n-22 Heat Flow (W/g; endo down) n=2 PR(2) P R(1) P R P R P Temperature ( o C) Figure S.2: DSC heating (3 C/min) thermograms of linear aliphatic diesters. shows the main endotherm, and P R shows the exotherm from the crystallization mediated by melt. P 1 and show the melting of the two most stable phases in order of decreasing stability. S8

9 (a) (b) Intensity (counts) Heat Flow (W/g; exo up) Scattering angle (2θ, degree) Temperature ( o C) Figure S.3: (a) WAXD plots for and diesters obtained at 0 C and -25 C, respectively using a cooling rate of 1 C/min; d-spacing values, in Angstroms, are given at the top of the characteristic peaks. (b) DSC cooling profiles of and obtained using the same thermal protocol as was used for determination of the WAXD profiles; arrows show the temperature at which the WAXD was taken. S9

10 12 (a) n6 n n3 n2 Shear stress (Pa) (b) n9 n10 40 n6,3 n Shear rate (1/s) Figure S.4: Shear rate versus shear stress plots of representative diester series measured at 40 C (a) 10-n-10 and (b) 22-n-22 diesters. Dashed lines are linear fits (r 2 > ) to the Herschel- Bulkley model. S10

11 Viscosity (mpa.s) (a) n2 n3 n4 n6 (b) n3 n4 n6 n9 n Temperature ( o C) Figure S.5: Temperature-Viscosity profiles of representative diester series (a) 10-n-10; and (b) 22-n-22. Cooling rate 3 C/min. Dashed lines are guides for the eye. S11