Long-chain aliphatic polyesters from plant oils for injection molding, film extrusion and electrospinning

Transcription

1 Electronic Supplementary Material (ESI) for Green Chemistry. This journal is The Royal Society of Chemistry 14 Electronic Supplementary Information (ESI) for Long-chain aliphatic polyesters from plant oils for injection molding, film extrusion and electrospinning Florian Stempfle, a Benjamin S. Ritter, b,c Rolf Mülhaupt*, b,c and Stefan Mecking* a Both authors contributed equally to this work. a Chair of Chemical Materials Science, University of Konstanz, Department of Chemistry, Universitätsstraße 1, Konstanz, Germany. stefan.mecking@uni-konstanz.de; Fax: ; Tel: b Freiburg Materials Research Center (FMF), Stefan-Meier-Straße 1, D-7914 Freiburg, Germany. rolf.muelhaupt@makro.uni-freiburg.de; Fax: ; Tel: c Institute for Macromolecular Chemistry of the University of Freiburg, Stefan-Meier-Straße 31, D-7914 Freiburg, Germany Table of content Dimethyl-1,19-nonadecanedioate Dimethyl-1,3-tricosanedioate Poly[1,19-nonadecadiyl-1,19-nonadecanedioate] (PE-19.19) Poly[1,3-tricosadiyl-1,3-tricosanedioate] (PE-3.3) Rheological properties Tensile properties Electrospinning Dynamic mechanical analysis Polyester compounds DMA-analyses of PE polymer compound DSC-analyses of PE polymer compound DMA-analyses of PE-3.3 polymer compound DSC-analyses of PE-3.3 polymer compound SEM images of the polymer compounds S S3 S4 S5 S6 S9 S1 S11 S1 S13 S18 S3 S8 S33 S1

2 Dimethyl-1,19-nonadecanedioate 5 1 O O O O 1 1 H NMR (CDCl 3, 5 C, 4 MHz): δ 3.66 (s, 6H, H-1),.3 (t, 3 J H-H = 7.6 Hz, 4H, H-3), (m, 4H, H), (m, 6H, H-5). 13 C NMR (CDCl 3, 5 C, 11 MHz): δ (s, C-), (s, C-1), 34.8 (s, C-3), (C-5), 5.1 (s, C). Figure S1: Gas chromatogram (1. min isothermal at 9 C, 3 K min -1 to 8 C, 8 min) isothermal of pure dimethyl-1,19-nonadecanedioate. S

3 Dimethyl-1,3-tricosanedioate 5 1 O O O O 1 1 H NMR (CDCl 3, 5 C, 4 MHz) δ 3.66 (s, 6H, H-1),.9 (t, 3 J H-H = 7.6 Hz, 4H, H-3), (m, 4H, H), (m, 34H, H-5). 13 C NMR (CDCl 3, 5 C, 11 MHz): δ (s, C-), (s, C-1), 34.7 (s, C-3), (C-5), 5.1 (s, C). Figure S: Gas chromatogram (1. min isothermal at 9 C, 3 K min -1 to 8 C, 8 min) of pure dimethyl-1,3- tricosanedioate. S3

4 Poly[1,19-nonadecadiyl-1,19-nonadecanedioate] (PE-19.19) Figure S3: GPC trace (16 C in 1,,4-trichlorobenzene, vs. linear polyethylene standards) of PE Figure S4: DSC trace (1 K min -1 and rate, respectively; data reported are from second cycles) of PE S4

5 Poly[1,3-tricosadiyl-1,3-tricosanedioate] (PE-3.3) Figure S5: GPC trace (16 C in 1,,4-trichlorobenzene, vs. linear polyethylene standards) of PE-3.3. Figure S6: DSC trace (1 K min -1 and rate, respectively; data reported are from second cycles) of PE S5

6 Rheological properties Figure S7: Isothermals of G` and G`` for rheological study of PE (gap =.5 mm). In order to obtain the master curves the isotherms were shifted only in horizontal dimension (b T = 1) at a reference temperature of T = 15 C using the following a T -values: Table S1: a T -values of PE entry temperature [K] a T -value Figure S8: temperature dependence of the a T -values measured from PE S6

7 Figure S9: Isothermals of G` and G`` for rheological study of PE-3.3 (gap =.5 mm). In order to obtain the master curves the isotherms were shifted only in horizontal dimension (b T = 1) at a reference temperature of T = 15 C using the following a T -values: Table S: a T -values of PE-3.3. entry temperature [K] a T -value Figure S1: temperature dependence of the a T -values measured from PE-3.3. S7

8 Figure S11: Master curves of G` and G`` for PE (from measurements at 11, 1, 13, 14, 15, 16, 18 and 19 C). Shifting temperature is 15 C. Figure S1: Master curves of G` and G`` for PE-3.3 (from measurements at 11, 1, 13, 14, 15, 16 and 18 C). Shifting temperature is 15 C. To determine zero-shear viscosity from experimental data, Carreau-Yasuda 1 equation is used: η` = η (1 + aω α ) β Were η stands for complex viscosity, η o is zero-shear viscosity, with ω for frequency and a, α and β are fitting parameters. The values of parameters in Carreau-Yasuda equation for the studied samples are reported in Table S3. Table S3: Fitted parameters for Carreau-Yasuda equation. S8

9 a α β η [Pa s] PE ± 6 PE ± 4 Tensile properties Figure S13: Left: Stress-strain curves (constant drawing rate of 5 mm min -1, room temperature) of PE-3.3. Right: Image of test bar for tensile testing before and after strain experiment. S9

10 Electrospinning Figure S14: SEM images of electrospun PE19.19 fibers. Figure S15: SEM images of electrospun PE3.3 fibers. S1

11 Dynamic mechanical analysis Dynamic mechanical analyses (DMA, at a frequency of 1 Hz) of PE-3.3 exhibit a glass transition a around -7 C; the second relaxation phenomenon at around -13 C can be ascribed to the motion of the methylene sequences of the polyester main-chain (Figure S16). Figure S16: Dynamic mechanical analysis (deformation of.1 % and frequency of 1Hz) of PE-3.3. a Glass transition temperatures (T g ) were determined from maximum in loss modulus (G``). S11

12 Polyester compounds Long-chain polyesters (PE and PE-3.3) were blended with various types of commercially available thermoplastics such as linear low density polyethylene (LLDPE, Affinity 8G) and high density polyethylene (HDPE, Hostalen GC 76), as well as a thermoplastic elastomer (SEBS, Kraton G1643 MS) and a biodegradable aliphatic-aromatic polyester (Ecoflex F Blend C1, BASF). Thermal properties of these blends were determined by means of both DMA and DSC measurements. The observation of the thermal transitions of the individual components (and also the moduli) support that the blended polymer combinations studied are not miscible (c.f. Table S4). Table S4: Thermo-mechanical properties of different polymer blends. T a g / T b g / T a m / T a c / (RT) b / (RT) b / ( C) ( C) ( C) ( C) (Pa) (Pa) PE (neat) PE-3.3 (neat) Affinity 8G (neat) PE-19.19/Affinity 8G (15:85 wt.) /13 44/9 48 PE-3.3/Affinity 8G (15:85 wt.) 66/16 46/9 34 Kraton G1643MS (neat) PE-19.19/Kraton G1643MS (15:85 wt.) PE-3.3/Kraton G1643MS (15:85 wt.) / Ecoflex F Blend C1 (neat) PE-19.19/Ecoflex F Blend C1 (15:85 wt.) PE-3.3/Ecoflex F Blend C1 (15:85 wt.) / Hostalen GC 76 (neat) PE-19.19/Hostalen GC 76 (15:85 wt.) - 4 1/134 87/ PE-3.3/Hostalen GC 76 (15:85 wt.) 16/136 93/ a Determined by DSC with a / rate of 15 K min 1. b Determined by DMA (1 Hz,.1 % deformation). S1

13 DMA-analyses of PE polymer compound ; [MPa] Figure S17: Dynamic mechanical analysis (deformation of.1 % and frequency of 1Hz) of PE filled with 5 wt.% talc ,3 ; [MPa] ,, Figure S18: Dynamic mechanical analysis (deformation of.1 % and frequency of 1Hz) of PE filled with 45 wt.% talc. S13

14 15 15,3 ; [MPa] ,,1 5, Figure S19: Dynamic mechanical analysis (deformation of.1 % and frequency of 1Hz) of 15 wt. % PE in Affinity 8G (LLDPE). 75,3 ; [MPa] 5 5,,1, Figure S: Dynamic mechanical analysis (deformation of.1 % and frequency of 1Hz) of 5 wt. % PE in Affinity 8G (LLDPE). S14

15 ,8,6 ; [MPa] ,4,, -5 5 Figure S1: Dynamic mechanical analysis (deformation of.1 % and frequency of 1Hz) of 15 wt. % PE in Kraton G1643 MS (SEBS) ,6 ; [MPa] ,4, 5, Figure S: Dynamic mechanical analysis (deformation of.1 % and frequency of 1Hz) of 5 wt. % PE in Kraton G1643 MS (SEBS). S15

16 3 5,3 ; [MPa] 15 1,,1 5, Figure S3: Dynamic mechanical analysis (deformation of.1 % and frequency of 1Hz) of 15 wt. % PE in Ecoflex F Blend C1. 3 5,3 ; [MPa] 15 1,,1 5, Figure S4: Dynamic mechanical analysis (deformation of.1 % and frequency of 1Hz) of 5 wt. % PE in Ecoflex F Blend C1. S16

17 35 3,4 5 ; [MPa] 15 1, 5, Figure S5: Dynamic mechanical analysis (deformation of.1 % and frequency of 1Hz) of 5 wt. % PE in Hostalen GC 76 (HDPE). S17

18 DSC-analyses of PE polymer compound 4 PE-19.19_talc_5 Heat Flow [W/g] - = 18 C = 9 J g -1 = 87 C -6 = - 86 J g Figure S6: DSC analysis (15 K min -1 and rate, respectively; data reported are from second cycles) of PE filled with 5 wt.% talc. 4 PE-19.19_talc_45 Heat Flow [W/g] - = 17 C = 75 J g -1 = 88 C = - 74 J g Figure S7: DSC analysis (15 K min -1 and rate, respectively; data reported are from second cycles) of PE filled with 45 wt.% talc. S18

19 Heat Flow [W/g] = 68 C = 4 J g -1 = 13 C = 8 J g -1 = 44 C = - 1 J g -1 = 9 C = - 1 J g PE-19.19_Affinity_85 Figure S8: DSC analysis (15 K min -1 and rate, respectively; data reported are from second cycles) of 15 wt. % PE in Affinity 8G (LLDPE). 4 PE-19.19_Affinity_95 3 Heat Flow [W/g] = 66 C = 5 J g -1 = 1 C = 6 J g -1 = 43 C = - 1 J g -1 = 86 C = - 7 J g -1 Figure S9: DSC analysis (15 K min -1 and rate, respectively; data reported are from second cycles) of 5 wt. % PE in Affinity 8G (LLDPE). S19

20 4 PE-19.19_SEBS_85 = 4 C Heat Flow [W/g] = 11 C = 9 J g -1 = 87 C = - 9 J g Figure S3: DSC analysis (15 K min -1 and rate, respectively; data reported are from second cycles) of 15 wt. % PE in Kraton G1643 MS (SEBS). 4 PE-19.19_SEBS_95 T g = 6 C Heat Flow [W/g] - -6 = 48 C = - J g -1 = 1 C = 5 J g -1 = 86 C = - 3 J g Figure S31: DSC analysis (15 K min -1 and rate, respectively; data reported are from second cycles) of 5 wt. % PE in Kraton G1643 MS (SEBS). S

21 5 PE-19.19_Ecoflex_ Heat Flow [W/g] T g = -34 C = 1 C = 11 J g -1-3 = 88 C = - 14 J g Figure S3: DSC analysis (15 K min -1 and rate, respectively; data reported are from second cycles) of 15 wt. % PE in Ecoflex. Heat Flow [W/g] T g = -34 C = 11 C = 1 J g -1 = 9 C = - 18 J g PE-19.19_Ecoflex_95 Figure S33: DSC analysis (15 K min -1 and rate, respectively; data reported are from second cycles) of 5 wt. % PE in Ecoflex F Blend C1. S1

22 4 PE-19.19_Hostalen_75 Heat Flow [W/g] - -6 = 134 C = 138 J g -1 = 1 C = 19 J g -1 = 87 C = - 18 J g = 115 C = - 13 J g Figure S34: DSC analysis (15 K min -1 and rate, respectively; data reported are from second cycles) of 5 wt. % PE in Hostalen GC 76 (HDPE). S

23 DMA-analyses of PE-3.3 polymer compounds 4 35,3 3 ; [MPa] ,,1 5, Figure S35: Dynamic mechanical analysis (deformation of.1 % and frequency of 1Hz) of PE-3.3 filled with 5 wt.% talc. 35,4 3 5 ; [MPa] 15 1, 5, Figure S36: Dynamic mechanical analysis (deformation of.1 % and frequency of 1Hz) of PE-3.3 filled with 45 wt.% talc. S3

24 15 15,3 ; [MPa] ,,1, Figure S37: Dynamic mechanical analysis (deformation of.1 % and frequency of 1Hz) of 15 wt. % PE-3.3 in Affinity 8G (LLDPE) ,3 ; [MPa] ,,1, Figure S38: Dynamic mechanical analysis (deformation of.1 % and frequency of 1Hz) of 5 wt. % PE-3.3 in Affinity 8G (LLDPE). S4

25 5,8,6 ; [MPa] ,4,, Figure S39: Dynamic mechanical analysis (deformation of.1 % and frequency of 1Hz) of 15 wt. % PE-3.3 in Kraton G1643 MS (SEBS).,8,6 ; [MPa] 1,4,, -5 5 Figure S4: Dynamic mechanical analysis (deformation of.1 % and frequency of 1Hz) of 5 wt. % PE-3.3 in Kraton G1643 MS (SEBS). S5

26 15,3, ; [MPa] 1 5,1, Figure S41: Dynamic mechanical analysis (deformation of.1 % and frequency of 1Hz) of 15 wt. % PE-3.3 in Ecoflex F Blend C1. 5,3 ; [MPa] ,,1, Figure S4: Dynamic mechanical analysis (deformation of.1 % and frequency of 1Hz) of 5 wt. % PE-3.3 in Ecoflex F Blend C1. S6

27 3 5,6 ; [MPa] 15 1,4, 5, Figure S43: Dynamic mechanical analysis (deformation of.1 % and frequency of 1Hz) of 15 wt. % PE-3.3 in Hostalen GC 76 (HDPE). S7

28 DSC-analyses of PE-3.3 polymer compound 4 PE-3.3_talc_5 = 18 C = 1 J g -1 Heat Flow [W/g] - -6 = 91 C = - 14 J g Figure S44: DSC analysis (15 K min -1 and rate, respectively; data reported are from second cycles) of PE-3.3 filled with 5 wt.% talc. 4 PE-3.3_talc_45 Heat Flow [W/g] - = 18 C = 93 J g = 94 C = - 86 J g Figure S45: DSC analysis (15 K min -1 and rate, respectively; data reported are from second cycles) of PE-3.3 filled with 45 wt.% talc. S8

29 4 PE-3.3_Affinity_85 Heat Flow [W/g] - = 66 C = 18 J g -1 = 16 C = 16 J g -1 = 46 C = - 1 J g -1 = 9 C = - 9 J g Figure S46: DSC analysis (15 K min -1 and rate, respectively; data reported are from second cycles) of 15 wt. % PE-3.3in Affinity 8G (LLDPE). 6 PE-3.3_Affinity_95 4 Heat Flow [W/g] - -6 = 66 C = 15 J g -1 = 47 C = - 1 J g -1 = 14 C = 5 J g Temperature [ C} Figure S47: DSC analysis (15 K min -1 and rate, respectively; data reported are from second cycles) of 5 wt. % PE-3.3 in Affinity 8G (LLDPE). S9

30 4 PE-3.3_SEBS_85 T g = -38 C Heat Flow [W/g] - = 54 C = - 1 J g -1 = 16 C = 17 J g -1 = 9 C = - 1 J g Figure S48: DSC analysis (15 K min -1 and rate, respectively; data reported are from second cycles) of 15 wt. % PE-3.3 in Kraton G1643 MS (SEBS). 6 PE-3.3_SEBS_95 4 Heat Flow [W/g] - T g = -37 C = 53 C = - J g -1 = 15 C = 4 J g Figure S49: DSC analysis (15 K min -1 and rate, respectively; data reported are from second cycles) of 5 wt. % PE-3.3 in Kraton G1643 MS (SEBS). S3

31 4 PE-3.3_Ecoflex_85 Heat Flow [W/g] - = 16 C = 16 J g -1-6 = 79/ 9 C = - 13 J g Figure S5: DSC analysis (15 K min -1 and rate, respectively; data reported are from second cycles) of 15 wt. % PE-3.3 in Ecoflex F Blend C1. 4 PE-3.3_Ecoflex_95 Heat Flow [W/g] = 15 C = 5 J g -1 - = 79/91 C = - J g Figure S51: DSC analysis (15 K min -1 and rate, respectively; data reported are from second cycles) of 5 wt. % PE-3.3 in Ecoflex F Blend C1. S31

32 6 PE-3.3_Hostalen_85 4 = 136 C = 16 J g -1 Heat Flow [g/w] - = 16 C = 9 J g -1 = 93 C = - 9 J g = 116 C = J g Figure S5: DSC analysis (15 K min -1 and rate, respectively; data reported are from second cycles) of 15 wt. % PE-3.3 in Hostalen GC 76 (HDPE). S3

33 SEM images of the polymer compounds Figure S53: SEM images of PE filled with 45 wt.% talc. Figure S54: SEM images of PE-3.3 filled with 45 wt.% talc. Figure S55: SEM images of 5 wt. % PE in Hostalen GC 76 (HDPE). S33

34 Figure S56: SEM images of 15 wt. % PE-3.3 in Hostalen GC 76 (HDPE). Figure S57: SEM images of 15 wt. % PE-3.3 in Affinity 8G (LLDPE). S34

35 Figure S58: SEM images of 15 wt. % PE-3.3 in Kraton G1643 MS (SEBS). Figure S59: SEM images of 15 wt. % PE-3.3 in Ecoflex F Blend C1. 1 J. R. Prakash. J. Rheol.,, 46, S35