Synthesis and Characterization of Poly(myrcene-co- dibutyl itaconate)
Supporting Information
A Green Approach Towards Sustainable Polymer: Synthesis and Characterization of Poly(myrcene-codibutyl itaconate) Preetom Sarkar and Anil K. Bhowmick*
Rubber Technology Centre, Indian Institute of Technology Kharagpur Kharagpur - 721302, West Bengal, India *Corresponding author: Email: [email protected] (AKB) Tel.: +91 (3222) 283180; Fax: +91 (3222) 220312
Total number of pages: 14 (Page S1 – Page S14) Total number of figures: 15 (Figure S1 – Figure S15) Total number of tables: 4 (Table S1 – Table S4)
S1
CONTENTS Figure S1. Temperature and time dependence of Poly(MY0DBI100) synthesis on yield and molecular weight ……………………………………………………………………………S3 Figure S2. Temperature and time dependence of Poly(MY100DBI0) synthesis on yield and molecular weight…………………………………………………………………………….S3 Figure S3. Monitoring of the polymerization kinetics………………………………………S4 Figure S4. Variation of Mn with Z-average diameter of latex particles for copolymers…....S4 Figure S5. DLS particle size distribution profiles for copolymer latices………….....……...S5 Figure S6. FESEM image of poly(MY50DBI50) latex……………………………….............S5 Calculation of theoretical solubility parameter……………………………………...........S6 Table S1. Group Contributions for Solubility Parameter Component……………................S6 Table S2. Assignments of FTIR Peaks for Various Homo and Co-polymers……………….S7 Figure S7. 1H and 13C NMR spectra of DBI monomer..........................................................S8 Figure S8. 1H and 13C NMR spectra of poly(MY0DBI100)....................................................S9 Figure S9. 1H and 13C NMR spectra of β-myrcene monomer...............................................S10 Table S3. Parameters used in FR and KT method ………………………………………...S11 Figure S10. Plot of DBI mole fraction in feed and copolymer.............................................S11 Figure S11. X-ray diffractograms of various polymers…….....…………………………...S12 Figure S12. DSC thermogram of various polymers……………………………………….S12 Table S4. Glass transition temperature of various polymers................................................S13 Figure S13. Temperature sweep plot for poly(MY50DBI50) copolymer..............................S13 Figure S14. Variation of Tan δ with DBI content at 25 and 60 °C……….................…….S14 Figure S15. TGA curves of pristine polymers and various copolymers…………………..S14
S2
Figure S1. Temperature and time dependence of Poly(MY0DBI100) synthesis on yield and molecular weight.
Figure S2. Temperature and time dependence of Poly(MY100DBI0) synthesis on yield and molecular weight.
S3
Figure S3. Monitoring of the polymerization kinetics (X = % conversion, R2 = regression coefficient, kapp = apparent rate constant).
Figure S4. Variation of Mn with Z-average diameter of latex particles for copolymers.
S4
Figure S5. DLS particle size distribution profiles for copolymer latices.
Figure S6. FESEM image of poly(MY50DBI50) latex.
S5
Calculation of theoretical solubility parameter. The theoretical solubility parameter was calculated following the method proposed by Hoftyzer and van Krevelen. According to the group contribution principle, the solubility parameter components may be predicted using the following set of equations:
=
∑
; =
∑
and =
∑
(S1)
Thus, the corresponding equation for determination of solubility parameter (δ) becomes:
= + +
(S2)
The solubility parameter components δd, δp, and δh are the contributions of dispersion forces, polar forces and hydrogen bonding respectively. Fdi and Fpi are the molar attraction constants for dispersion and polar forces. Ehi is the cohesive energy for hydrogen bonding and V is molar volume of the structural unit of the polymer. Table S1 enlists values of these parameters for various structural units. Table S1. Group Contributions for Solubility Parameter Component (Reference 34)
structural
Fdi
Fpi
Ehi
V
units
(MJ/m3)1/2. Mol-1
(MJ/m3)1/2. Mol-1
J. mol-1
cm3. mol-1
–CH3
420
0
0
33.5
–CH2–
270
0
0
16.1
=CH-
200
0
0
13.5
>CH-
80
0
0
-1.0
=CH2
400
0
0
28.5
=C
C
A Green Approach Towards Sustainable Polymer: Synthesis and Characterization of Poly(myrcene-codibutyl itaconate) Preetom Sarkar and Anil K. Bhowmick*
Rubber Technology Centre, Indian Institute of Technology Kharagpur Kharagpur - 721302, West Bengal, India *Corresponding author: Email: [email protected] (AKB) Tel.: +91 (3222) 283180; Fax: +91 (3222) 220312
Total number of pages: 14 (Page S1 – Page S14) Total number of figures: 15 (Figure S1 – Figure S15) Total number of tables: 4 (Table S1 – Table S4)
S1
CONTENTS Figure S1. Temperature and time dependence of Poly(MY0DBI100) synthesis on yield and molecular weight ……………………………………………………………………………S3 Figure S2. Temperature and time dependence of Poly(MY100DBI0) synthesis on yield and molecular weight…………………………………………………………………………….S3 Figure S3. Monitoring of the polymerization kinetics………………………………………S4 Figure S4. Variation of Mn with Z-average diameter of latex particles for copolymers…....S4 Figure S5. DLS particle size distribution profiles for copolymer latices………….....……...S5 Figure S6. FESEM image of poly(MY50DBI50) latex……………………………….............S5 Calculation of theoretical solubility parameter……………………………………...........S6 Table S1. Group Contributions for Solubility Parameter Component……………................S6 Table S2. Assignments of FTIR Peaks for Various Homo and Co-polymers……………….S7 Figure S7. 1H and 13C NMR spectra of DBI monomer..........................................................S8 Figure S8. 1H and 13C NMR spectra of poly(MY0DBI100)....................................................S9 Figure S9. 1H and 13C NMR spectra of β-myrcene monomer...............................................S10 Table S3. Parameters used in FR and KT method ………………………………………...S11 Figure S10. Plot of DBI mole fraction in feed and copolymer.............................................S11 Figure S11. X-ray diffractograms of various polymers…….....…………………………...S12 Figure S12. DSC thermogram of various polymers……………………………………….S12 Table S4. Glass transition temperature of various polymers................................................S13 Figure S13. Temperature sweep plot for poly(MY50DBI50) copolymer..............................S13 Figure S14. Variation of Tan δ with DBI content at 25 and 60 °C……….................…….S14 Figure S15. TGA curves of pristine polymers and various copolymers…………………..S14
S2
Figure S1. Temperature and time dependence of Poly(MY0DBI100) synthesis on yield and molecular weight.
Figure S2. Temperature and time dependence of Poly(MY100DBI0) synthesis on yield and molecular weight.
S3
Figure S3. Monitoring of the polymerization kinetics (X = % conversion, R2 = regression coefficient, kapp = apparent rate constant).
Figure S4. Variation of Mn with Z-average diameter of latex particles for copolymers.
S4
Figure S5. DLS particle size distribution profiles for copolymer latices.
Figure S6. FESEM image of poly(MY50DBI50) latex.
S5
Calculation of theoretical solubility parameter. The theoretical solubility parameter was calculated following the method proposed by Hoftyzer and van Krevelen. According to the group contribution principle, the solubility parameter components may be predicted using the following set of equations:
=
∑
; =
∑
and =
∑
(S1)
Thus, the corresponding equation for determination of solubility parameter (δ) becomes:
= + +
(S2)
The solubility parameter components δd, δp, and δh are the contributions of dispersion forces, polar forces and hydrogen bonding respectively. Fdi and Fpi are the molar attraction constants for dispersion and polar forces. Ehi is the cohesive energy for hydrogen bonding and V is molar volume of the structural unit of the polymer. Table S1 enlists values of these parameters for various structural units. Table S1. Group Contributions for Solubility Parameter Component (Reference 34)
structural
Fdi
Fpi
Ehi
V
units
(MJ/m3)1/2. Mol-1
(MJ/m3)1/2. Mol-1
J. mol-1
cm3. mol-1
–CH3
420
0
0
33.5
–CH2–
270
0
0
16.1
=CH-
200
0
0
13.5
>CH-
80
0
0
-1.0
=CH2
400
0
0
28.5
=C
C
