Star-Shaped and Linear POSS-Polylactide Hybrid Copolymers
Abstract
:1. Introduction
2. Results and Discussion
2.1. Synthesis of Reactive Initiators—6-Hydroxy-n-Hexylthio-2-Ethyl Functionalized POSS.
Symbol of Silsesquioxane | Precursors | –CH=CH2/ HS(CH2)6OH [mol/mol] | Time of Reaction [min] (a) | Conversion of Vinyl Groups (b) [mol%] | Sulfur Content [wt %] (c) | Contents of R (d) [mmol/1 g] |
---|---|---|---|---|---|---|
1 | POSS-Vi | 1 : 1.05 | 240 | 99.45 | 15.06 | 4.70 |
2 | POSS-Vi | 1 : 1.05 | 150 | 95.37 | 14.79 | 4.62 |
3 | POSS-Vi | 1 : 0.53 | 420 | 74.60 | 13.01 | 4.06 |
4 | iBu-POSS-Vi | 1 : 1.05 | 240 | 92.54 | 3.24 | 1.01 |
2.1.1. Spectroscopic Characterization of Functionalized POSS
2.1.2. MALDI-TOF Mass Spectra of 6-Hydroxy-n-Hexylthio-2-Ethyl Functionalized POSS (Macroinitiators for Polymerization of LA)
2.2. Synthesis of Star-Shaped and Linear POSS–Lactide Hybrids
Hybrid Polymers | Initiator Used | Content of R (a) in POSS Molecule | [LA]/[OH] [mol/mol] | Polymerization | ||
---|---|---|---|---|---|---|
[mol] % (b) | [mmol/g] (c) | Conversion of LA% (b) | Yield% | |||
5 | POSS-S-OH (1) | 99.45 | 4.66 | 22.78 | 94.05 | 91.70 |
6 | POSS-S-OH (2) | 95.37 | 4.47 | 9.91 | 84.47 | 82.40 |
7 | iBu-POSS-S-OH (4) | 92.54 | 0.95 | 34.74 | 78.9 | 73.51 |
2.2.1. SEC Analysis
Hybrid Polymers | Mn of Hybrids | PDI | Number of Chains per POSS | Mn of Chain/ DP | |||||||
---|---|---|---|---|---|---|---|---|---|---|---|
Theor. | Micr. Anal. | NMR | RI (a) | MALS | RI | MALS | Theor. (b) | NMR (c) | MALS | ||
5 | 26,350 | 28,430 | 34,000 | 32,000 | 28,500 | 1.15 | 1.15 | 8 | 3,080/21.4 | 3,170/22 | 3,340/23 |
6 | 11,400 | – | 9,800 | 13,400 | 9,050 | 1.06 | 1.07 | 7.63 | 1,210/8.4 | 1,060/7.4 | 960/6.7 |
7 | 4,960 | 4,600 | 4,550 | 4,950 | 3,600 | 1.28 | 1.04 | 1 | 3,980/27.6 | 3,570/25 | 2,600/18.2 |
POSS–S–OH (1) | 1,706.4 | – | – | – | 1,820 | – | 1.007 | – | – | – | – |
iBu–POSS–S–OH (4) | 977.7 | – | – | – | 1,085 | – | 1.14 | – | – | – | – |
2.2.2. NMR Analysis of the Hybrid Polymers
2.2.3. MALDI TOF of Polymer Hybrids
2.2.4. Thermogravimetric Analysis
Sample | Tonset (a) [°C] | Tmax1 (b) [°C] | Tmax2 (b) [°C] | Residue wt % |
---|---|---|---|---|
(POSS-S-OH)(1) | 350 | 374 | 460 | 31.31 |
(iBu-POSS-S-OH)(4) | 250 | 316 | 348 | 0.18 |
(POSS-S-PLA)(5) | 192 | 232 | 389 | 3.19 |
(POSS-S-PLA)(6) | 192 | 225 | 395 | 8.16 |
(iBu-POSS-S-PLA)(7) | 210 | 231 | 317 | 3.51 |
Bu-PLA (c)(8) | 237 | 277 | – | 0.02 |
3. Experimental Section
3.1. Materials
3.2. Methods
3.3. Synthesis of Functionalized POSS
3.3.1. Octakis-2[(6-Hydroxyhexyl)thio]ethyl-Octasilsesquioxane (POSS-S-OH)(1)
3.3.2. Octakis-2[(6-Hydroxyhexyl)thio]ethyl-Octasilsesquioxane (POSS-S-OH)(3)
3.3.3. Preparation of 2[(6-Hydroxyhexyl)thio]ethyl-Heptaisobutyl-Octasilsesquioxane (iBu-POSS-S-OH)(4)
3.4. General Polymerization Procedure (5)
4. Conclusions
Supplementary Materials
Acknowledgments
Author Contributions
Conflicts of Interest
References
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Rozga-Wijas, K.; Stanczyk, W.A.; Kurjata, J.; Kazmierski, S. Star-Shaped and Linear POSS-Polylactide Hybrid Copolymers. Materials 2015, 8, 4400-4420. https://doi.org/10.3390/ma8074400
Rozga-Wijas K, Stanczyk WA, Kurjata J, Kazmierski S. Star-Shaped and Linear POSS-Polylactide Hybrid Copolymers. Materials. 2015; 8(7):4400-4420. https://doi.org/10.3390/ma8074400
Chicago/Turabian StyleRozga-Wijas, Krystyna, Wlodzimierz A. Stanczyk, Jan Kurjata, and Slawomir Kazmierski. 2015. "Star-Shaped and Linear POSS-Polylactide Hybrid Copolymers" Materials 8, no. 7: 4400-4420. https://doi.org/10.3390/ma8074400