2022
DOI: 10.1002/anie.202114896
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Inverse Vulcanization of Norbornenylsilanes: Soluble Polymers with Controllable Molecular Properties via Siloxane Bonds

Abstract: The inverse vulcanization produces high sulfur content polymers from alkenes and elemental sulfur. Control over properties such as the molar mass or the solubility of polymers is not well established, and existing strategies lack predictability or require large variations of the composition. Systematic design principles are sought to allow for a targeted design of materials. Herein, we report on the inverse vulcanization of norbornenylsilanes (NBS), with a different number of hydrolysable groups at the silicon… Show more

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Cited by 20 publications
(20 citation statements)
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“…As shown in Figure 2e, poly(S n -r-NM) has no unreacted crystalline sulfur residue and exhibits a clear T g of −25 °C, suggesting an amorphous polymer with low T g , which is similar to the reported inverse vulcanized polymer. 25 Additionally, in comparison with that of NM, the FTIR curve of poly (S n -r-NM) displays that the peak of C�C stretching at ∼1570 cm −1 and typical signals of H−C� stretching at ∼3060 cm −1 vanish, indicating that vinyl groups in norbornene are consumed during the reaction (Figure 2d). Meanwhile, the newly emerged peak at ∼582 cm −1 belonging to the C−S bending proves that elemental sulfur is involved in the formation of the polymer.…”
Section: Fabrication Of Elastic S-pu Foammentioning
confidence: 99%
“…As shown in Figure 2e, poly(S n -r-NM) has no unreacted crystalline sulfur residue and exhibits a clear T g of −25 °C, suggesting an amorphous polymer with low T g , which is similar to the reported inverse vulcanized polymer. 25 Additionally, in comparison with that of NM, the FTIR curve of poly (S n -r-NM) displays that the peak of C�C stretching at ∼1570 cm −1 and typical signals of H−C� stretching at ∼3060 cm −1 vanish, indicating that vinyl groups in norbornene are consumed during the reaction (Figure 2d). Meanwhile, the newly emerged peak at ∼582 cm −1 belonging to the C−S bending proves that elemental sulfur is involved in the formation of the polymer.…”
Section: Fabrication Of Elastic S-pu Foammentioning
confidence: 99%
“…Therefore, the development of a new synthetic strategy is necessary for thermomechanically robust and highly IR-transparent sulfur-rich copolymers. [27][28][29][30][31] Herein, we present an in situ microphase separation strategy for the inverse vulcanization to significantly improve the thermomechanical properties of sulfur-rich copolymers while maintaining both high IR transparency and n values. For the inverse vulcanization of ES, we selected 1,3,5-trivinylbenzene (TVB) as a trifunctional organic crosslinker.…”
Section: Introductionmentioning
confidence: 99%
“…This is mainly due to their broad application possibilities, ranging from flame retardancy and environment protection to various high-value-added specialty fields, such as biomaterials, drug delivery, sensors, optical, battery and other energy-related areas, etc. (see, e.g., [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] and the references therein). Although the reaction of phosphorus pentasulfide (P 4 S 10 ), a widely available commercial material, with alcohols has been known for a long time [20] to result in the formation of dialkyl dithiophosphates (DTPs), i.e., O,O-diesters of dithiophosphoric acid [21] (Scheme 1), surprisingly, systematic investigations on the utilization of this process for polymer synthesis have not been reported yet, according to the best of our knowledge.…”
Section: Introductionmentioning
confidence: 99%