## 3 Results and Discussion  
As previously reported, the PSt-\(l\)-PDMS and PSt-\(l\)-PDMS/DVB conetworks possess bicontinuous nanophase-separated morphology with distinct polystyrene and poly(dimethylsiloxane) nanodomains, as determined by small angle X-ray scattering (SAXS) and atomic force microscopy (AFM) measurements [73]. For the examined cases in this study, DSC curves also indicated the phase separation in these conetworks with two separate glass transition temperatures (\(T_{\text{g}}\)) for the PSt and the PDMS components [73]. While these measurements showed the \(T_{\text{g}}\) of PDMS within the range of its homopolymer, the observed \(T_{\text{g}}\) of PSt in the conetworks fell below that of the expected \(T_{\text{g}}\) of the PSt homopolymer. In order to gain insight into the glass transition behavior of PSt in the PDMS-crosslinked conetworks, and in line with previous findings on the scissors effect of macrocrosslinking in other conetworks [12,13], a library of PSt-\(l\)-PDMS and PSt-\(l\)-PDMS/DVB conetworks was synthesized and analyzed by DSC measurements. Scheme 1 shows the synthesis routes for obtaining such conetworks in the absence or presence of DVB, as an additional low molecular weight crosslinker, which is a widely used crosslinker for preparing PSt networks. As displayed in this scheme, the conetworks were prepared by free radical polymerization in a common solvent for all the components, including the resulting PSt. As shown in Table 1, this process with all the applied methacrylate-telechelic PDMS macrocrosslinkers resulted in conetworks with relatively high gel fractions after careful extraction, and their composition was close to that of the feed. The addition of DVB led to higher gel fractions, and it did not prevent the incorporation of the PDMS macrocrosslinkers. Figures 1 and 2 show the DSC scans in the temperature ranges of \(-\)150-0 \({}^{\circ}\)C and 0-200 \({}^{\circ}\)C for detecting the thermal transitions of the PDMS and PSt components, respectively. These figures clearly indicate that the \(T_{\rm g}\)s of both components can be detected in the PSt-\(l\)-PDMS and PSt-\(l\)-PDMS/DVB conetworks. Specifically, there is one glass transition near the \(T_{\rm g}\) of the PDMS homopolymers, and another one for the PSt component in the higher temperature region of the DSC measurements. Evidently, the two separate glass transitions mean microphase separation of the PSt and the PDMS domains with significant segregation in these conetworks, which is consistent with previous reported SAXS and AFM results [73]. It must be noted that the glass transition of the PSt component with sufficient certainty cannot be detected in conetworks with low PSt contents (i.e., less than \(\sim\)25 wt%), as shown in Figure 2A-C. As displayed in Figure 1, the PDMS homopolymers have \(T_{\rm g}\)s, cold crystallization, and melting transitions in the temperature ranges as expected on the basis of literature reports [78; 79; 80; 81; 82; 83; 89]. However, signals indicating crystallization of PDMS cannot be detected in both the PSt-\(l\)-PDMS and PSt-\(l\)-PDMS/DVB conetworks with PDMS macrocrosslinkers having \(M_{\rm n,PDMS}\) of 4.7 and 9 kDa. This means that crystallization of the PDMS component in these conetworks is fully prevented, which is attributed to  
the nanoconfined constraints of the PDMS nanodomains by the PSt nanophases in the bicontinuous nanophasic morphological structure of these conetworks [73]. Similar findings were recently reported for block copolymers of poly(poly(ethylene glycol) acrylate) (PEGA\({}_{76}\)) with poly(2-hydroxyethyl acrylate-polyhexanoate), that is, decrease in the crystalline fraction of PEGA76 by decreasing its fraction, but having nearly constant \(T_{\mathrm{g}}\) of this component [91]. Weak cold crystallization and melting peaks appear in the DSC scan of the conetwork prepared with the MA-PDMS-MA macrocrosslinker with \(M_{\mathrm{n,PDMS}}\) of 22.2 kDa (Figure 1B). This is presumably due to the higher mobility of the longer PDMS chains in this case.