Hereby the polymer backbone becomes amendable to modifications, a concept which recently attracted attention under the term "skeletal or backbone editing". In order to modify the polymer backbone we heated a finely ground mixture of a PO terpolymer (Table run #9) and 5 or 10 w% elemental sulfur at 140º for 120 min in an attempt to incorporate further sulfur into the polymer. Assessing the 1 H NMR spectrum indeed shows diagnostic changes of the CH2-Sx-region with signals increasing in relative intensity that correspond to longer oligosulfide chains (see ESI Figure ). This observation could be more clearly observed in the 1 H NMR spectrum of the IBO terpolymer which does not feature diastereotopic protons (see ESI Figure ). Raman spectroscopy confirms this observation. As shown in Figure while the Raman band at 510 cm -1 corresponding to disulfide links is most intense in the starting polymer, this decreases in intensity upon reaction with elemental sulfur with bands below 490 cm - 1 corresponding to higher order oligosulfides increasing in intensity; these observations are more pronounced at 10 w% than at 5 w% elemental sulfur in the starting mixture. GPC analysis confirms that the polymer remains intact upon sulfur insertion with Mw shifting from 28 kDa (Đ = 1.6) to 29 kDa (Đ = 1.6) with 5 w% S8 and 23 kDa (Đ = 1.7) with 10 w% S8 indicating some chain cleavage or rearrangement via sulfur bond metathesis in the process. Backbone editing could also be expanded to cyclic disulfide such as lipoic acid. Hence, we heated a 1:1 mixture in w% of lipoic acid with a S8/PTA/PO terpolymer at 140ºC for 240 min followed by precipitation of the product mixture to remove unconsumed lipoic acid. The so formed polymer exhibits additional resonances in its 1 H NMR spectrum in the aliphatic region between 1.8 and 3.6 ppm (see ESI Figure ). These correspond to ring-opened lipoic acid and are broadened and shifted relative to the starting lipoic acid reactant in 47% of the repeat units by integration. Editing of the polymer backbone is also supported by a redistribution of the Raman Sx bands (see ESI Figure ). GPC analysis shows slightly broadened molecular weight distribution (see ESI Figure ) which we again attribute to chain cleavage and rearrangement via sulfur-sulfur bond metathesis. As can be seen in Figure (c), insertion of lipoic acid does decrease the glass transition temperature from 30 to 17ºC. Hence backbone editing provides a mean to alter the thermal properties after synthesis. Notably this also allows the incorporation of functional groups which are intrinsically incompatible with the polymerisation methodology as attempting to perform ROTERP in presence of lipoic acid (Figure The large monomer scope of the ROTERP methodology enables the incorporation of functional groups into the polymer side chains that also allow for post polymerisation modification of these. In this regard the S8/PTA/VGE terpolymer (Table run #15) features aldehyde functionalities that can undergo imine condensation offering an opportunity for the incorporation of degradable crosslinks to enhance mechanical properties. Reaction of the VGE terpolymer ( ). However, due to the dynamicity of sulfur-sulfur and imine bonds, this network can be processed by compression moulding into flexible films that exhibit a maximum stress of 43.3 MPa at 2.2% break (see ESI Figure and). The thermally reprocessed material recovers 92% of both maximum stress and strain resistance (Figure ). The potential for thermal reprocessing of these networks enables their application as reusable adhesives as has been for example demonstrated for polymers from inverse vulcanisation. In contrast to other approaches to such networks, our stepwise access allows to combine polymer links during synthesis to rationally impart functionality onto the material. Accordingly, to evaluate the adhesion performance of the imine crosslinked polysulfide, it was tested on wood as well as abraded steel and aluminium sheets (100×25 mm) with the polymer applied to an overlapping area of 25×16 mm and the two sheets were bonded together by compression moulding (see ESI methods section). Lap shear experiments were subsequently performed at a pull rate of 5 mm/min showing a typical maximum stress of ca. 3.5 MPa on steel (reproduced 3 times). These performance properties are competitive, when comparing to other sulfur based adhesives reported previously and for example exceed the performance of commercial glues. Importantly after material failure the respective parts can be rebounded by compression moulding under full restoration of the adhesion performance. Adhesive testing on wood reveals that material failure of the wood specimen occurs before, failure of the adhesive. On aluminium however only a low maximum stress of 0.96 MPa was achieved. We opted to improve performances by the introduction of polar groups which are expected to aid interaction with the substrate surface and applied the above established backbone editing protocol as lipoic acid features polar carboxylic acid groups. Gratifyingly, heating a finely ground mixture of the crosslinked material with 20 w% lipoic acid at 140 ºC results in formation of a homogenous material. Only trace amounts of lipoic acid could be identified in the sol-fraction of a sol-gel test supporting incorporation into the network.