Photo initiators disulfides

Since the dithiocarbatnyl end groups 8 are thermally stable but pholochemically labile at usual polymerization temperatures, only photo-initiated polymerizations have the potential to show living characteristics. However, various disulfides, for example, 9 and 10, have been used to prepare end-functional polymers37 and block copolymers38 by irreversible chain transfer in non-living thermally-initiated polymerization (Section 7.5.1). 

The processes described in this section should be contrasted with RAFT polymerization (Section 9.5.3), which can involve the use of similar thioearbonylthio compounds. A. A -dialkyl dithiocarbamates have very low transfer constants in polymerizations of S and (mctb)acrylatcs and arc not effective in RAFT polymerization of these monomers. However, /V,A -dialkyl dithiocarbamates have been successfully used in RAFT polymerization of VAc. Certain O-alkyl xanthates have been successfully used to control RAFT polymerizations of VAc, acrylates and S. The failure of the earlier experiments using these reagents and monomers to provide narrow molecular weight distributions by a RAFT mechanism can he attributed to the use of non-ideal reaction conditions and reagent choice. A two part photo-initiator system comprising a mixture of a benzyl dithiocarhamate and a dithiuram disulfide has also been described and provides better control (narrower molecular weight distributions).43... 

Figure 5.23 SAND can be used to modify amine-containing molecules, and then photo-initiate crosslinking to another amine-containing molecule via a ring-expansion process. The conjugates may be disrupted by reduction of the cross-bridge disulfide with DTT.

To determine if either of these answers were correct, the properties of a series of polyurethane networks which contained photo labile disulfide bonds were studied (7). The creep curve of the s imple in the initial crosslink density state (comparable to Vq) was determined in the usual way. Then, after complete recovery, another creep experiment was started but, at time t during this run, the sample was subjected to ultraviolet irradiation which photochemlcally broke some of the network chains. 

Disulfide derivatives and hexasubstituted ethanes may also be used in this context to make end-functional polymers and block copolymers. The use of dilhiuram disulfides as thermal initiators was explored by Clouet, Nair and coworkers. Chain ends are formed by primary radical termination and by transfer to the dilhiuram disulfide. The chain ends formed are thermally stable under normal polymerization conditions. I he use of similar compounds as photo-iniferters, when some living characteristics may be achieved, is described in Section 9.3.2.1.1. 

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