Diacetylene-containing polymers

In addition Badarau and Wang reported preparation of a series of diacetylene-containing polymers that were formed by oxidative coupling polymerization of 9,9-bis(4-propargyloxyphenyl)fluorene and dipropargyl 4,4 -(hexafluoroisopropylidene)diphthalimide. 

The physical properties of diacetylene-containing phospholipid liposomes (25) have been investigated by D. Chapman 102 103 104> by means of UV/VIS and 13C-NMR spectroscopy. They found that short linear segments of polymer are interconnected through the glycerol backbone of the lipid in identical-chain phosphatidyl cholines, but the molecular weights of the polymers are still unknown. 

As utilized in the synthesis of PPV-based polymers, soluble precursor routes have been developed for the synthesis of various heterocyclic Jt-conjugated polymers. The two most widely employed of these methods for heterocycle formation, shown in Scheme 66, center around ring closure of pre-polymers containing diacetylene 65 or 1,4-diketone units 66 [335-339]. The synthesis of heterocyclic structures from 1,4-diketones has been a known transformation in organic chemistry for decades. While once mainly used for monomer preparation through various cyclizations, it is now being employed to make heterocycle-containing polymers and copolymers [340-342]. 

A few methacrylates (5) and dimethacrylate (6) which contain al hatic DA groiq>s were synthesized 2G) and are shown in Chart 2. In order to conq)are the NLO properties of PDA-containing polymers with those of the PDAs obtained by the molten state polymerization, several novel diacetylenes were synthesized, and their chemical structures are shown in Chart 2 for aromatic diesters (7, 8) and aromatic diamide (9). These conq)ounds were synthesized by the Heck reaction of the corresponding bromo compounds with trimethylsilylacetylene, as shown in Chart 3. 

Polymers containing Hf(TV) in the main chain or side chains can be prepared by any of the known processes for synthesis of metal-containing polymers. An attractive approach is the polycondensation of dicyclo-pentadienyl derivatives of hafnium(IV) with diols or oxygen-free diacetylenic hgands. An alternative approach is polymerization of the Hf(TV) monomers with (meth)acrylate and fumarate groups, synthesized for the first time in this study. We investigated the thermolysis of the synthesized... 

The linear polymers were readily formed by both methods. A salient feature in both of the syntheses was the in situ production of a desired carboranylenesiloxane oligomer by the reaction of a lithiated carborane and a chlorinated siloxane species rather than the use of the commercial Dexsil monomer as in the case of Henderson et al. [25] and Houser et al. [29], This has afforded an enormous degree of variation in the compositions of diacetylene-containing carboranylenesiloxane polymers that is not available by the conventional route of Henderson et al. [25]. The effect of the reduction in the diacetylene concentration was apparent in the positions and the intensities of the DSC peak maxima of the crossUnking endotherms of 5a-c. Thus, it was observed that as the concentration of the diacetylene units in the polymer... 

A recent alternative approach is the use of diacetylene-containing alkylthiol monomer units that, when attached to metals via the thiolate bond, form planar arrays that are photopolymerized [20-22]. Sueh a strategy, shown in Fig. 1, eombines the advantages of SAM formation with the improvements of a more robust polymer end-product. Previous work with L-B films of diacetylenic amphiphiles has demonstrated in-plane requirements for topo-ehemie-ally controlled polymerization [23]. Templating of the diacetylene topochemistry via the thiol docking to metal surface lattice sites spaced according to the metal... 

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