Polymeric ethers, synthesis with

A long-standing goal in polyolefins is the synthesis of polymers bearing polar functional groups such as acrylate, esters, or vinyl ethers, etc [24,40]. These copolymers might endow polyolefins with useful properties such as adhesiveness, dyeability, paintability, and print-ibility. Advances have recently been made in polymerizing polar monomers with cationic metallocene catalysts... 

The syntheses of 1 utilized the Ullmann ether synthesis.13 Reaction of 2 mol of 1-bromonaphthalene with 4,4-(hexafluoroisopropylidiene)diphenol afforded the desired product 1. The reaction was carried out in DM Ac at 160°C in the presence of potassium carbonate as the base and copper (I) iodine as the reaction catalyst to yield 1, as depicted in Scheme 1. The reaction proceeded slowly but in good yield with easy isolation of the desired compound. Acylation of 1 with 4-fluorobenzoyl chloride to prepare 2 was carried out under modified Friedel-Crafts reaction conditions14 using dimethyl-sulfone as catalyst moderator. Both 1 and 2 were easily recrystallized to yield high-purity monomers suitable for polymerizations. 

This article reports on the synthesis of photosensitive polymers with pendant cinnamic ester moieties and suitable photosensitizer groups by cationic copolymerizations of 2-(cinnamoyloxy)ethyl vinyl ether (CEVE) (12) with other vinyl ethers containing photosensitizer groups, and by cationic polymerization of 2-chloroethyl vinyl ether (CVE) followed by substitution reactions of the resulting poly (2-chloroethyl vinyl ether) (PCVE) with salts of photosensitizer compounds and potassium cinnamate using a phase transfer catalyst in an aprotic polar solvent. The photochemical reactivity of the obtained polymers was also investigated. 

Table 4 shows typical reaction conditions and results of the living cationic polymerization of isobutyl vinyl ether (IBVE) with the HCl/ZnCh [127] and the CFjCC H/ZnCL [227] initiating systems. The former system is now among the most convenient for the synthesis of poly(alkyl vinyl... 

Surfactant- and Amphiphilic Acid-Assisted Synthesis PANI-NTs have been prepared by the oxidative polymerization of aniline with APS in an aqueous solution in the presence of SDS [82,328], SDBS [329], a mixture of ionic surfactants (CTAB and SDBS) [204], polymeric acids [330] e.g. poly(methyl vinyl ether-alt-maleic acid) [331-334] (Figure 2.16), poly(3-thiopheneacetic acid) [70], PSSA and PAA (Figure 2.16) [333],... 

Stoddart et al. reported the synthesis of the first tetracationic cyclophane-aromatic crown ether-type side-chainpoly[2]catenanes 51 [97,108] via route i (Scheme 17.16). In this case, the dihydroxy-functionalized [2]catenane monomer 50 was first prepared by employing a template method similar to that discussed above. Side-chain poly[2]catenane 51 was prepared by the polymerization of 50 with... 

Lipase-catalyzed synthesis of PBS is a recently developed method, which is fulfilled at milder conditions without remnant metal salt. In 2006, Azim et al. (2006) reported Candida antarctica lipase B catalyzed synthesis of PBS from the monophasic reaction mixtures of diethyl succinate and 1,4-butanediol. The reaction temperature played an important role in determining the molecular weight of PBS. After polymerization for 24 h in diphenyl ether, PBS with of 2,000,4,000, 8,000, and 7,000 was produced at 60, 70, 80, and 90°C, respectively. The low molecular weight was due to precipitation after polymerization for 5-10 h, limiting the growth of the polyester chain length. Increasing the polymerization temperature from 80 to 95°C can result in the maintenance of a monophasic reaction mixture after 21 h, which led to production of PBS with of 38,000 and polydispersity index of 1.39. 

S. Aoshima, H. Oda, E. Kobayashi, Synthesis of thermally-induced phase separating polymer with well-defined polymer structure by living cationic polymerization. I. Synthesis of polyfvinyl ether)s with oxyethylene units in the pendant and its phase separation behavior in-aqueous solution,/owmo/ of Polymer Science, Part A Polymer Chemistry, 30,2407-13,1992. 

Comparisons with reference systems are also provided e.g. NDIO is a much better photoinitiator than the well known camphorquinone CQ (Table 1) upon a low intensity source (halogen lamp). This system leads to final tack-free coatings whereas no polymerization is observed with the CQ based system. TMPTA (trimethylol propane acrylate), EPOX ((3,4-epo>ycyclohexane)methyl 3,4-epo ycyclohe ylcarbo5ylate) and DVE-3 (triethylene glycol divinyl ether) are used as representatives of low viscosity monomers. Figure 6 shows that the synthesis of IPN (Fig. 6A epoxide and acrylate conversions 60%) or thiol-ene (Fig. 6B vinylether and trithiol conversions around 100 and 40%, respectively) is very efficient even upon a low intensity LED bulb. 

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