Anhydrous copolymerization with

V-Acryloxysuccinimide anhydrous copolymerization with V-isopropylacrylamide, 246 preparation, 246 V-Acryloxysuccinimide-V-isopropylacrylamide copolymer anhydrous preparation, 248,250/... 

Anhydrous Copolymerization of NIPAAM and N-Acryloxysuccinimide (NASI). In a modification of the procedure of Poliak et al., (4), NIPAAM (5 g, 44 mmol), NASI (0.372 g, 2.2 mmol) and 2,2 azobisisobutyronitrile (AIBN, 0.021 g, 0.13 mmol) were dissolved in 50 ml of dry tetrahydrofuran. The magnetically stirred solution was degassed, heated to 50 C for 24 hours under positive nitrogen pressure, and allowed to cool. The reaction mixture was filtered (0.45 i teflon filter) and the filtrate volume reduced by half. Ether was added with mixing to precipitate the copolymer. 

Copolymer is prepared by copolymerization of the N-carboxyanhydrides of tyrosine, alanine, lysine, and glutamic acid. The polymerisation was carried out at ambient temperature in anhydrous dioxane with diethylamine as initiator. Glatiramer Acetate have the ratio alanin glutamic acid lysine tyrosine = 1 6 4.54 2. 

Ethylene for polymerization to the most widely used polymer can be made by the dehydration of ethanol from fermentation (12.1).6 The ethanol used need not be anhydrous. Dehydration of 20% aqueous ethanol over HZSM-5 zeolite gave 76-83% ethylene, 2% ethane, 6.6% propylene, 2% propane, 4% butenes, and 3% /3-butane.7 Presumably, the paraffins could be dehydrogenated catalyti-cally after separation from the olefins.8 Ethylene can be dimerized to 1-butene with a nickel catalyst.9 It can be trimerized to 1-hexene with a chromium catalyst with 95% selectivity at 70% conversion.10 Ethylene is often copolymerized with 1-hexene to produce linear low-density polyethylene. Brookhart and co-workers have developed iron, cobalt, nickel, and palladium dimine catalysts that produce similar branched polyethylene from ethylene alone.11 Mixed higher olefins can be made by reaction of ethylene with triethylaluminum or by the Shell higher olefins process, which employs a nickel phosphine catalyst. 

The same electropolymerization technique can be applied to the copolymerization of [Ru(ttpy-pyr)2](PF6)2 and the isothianaphthene (ITN) monomer. Previously it has been shown that ITN will copolymerize with pyrrole [149]. In that case it was shown that the ITN monomer is covalently bound to the ortho position of the pyrrole. Under conditions of 10 1 molar excess of ITN in anhydrous aceto-... 

By a similar technique, (p-vinylphenyl) boric acid esters such as di-)5-phenylethyl(p-vinylphenyl) borate and esters derived from citronellol, geraniol, 1-menthol, borneol, and di- and tri-chloro-phenoxyethanol were copolymerized with N-vinylpyrrolidone in anhydrous dioxane solution under nitrogen with AIBN at 50°C for 72 hr [64]. 

Parallel approaches have been described for the preparation of polyacrylate-protease conjugates [396-400]. Acryloylation of subtilisin and a-chymotrypsin, followed by mixed polymerization with methyl methacrylate, vinyl acetate, styrene, or ethylvinyl ether, provides insoluble, doped polymethyl methacrylate, polyvinyl acetate, polystyrene, and polyethyl vinyl ether polymers [396]. These biocatalytic plastics perform especially well in hydrophilic and hydrophobic solvents, and have been used for peptide synthesis and the regioselective acylation of sugars and nucleosides. Similarly, modification of subtilisin and thermolysin with PEG monomethacrylate, then copolymerization with methyl methacrylate and trimethylolpropane trimethacrylate furnishes protease-polymethyl methacrylate plastics, which show good activities and stabilities in aqueous, mixed, and low-water and anhydrous organic media [397-400]. The protein-acrylate composites are unique in that they enable catalytic densities as high as 50% w/w. 

Macromonomers bearing unsaturation at the chain-end were recently reported via the ROP of CL and DXO at 60°C, under anhydrous conditions, using 2-hydroxyethyl methacrylate (HEM A) as an initiator. The DP of the macromonomers was controlled by regulating the monomer-to-HEMA ratio, after which the macromonomers were homopolymerized or copolymerized with methyl methacrylate by free radical initiators [6]. 

After hydrolysis by 2N methanol solution of H2SO4, the product was neutralized with KOH to pH=5 and methanol evaporated. The dry residue was expected to be poly(allilamine), polymethacrylic acid, and K2SO4. Indeed, after extraction with anhydrous methanol and acetone, poly(allilamine) was identified by NMR and IR spectrometries. After evaporation, solvent from the methanol part of the extract insoluble in chloroform part was obtained. After esterification by diazomethane the product was identified as polyfmethyl methacrylate) on the basis of IR and H-NMR spectroscopy. IR spectroscopy was applied in order to examine the copolymerization of multimethacrylate (p-cresyl-formaldehyde oligomers with methacrylic groups) with st3rrene. It was found that double bond peak at 1650 cm disappeared during the process and it was absent in the product of polymerization. Polymerization and... 

The scope of this reaction is eloquently given in a patent (72) describing the copolymerization of polar with nonpolar monomers in the presence of a Friedel-Crafts and a free radical initiator. In the process a polar monomer which contains strongly negative groups and that responds to free radical initiation but not Friedel-Crafts type of polymerization is complexed with a Friedel-Crafts halide, and then the complexed monomer is copolymerized, under anhydrous conditions, in the presence of a free radical initiator with a nonpolar monomer that responds to Friedel-Crafts but not free radical polymerization. ... 

Once all reagents were anhydrous and the initial issues with the copolymerization were resolved, the next challenge was to identify the exact weight ratio of lactide... 

Acetal homopolymers are polymerized from purified anhydrous formaldehyde. Acetal copolymers are copolymerized from cychc 1,3,5-tri-oxane cychc trimer (CsHeOa) of formaldehyde, tjrpically with a cychc ether comonomer such as ethylene oxide [1]. Ethylene glycol is the product of hydrolysis of ethylene oxide. 

Methylthiophene/styrene copolymers Methyl methacrylate does not homopolymerize or copolymerize if present in the monomer feed during the oxidation of 3-methylthiophene. This is the reason that its copolymer with 3-MT is prepared indirectly as described above. Its homopolymerization is generally initiated by anions or free radicals. Styrene, however, undergoes a random copolymerization when present during the chemical oxidation of 3-methylthiophene initiated with anhydrous FeCls [73]. Monomer reactivity ratios for the copolymerizations in methylene chloride and nitrobenzene at 5°C are reported, but there is considerable scatter in the Fineman-Ross plots. The proposed structure of the 3-MT/stryrene copolymer is shown in Figure 11.16, where R = H. 

The findings by Sakamoto are in agreement with earlier observations by Yaron and Berger, who also identified linear homopolypeptide by-products when NCA graft copolymerizations were carried out in dry dioxane or DMF. Tewksbury and Stahmann, in contrast, reported that the synthesis of multichain poly(amino acids) using poly(L-lysine) initiator and o/L-phenylalanine NCA, L-leucine NCA, or Bn-Glu NCA in anhydrous DMSO was not accompanied by the formation of linear by-products. These contradictory observations are characteristic for primary amine-initiated NCA... 

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