Diethyl polymerization

To a solution of 0.25 mol of the trimethylsilyl ether in 120 ml of dry diethyl ether was added in 20 min at -35°C 0.50 mol of ethyllithium in about 400 ml of diethyl ether (see Chapter II, Exp. 1). After an additional 30 min at -30°C the reaction mixture was poured into a solution of 40 g of ammonium chloride in 300 ml of water. After shaking, the upper layer was separated off and dried over magnesium sulfate and the aqueous layer was extracted twice with diethyl ether. The ethereal solution of the cumulenic ether was concentrated in a water-pump vacuum and the residue carefully distilled through a 30-cm Vigreux column at 1 mmHg. The product passed over at about 55°C, had 1.5118, and was obtained in a yield of 874. Distillation at water-pump pressure (b.p. 72°C/I5 mmHg) gave some losses due to polymerization. 

Anionic polymerization of vinyl monomers can be effected with a variety of organometaUic compounds alkyllithium compounds are the most useful class (1,33—35). A variety of simple alkyllithium compounds are available commercially. Most simple alkyllithium compounds are soluble in hydrocarbon solvents such as hexane and cyclohexane and they can be prepared by reaction of the corresponding alkyl chlorides with lithium metal. Methyllithium [917-54-4] and phenyllithium [591-51-5] are available in diethyl ether and cyclohexane—ether solutions, respectively, because they are not soluble in hydrocarbon solvents vinyllithium [917-57-7] and allyllithium [3052-45-7] are also insoluble in hydrocarbon solutions and can only be prepared in ether solutions (38,39). Hydrocarbon-soluble alkyllithium initiators are used directiy to initiate polymerization of styrene and diene monomers quantitatively one unique aspect of hthium-based initiators in hydrocarbon solution is that elastomeric polydienes with high 1,4-microstmcture are obtained (1,24,33—37). Certain alkyllithium compounds can be purified by recrystallization (ethyllithium), sublimation (ethyllithium, /-butyUithium [594-19-4] isopropyllithium [2417-93-8] or distillation (j -butyUithium) (40,41). Unfortunately, / -butyUithium is noncrystaUine and too high boiling to be purified by distiUation (38). Since methyllithium and phenyllithium are crystalline soUds which are insoluble in hydrocarbon solution, they can be precipitated into these solutions and then redissolved in appropriate polar solvents (42,43). OrganometaUic compounds of other alkaU metals are insoluble in hydrocarbon solution and possess negligible vapor pressures as expected for salt-like compounds. 

Rubber. The mbber industry consumes finely ground metallic selenium and Selenac (selenium diethyl dithiocarbamate, R. T. Vanderbilt). Both are used with natural mbber and styrene—butadiene mbber (SBR) to increase the rate of vulcanization and improve the aging and mechanical properties of sulfudess and low sulfur stocks. Selenac is also used as an accelerator in butyl mbber and as an activator for other types of accelerators, eg, thiazoles (see Rubber chemicals). Selenium compounds are useflil as antioxidants (qv), uv stabilizers, (qv), bonding agents, carbon black activators, and polymerization additives. Selenac improves the adhesion of polyester fibers to mbber. 

Epichlorohydrin Elastomers without AGE. Polymerization on a commercial scale is done as either a solution or slurry process at 40—130°C in an aromatic, ahphatic, or ether solvent. Typical solvents are toluene, benzene, heptane, and diethyl ether. Trialkylaluniinum-water and triaLkylaluminum—water—acetylacetone catalysts are employed. A cationic, coordination mechanism is proposed for chain propagation. The product is isolated by steam coagulation. Polymerization is done as a continuous process in which the solvent, catalyst, and monomer are fed to a back-mixed reactor. Pinal product composition of ECH—EO is determined by careful control of the unreacted, or background, monomer in the reactor. In the manufacture of copolymers, the relative reactivity ratios must be considered. The reactivity ratio of EO to ECH has been estimated to be approximately 7 (35—37). 

Certain, Y, Y-dialkyl dithioearbamates [e,g. benzyl A)/V-diethyl dithiocarbamate (14)] and xanthates have been used as photoinitiators. Photodissociation of the C-S bond of these compounds yields a reactive alkyl radical (to initiate polymerization) and a less reactive sulfur-centered radical (to undergo primary-radical termination) as shown in Scheme 9.9.30 41 4 ... 

ABA type poly(hydroxyethyl methacrylate) (HEMA) and PDMS copolymers were synthesized by the coupling reactions of preformed a,co-isocyanate terminated PDMS oligomers and amine-terminated HEMA macromonomers312). Polymerization reactions were conducted in DMF solution at 0 °C. Products were purified by precipitation in diethyl ether to remove unreacted PDMS oligomers. After dissolving in DMF/toluene mixture, copolymers were reprecipitated in methanol/water mixture to remove unreacted HEMA oligomers. Microphase separated structures were observed under transmission electron microscope, using osmium tetroxide stained thin copolymer films. 

Dimethyl peroxide Diethyl peroxide Di-t-butyl-di-peroxyphthalate Difuroyl peroxide Dibenzoyl peroxide Dimeric ethylidene peroxide Dimeric acetone peroxide Dimeric cyclohexanone peroxide Diozonide of phorone Dimethyl ketone peroxide Ethyl hydroperoxide Ethylene ozonide Hydroxymethyl methyl peroxide Hydroxymethyl hydroperoxide 1-Hydroxyethyl ethyl peroxide 1 -Hydroperoxy-1 -acetoxycyclodecan-6-one Isopropyl percarbonate Isopropyl hydroperoxide Methyl ethyl ketone peroxide Methyl hydroperoxide Methyl ethyl peroxide Monoperoxy succinic acid Nonanoyl peroxide (75% hydrocarbon solution) 1-Naphthoyl peroxide Oxalic acid ester of t-butyl hydroperoxide Ozonide of maleic anhydride Phenylhydrazone hydroperoxide Polymeric butadiene peroxide Polymeric isoprene peroxide Polymeric dimethylbutadiene peroxide Polymeric peroxides of methacrylic acid esters and styrene... 

The enzymatic synthesis of polyesters from activated diesters was achieved under mild reaction conditions. The polymerization of bis(2,2,2-trichloroethyl) glutarate and 1,4-butanediol proceeded in the presence of PPL at room temperature in diethyl ether to produce the polyesters with molecular weight of 8.2 x 10. Vacuum was applied to shift the equilibrium forward by removal of the activated alcohol formed, leading to the production of high molecular weight polyesters. The polycondensation of bis(2,2,2-trifluoroethyl) sebacate and aliphatic diols took place using lipases BC, CR, MM, and PPL as catalyst in diphenyl ether. Under the... 

Divinyl esters reported first by us are efficient monomers for polyester production under mild reaction conditions. In the lipase PF-catalyzed polymerization of divinyl adipate and 1,4-butanediol in diisopropyl ether at 45°C, a polyester with molecular weight of 6.7 x 10 was formed, whereas adipic acid and diethyl adipate did not afford the polymeric materials under similar reaction conditions (Scheme 3). 

Room-temperature ionic liquids have received much attention as green designer solvents. We first demonstrated that ionic liquids acted as good medium for lipase-catalyzed production of polyesters. The polycondensation of diethyl adipate and 1,4-butanediol using lipase CA as catalyst efficiently proceeded in l-butyl-3-methylimidazolinium tetrafluoroborate or hexafluorophosphate under reduced pressure. The polymerization of diethyl sebacate and 1,4-butanediol in l-butyl-3-methylimidazolinium hexafluorophosphate took place even at room temperature in the presence of lipase BC. ... 

PPF catalyzed an enantioselective polymerization of bis(2,2,2-trichloroethyl) tra 5-3,4-epoxyadipate with 1,4-butanediol in diethyl ether to give a highly optically active polyester (Scheme 9). °° The molar ratio of the diester to the diol was adjusted to 2 1 to produce the (-) polymer with enantiomeric purity of >96%. The polymerization of racemic bis(2-chloroethyl) 2,5-dibromoadipate with excess of 1,6-hexanediol using lipase A catalyst produced optically active trimer and pentamer. The polycondensation of 1,4-cyclohexanedimethanol with fumarate esters using PPL catalyst afforded moderate diastereoselectivity for the cis/trans monocondensate and markedly increased diastereoselectivity for the dicondensate product. 

Thus the reaction product of diethyl ether and diphosphorus pentoxide, a pale yellowish syrupy mass, was designated as ethyl metaphosphate (147), other ethoxy-containing compounds give the same product 102-103) it can be reprecipitated from chloroform/ether and reacts with aniline to give the phosphoramidate 148 104) which is conceivably a trapping product of ethyl metaphosphate 147, or a cleavage product of polymeric metaphosphates. 

Nair et al. studied the kinetics of the polymerization of MMA at 60-95 °C using N,1SP-diethyl-NjW-di(hydroxyethyl)thiuram disulfide (30a) as the thermal in-iferter [142]. The dependence of the iniferter concentration on the polymerization rate was examined. The chain transfer constant of the propagating radical of MMA to 30a was determined to be 0.23-0.46 at 60-95 °C, resulting in the activation energy of 37.6 kj/mol for the chain transfer. Other derivatives 30b-30d were also prepared and used to derive telechelic polymers with the terminal phosphorus, amino, and other functional aromatic groups [143-145]. Thermal polymerization was also investigated with the end-functional poly(St) and poly(MMA) which were prepared using the iniferter 13 [146]. 

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