Tetrahydrofuran polymerization addition

Radiation-induced polymerization of nitroethylene in the liquid state was studied by Yamaoka and one of the present authors (K. H.). They verified that nitroethylene polymerizes in the anionic mechanism by radiation too, from the following three observations (7). Tetrahydro-furan is the most favorable solvent for the polymerization, among nitro-ethane, ethylether and tetrahydrofuran. The addition of hydrogen chloride remarkably retards the polymerization. Finally, nitroethylene copolymerizes with acrylonitrile. 

The initiation of tetrahydrofuran polymerization by direct addition of oxonium salts is of interest because it reveals a good deal about the mechanism, but for practical purposes the salts may be formed in the reaction mixture. The obvious method is, of course, to add a little epichlorohydrin to the mixture of monomer and Friedel Crafts reagent for only antimony pentachloride is sufficiently active to start the reaction with monomer alone, but other reactions which accomplish the same purpose are ... 

Thus there are many examples of PEG acting as a PTC (refer also to other contributions to the Symposium). It is of interest to inquire as to the effectiveness of other polyethers. Yamazaki and coworkers have examined the effect of various polymeric additives on the reaction between sodium phenoxide and n-butyl bromide in dioxane. Poly(oxetane), poly(tetrahydrofuran), and poly(ethyl-vinylether) were found to be ineffective, while PEG gave a rate enhancement of approximately 100. Interestingly, polyvinylpyrrolidone of several molecular weights was even more effective than PEG. ... 

In ionic polymerizations termination by combination does not occur, since all of the polymer ions have the same charge. In addition, there are solvents such as dioxane and tetrahydrofuran in which chain transfer reactions are unimportant for anionic polymers. Therefore it is possible for these reactions to continue without transfer or termination until all monomer has reacted. Evidence for this comes from the fact that the polymerization can be reactivated if a second batch of monomer is added after the initial reaction has gone to completion. In this case the molecular weight of the polymer increases, since no new growth centers are initiated. Because of this absence of termination, such polymers are called living polymers. 

GopolymeriZation Initiators. The copolymerization of styrene and dienes in hydrocarbon solution with alkyUithium initiators produces a tapered block copolymer stmcture because of the large differences in monomer reactivity ratios for styrene (r < 0.1) and dienes (r > 10) (1,33,34). In order to obtain random copolymers of styrene and dienes, it is necessary to either add small amounts of a Lewis base such as tetrahydrofuran or an alkaU metal alkoxide (MtOR, where Mt = Na, K, Rb, or Cs). In contrast to Lewis bases which promote formation of undesirable vinyl microstmcture in diene polymerizations (57), the addition of small amounts of an alkaU metal alkoxide such as potassium amyloxide ([ROK]/[Li] = 0.08) is sufficient to promote random copolymerization of styrene and diene without producing significant increases in the amount of vinyl microstmcture (58,59). 

Solvent polarity is also important in directing the reaction bath and the composition and orientation of the products. For example, the polymerization of butadiene with lithium in tetrahydrofuran (a polar solvent) gives a high 1,2 addition polymer. Polymerization of either butadiene or isoprene using lithium compounds in nonpolar solvent such as n-pentane produces a high cis-1,4 addition product. However, a higher cis-l,4-poly-isoprene isomer was obtained than when butadiene was used. This occurs because butadiene exists mainly in a transoid conformation at room temperature (a higher cisoid conformation is anticipated for isoprene) ... 

Addition of styrene to a green solution of naphthalene" Na+ in tetrahydrofuran leads to an instantaneous change of color from green to red. Styrene polymerizes rapidly and quantitatively within a few seconds, and when the reaction is completed, addition of water converts the red solution of polystyryl carbanions into colorless solution of polystyrene. After precipitation of the polymer it was shown spectroscopically25 that the residual solution contains an amount of naphthalene equal to that used in the preparation of the initiating catalyst. This observation confirms the proposed mechanism of initiation of the polymerization. 

The addition of a cyclic vinyl sulfoxide anion to aldehydes has been reported only once14. Interestingly, 2,3,4,5-tetrahydro-l//-thiepane S-oxide cannot be metalated by lithium diiso-propylamide in tetrahydrofuran at — 78 °C. At higher temperatures ( — 20° to 0°) a white polymeric precipitate is formed. This polymeric product is also formed when the sulfoxide is treated with butyllithium or. wr-butyllithium in tetrahydrofuran even at — 78 C. However, metalation can be accomplished with. sec-butyllithium using an excess of N,N,N, N -tetramcthylethylenediamine in tetrahydrofuran at —78 C. In this case, a pale yellow solution is formed immediately and upon addition of benzaldehydc instantaneous dccolorization occurs yielding a mixture of diastereomeric alcohols in 90% yield. 

B. Polymeric Urea [Benzene, diethenyl-, polymer with ethenylbenzene, [[[[(1 methylethyl)amino]carbonyt]amino]methyl] deriv.] A 10.0-g. portion of benzylamine polymer beads prepared as in Part A and 125 ml. of tetrahydrofuran (Note 6) are combined in a 300-ml., three-necked, round-bottomed flask equipped with a magnetic stirrer, a dropping funnel, and a condenser fitted with a gas-inlet tube A nitrogen atmosphere is established in the system, and the slurry is stirred while 1.35 g. (0.0159 mole) of isopropyl isocyanate [Propane, 2-isocyanato-] is added. This causes an exothermic reaction, which subsides after about 20 minutes. The mixture is then stirred at room temperature for 22 hours and at reflux for an additional 4 hours. The beads are collected by filtration, washed with 150-ml. portions of tetrahydrofuran (Note 6) and methanol, and dried under reduced pressure over calcium chloride to yield 9.09 g, of the isopropyl urea polymer. 

This reaction includes modified acrylates with or without addition of styrenes in combination with one or more initiators in a solvent [126], In an example, tetrahydrofuran was used as solvent and the polymer concentrations amounted to about 5.6 g Thus, the polymerization is carried out as solvent process. 

In addition to the desired polymerization reaction, the dialcohol reactants can participate in deleterious side reactions. Ethylene glycol, used in the manufacture of polyethylene terephthalate, can react with itself to form a dialcohol ether and water as shown in Fig. 24.4a). This dialcohol ether can incorporate into the growing polymer chain because it contains terminal alcohol units. Unfortunately, this incorporation lowers the crystallinity of the polyester on cooling which alters the polymer s physical properties. 1,4 butanediol, the dialcohol used to manufacture polybutylene terephthalate, can form tetrahydrofuran and water as shown in Fig. 24.4b). Both the tetrahydrofuran and water can be easily removed from the melt but this reaction reduces the efficiency of the process since reactants are lost. 

Hiller and Funke obtained easily dissolvable linear macromolecules of PVS by anionic polymerization of 1,4-DVB up to conversions of 80-90% [230,231]. In these experiments very low concentrations of n-butyl lithium (n-BuLi) were used and tetrahydrofuran (THF) as solvent. The reactions were carried out at -78 °C and for 7 min. The contents of pendant vinyl groups in the polymer were determined by infrared spectroscopy, mercury-II-acetate addition and catalytic... 

It has been shown for many metal halides and monomers that binary mixtures of these can be prepared (usually in a solvent) without any polymerization taking place. Such a quiescent mixture can be made to react by the addition of a suitable third compound, which is called the co-catalyst. This term is preferable to the word promoter , because in certain contexts a substance is called promoter which enhances the rate or yield of a reaction that will also go in the absence of the promoter herein lies the true distinction between promoter and co-catalyst [28]. (For example, small quantities of epoxides or epichlorohydrin act as promoters in the cationic polymerization of tetrahydrofuran.) I will take it that in the above quotation the word promoter was inadvertently used in place of co-catalyst , for only thus does it become really meaningful. 

Since Lewis base additives and basic solvents such as tetrahydrofuran are known to deaggregate polymeric organolithium compounds, (21,23,26) it was postulated that ketone formation would be minimized in the presence of sufficient tetrahydrofuran to effect dissociation of the aggregates. In complete accord with these predictions, it was found that the carbonation of poly(styryl)lithium (eq. 9), poly(isoprenyl)-lithium, and poly(styrene-b-isoprenyl)lithium in a 75/25 mixture (by volume) of benzene and tetrahydrofuran occurs quantitatively to produce the carboxylic acid chain ends (8 ). 

When a cychc monomer such a tetrahydrofuran or caprolactam is used as the monomer, the polymerization can be made to occur primarily by monomer reacting with the polymer rather than aU polymers reacting with each other. These kinetics are more tike addition polymerization, where only the monomer can react with the polymer. However, we stiU call this condensation polymerization because it produces this type of polymer. 

In this paper a generalized approach is presented to the derivation of H-H-S equations for multispecies polymers created by addition polymerization across single double bonds in the monomers. The special cases of copolymers and terpolymers are derived. This development is combined with experimental results to evaluate the numerical parameters in the equations for poly(styrene-acrylonitrile ) (SAN) in three separate solvents and for poly(styrene-maleic anhydride-methyl methacrylate) (S/HA/MM) in a single solvent. The three solvents in the case of SAN are dimethyl formamide (DMF), tetrahydrofuran (THF), and methyl ethyl ketone (MEK) and the solvent for S/HA/HH is HER. 

Another complex obtained by template polymerization of dimethylaminoethyl methacrylate in the presence of polyCacrylic acid) was synthesized and analyzed by Abd-Ellatif. The procedure of separation was as follows to the complex dissolved in 10% NaCl solution, 10% NaOH solution was added dropwise and white gel was precipitated. Addition of sodium hydroxide was continued until no more precipitate was separated. The soluble polymer after dialysis was dried and identified as poly(acrylic acid). The insoluble polymer fraction was found to be insoluble in toluene, benzene, tetrahydrofurane, but soluble in acetone/water (2 1 v/v). Elemental analysis and IR spectra lead to the conclusion that this fraction consists of pure poly(dimethyl aminoethyl methacrylate) which was expected as a daughter polymer. 

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