Tetrahydrofuran polymerization solvent

With conventional techniques and electrolytes, it was not possible to obtain living anions because they are rapidly protonated by tetraalkylammonium salts and residual water. The first report of the production of living polymers by an electrolytic method has to be attributed to Yamazald et al. [247], who used tetrahydrofuran as solvent, and LiAlH4 or NaAl(C2H5)4 as electrolyte for the polymerization of a-methylstyrene. A similar technique was used to polymerize styrene as well as derivatives [248-252]. 

GPC is a promising method for examination of template polymerization, especially copolymerization. Copolymerization of methacrylic acid with methyl methacrylate in the presence of polyCdimethylaminoethyl methacrylate) can be selected as an example of GPC application for examination of template processes. The process was carried out in tetrahydrofurane as solvent at 65°C. After proper time of polymerization, the samples were cooled, diluted by THF, filtered, and injected to GPC columns. Two detectors on line UV and differential refractometer, DRI, were applied. UV detector was used to measure concentration of two monomers, while the template was recorded by DRI detector (Figure 11.3) The decrease in concentration ofboth monomers can be measured separately. It was found that a big difference in the rate of polymerization between template process and blank polymerization exists. The rate measured separately for methacrylic acid (decrease of concentration of methacrylic acid in monomers mixture) was much higher in the template process. Furthermore, the ratio ofboth monomers changes in a different manner. Reactivity ratios for both monomers can be computed. Decrease in concentration during the process is shown in Figure 11.4. 

Solvents and Initiators. All polymerization solvents, ethyl acetate (EA),1,2-dichloroethane (DCE), methyl ethyl ketone (MEK), cyclohexanone (CH), toluene and tetrahydrofuran (THF) were purified by standard procedures (12) and stored under N2 or over molecular sieves. All other solvents used, N,N-dimethylformamide (DMF), di-methylsulfoxide (DMSO), y-butyrolactone, hexane, diethyl ether, acetone, etc., were AR grade materials. Initiators, azobisiso-butyronitrile (AIBN), di-t-butylperoxide (DTBP), lauryl peroxide (LP) and benzoyl peroxide (BPO) were recrystallized (AIBN and BPO) or used as received from suppliers. 

Solution Polymerization. Solution polymerization is over 45 years old, but only about 3% of the PVC produced in the United States is made this way. The solution process differs from the other processes already discussed in that a solvent is added to the polymerization system. The system may be heterogeneous, in which case the monomer is soluble but the polymer is insoluble. Examples are the use of hexane, butane, ethyl acetate, or cyclohexane as solvents. After addition of a peroxide initiator and heating to 40 C, the polymerization starts and polymer precipitates out of solution as formed. In homogeneous reactions, both monomer and polymer are soluble therein. Examples are the use of dibutyl phthalate and tetrahydrofuran as solvents. 

In Table 2, the data for tetrahydrofuran (THF) solvent based on the results of Figure 1 indicate the reverse order of reactivities (in comparison with those of DIOX). The reasons, already mentioned above and elaborated in the next section, are fundamental for ionic polymerizations, which appear practically in any textbook on polymer chemistry. 

The composition of the polymerization mixture was as follows quinine (0.5 mmol) MAA or ITA (18 mmol) EDMA (540 mmol) AIBN (0.25 mmol) and tetrahydrofuran, as solvent. The MAA or ITA/quinine ratio was 36 1. After degasification and purging under nitrogen for 5 min, polymerization was carried out by photolytic initiation with UV light (A. = 366 nm) at 4 C for 24 h. 

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. 

Aqueous mineral acids react with BF to yield the hydrates of BF or the hydroxyfluoroboric acids, fluoroboric acid, or boric acid. Solution in aqueous alkali gives the soluble salts of the hydroxyfluoroboric acids, fluoroboric acids, or boric acid. Boron trifluoride, slightly soluble in many organic solvents including saturated hydrocarbons (qv), halogenated hydrocarbons, and aromatic compounds, easily polymerizes unsaturated compounds such as butylenes (qv), styrene (qv), or vinyl esters, as well as easily cleaved cycHc molecules such as tetrahydrofuran (see Furan derivatives). Other molecules containing electron-donating atoms such as O, S, N, P, etc, eg, alcohols, acids, amines, phosphines, and ethers, may dissolve BF to produce soluble adducts. 

Alkali Metal Catalysts. The polymerization of isoprene with sodium metal was reported in 1911 (49,50). In hydrocarbon solvent or bulk, the polymerization of isoprene with alkaU metals occurs heterogeneously, whereas in highly polar solvents the polymerization is homogeneous (51—53). Of the alkah metals, only lithium in bulk or hydrocarbon solvent gives over 90% cis-1,4 microstmcture. Sodium or potassium metals in / -heptane give no cis-1,4 microstmcture, and 48—58 mol % /ram-1,4, 35—42% 3,4, and 7—10% 1,2 microstmcture (46). Alkali metals in benzene or tetrahydrofuran with crown ethers form solutions that readily polymerize isoprene however, the 1,4 content of the polyisoprene is low (54). For example, the polyisoprene formed with sodium metal and dicyclohexyl-18-crown-6 (crown ether) in benzene at 10°C contains 32% 1,4-, 44% 3,4-, and 24% 1,2-isoprene units (54). 

Polymerization of alkynes by Ni" complexes produces a variety of products which depend on conditions and especially on the particular nickel complex used. If, for instance, O-donor ligands such as acetylacetone or salicaldehyde are employed in a solvent such as tetrahydrofuran or dioxan, 4 coordination sites are available and cyclotetramerization occurs to give mainly cyclo-octatetraene (cot). If a less-labile ligand such as PPhj is incorporated, the coordination sites required for tetramerization are not available and cyclic trimerization to benzene predominates (Fig. A). These syntheses are amenable to extensive variation and adaptation. Substituted ring systems can be obtained from the appropriately substituted alkynes while linear polymers can also be produced. 

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) ... 

In summary, silica gel can be an excellent stationary phase for use in exclusion chromatography in the separation of high molecular weight, weakly polar or polarizable polymers. It cannot be used for separating mixtures that require an aqueous mobile phase or operate at a pH outside the range of 4-8. Examples of the type of materials that can be separated by exclusion chromatography using silica gel are the polystyrenes, polynuclear aromatics, polysiloxanes and similar polymeric mixtures that are soluble and stable in solvents such as tetrahydrofuran. 

Hall and Steuck polymerized 2 with a variety of Lewis and Bronsted acids or oxonium salts. The best conditions for the polymerization proved to be the use of phosphorus pentafluoride in methylene chloride solution at -78 °C. Yields of methanol-insoluble polymers ranging from 68 to 84% were obtained with inherent viscosities of 0.26—0.33 dl/g. Lower or higher temperatures gave lower yields. Tetra-hydrofuran as solvent at —78 °C gave 68-92% yields of materials having inherent viscosities of 0.12-0.14 dl/g. No incorporation of tetrahydrofuran into the polymer occurred. 

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. 

Both polymers 10 and 11 are soluble in common organic solvents, melt without decomposition, and can be drawn into the fibers. Molecular weights of the polymers 10 and 11, determined by gel permeation chromatography with tetrahydrofuran as the eluant after purification by reprecipitation from benzene-ethanol, showed a broad monomodal molecular weight distribution. The degree of polymerization depends on particle size of sodium metal. Polymers with molecular weights of 23,000-34,000 are always obtained, if fine sodium particles are used. 

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