2,3-butene oxide polymerization

By using TPPAICI as the catalyst, propylene oxide, ethylene oxide, and 1,2-butene oxide polymerize rapidly at room temperature (Fig. 1). Under the same conditions, Et2AlCl exhibits a low catalytic activity. 

PO. In addition, the produced polymer does not include a phenolate terminal group which should be derived from 2a. These facts indicate that 2a does not initiate but accelerates the polymerization through coordination to PO. The living nature of the PO polymerization by using lb/2a system is advantageous for the production of a block co-polymer the polymerization of PO followed by addition of 1,2-butene oxide to the polymerization mixture gives diblock co-polymer with a narrow MWD (Scheme 4). 

As an active initiator for a co-polymerization, acyl-cobalt complexes also work well. As demonstrated by Alper and Lee, an equimolar mixture of Go2(GO)s, benzyl bromide (BnBr), and dihydro-1,10-phenanthroline 17, possibly generating BnGOGo(GO)4 under the reaction conditions, co-polymerized PO or 1,2-butene oxide with GO, and the... 

The remaining 30 percent of 1-butene is divided among several uses. About 10-15 percent of the 1-butene is polymerized in the presence of a Ziegler-type catalyst to produce polybutene-1 resin. The markets for this resin are pipe, specialty films, and polymer alloys. Approximately the same volume of 1-butene is reacted with synthesis gas in an oxo reaction to produce valeraldehydes. These C5 aldehydes are then hydrogenated to amyl alcohols or oxidized to valeric acid. Amyl alcohols are consumed in the production of lube oil additives and amyl acetate and in solvent uses. Valeric acid goes into lubricant base stocks and specialty chemicals. 

In the large mqority of the cationic polymerizations of heterocycles the propaption step proceeds with complete inversion of conf uration. Ihis vras diown for the first time by Vandenberg in the polymerization of ds- and trans-2,3-butene oxides as... 

In the polymerization of cis- and trans-23-butene oxides, stereoreplar polymers are obtained by a low-tenqierature cationic proc ... 

The polymerization of cis oxides gives, in contrast to trans monomers, polymers of different stereochemistry, namely cis-2,3-butene oxide forms racemic (RR, SS) disyndiotactic polymers whereas cis-1,4-dichloro-2,3-butene oxide gives racemic mixtures of (RR, RR) and (SS, SS) diisotactic polymers. 

Finally, the stereospecificity of the phosphorane-promoted cyclodehydration is adequately demonstrated in the reaction of d,Z-2,3-butanediol (9) with DTPP in CD2CI2 (35 C, 10 h). The stepwise nature of the cyclodehydration process gives exclusively d5-2,3-epoxybutane (10 >99%) by NMR analysis [6 12.9 (CH3) and 52.4 (CHO)] (76). This latter result is consonant with the previous findings of Denney etal. 24) where a mixture containing 88% d,/- and 12% zne5o-4,5-dimethyl-2,2,2-triethoxy-1,3,2X5-dioxaphospholanes (11) gave a mixture of 85% cis- and 15% /rans-2,3-butene oxides (10), respectively, during tiiermolysis (117°C, 42 h) (equations 2 and 3). Polymeric Dioxaphospholanes. 

It has been reported previously that bls-trlfluoromethane-sulfonyl methane ("dlsulfone ) and its derivatives are good epoxy homo-polymerization catalysts (11,12). Calorimetric studies have shown that l,l,3,3-tetrakl8(trlfluoro methanesulfonyl) propane ("tetra-sulfone") is probably the only effective catalyst for homopolymerization of an aliphatic epoxide, e.g. butene oxide, in a non-polar solvent at room temperature (Figure 2). The other dlsulfone catalyst along with Bronsted acids are poor catalysts. 

BUTENE OXIDE (106-88-7) Forms explosive mixture with air (flash point -7°F/-22°C). Unless inhibited, violent polymerization can be caused by elevated temperatures, sunlight, acids, aluminum chlorides, bases, iron, tin, potassium, sodium, sodium hydroxide, or certain salts. Reacts violently with oxidizers, alcohols. Reacts with hydroxides, metal chlorides, oxides. Flow or agitation of substance may generate electrostatic charges due to low conductivity. Storage tanks and other equipment should be absolutely dry and free from air, ammonia, acetylene, hydrogen sulfide, rust, and other contaminants. 

Among new initiators for the polymerization of propylene oxide, ethylene oxide, 1-butene oxide, and isobutylene oxide are zinc hexacyanocobaltate [54] and aluminum porphyrin [55]. 

A similar procedure affords 1,2-butene oxide-propylene oxide and l,2 -butene oxide-ethylene oxide block copolymers, both with narrow molecular weight distribution. The formation of these block copol3nners confirms the living nature of the epoxide polymerization by TPPAICI. 

The activating effect of electron donor groups, such as methyl groups, Is also shown by the polymerization of els- and trans-2-butene oxides. Vandenberg used these monomers to offer the first proof that the ring opening reaction in cationic polymerization proceeded with clean Inversion of configuration (22). 

Soluble poly(l-butylperylene) (58) was prepared in very high yields by Anton and Mullen [70] who used the procedure of Taylor [71], which involves the oxidative coupling of bis-Grignard reagents with as-l,4-dichloro-2-butene as an oxidant. The products contain 4,9- and 4,10-perylenylene moieties, are fully soluble and possess average degrees of polymerization of ca. 22. 

Small olefins, notably ethylene (ethene), propene, and butene, form the building blocks of the petrochemical industry. These molecules originate among others from the FCC process, but they are also manufactured by the steam cracking of naphtha. A wealth of reactions is based on olefins. As examples, we discuss here the epoxida-tion of ethylene and the partial oxidation of propylene, as well as the polymerization of ethylene and propylene. 

The experimental activation energies given in the last column of Table II are in the anticipated order of magnitudes. The activation energy of 24.0 kcal. per mole for the oxidation of 1-hexadecene to hydroperoxide is close to the value of 25.3 kcal. per mole recently reported for the constant velocity of peroxide accumulation. .. for butene-1 (9). The activation energy for the alkenyl hydroperoxide decomposition is reasonable. The activation energy of 48.1 kcal. per mole for the decomposition polymeric dialkyl peroxide is considerably higher than the value of about 37 kcal. per mole for tert-butyl peroxide decomposition. The... 

Pseudoliquid-phase catalysis (bulk type I catalysis) was reported in 1979, and bulk type II behavior in 1983. In the 1980s, several new large-scale industrial processes started in Japan based on applications of heteropoly catalysts that had been described before (5, 6, 72) namely, oxidation of methacro-lein (1982), hydration of isobutylene (1984), hydration of n-butene (1985), and polymerization of tetrahydrofuran (1987). In addition, there are a few small- to medium-scale processes (9, 10). Thus the level of research activity in heteropoly catalysis is very high and growing rapidly. 

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