Zinc oxide reactions with propylene

Having established that the polymerization of propylene oxide by the zinc hexacyanocobaltate complex catalyst proceeds in the absence of a chain termination reaction, it was of interest to study separately the chain propagation reaction. A non-termi-nated polymer "seed" was prepared and its rate of reaction with propylene oxide was studied. The results of a series of these seeded polymerizations carried out at 30°, 40° and 50° are given in Figvire 6, where log [M]o/[M]t is plotted against time. 

Results with butene are not as extensive as those with propylene. Nevertheless, on the basis of the ground work laid by the more extensive propylene studies, we are able to apply similar criteria to the more limited data for butene and conclude that a x-allyl species forms. Some preliminary studies suggest that two x-allyl species form from 1-butene (65), corresponding to the syn and anti forms. The results for propylene, the fact that x-allyl species form from butene, and the fact that zinc oxide is an effective catalyst for butene isomerization strongly suggest that these x-allyls are intermediates in the isomerization reaction. 

Preparation of Poly (propylene ether) Polyols. The polymerization of propylene oxide with zinc hexacyanocobaltate complexes in the presence of proton donors results in the production of low-molecular-weight polymers. Table V shows the variety of types of compounds that have been found to act this way. Since these compounds end up in the polymer chains, it seems reasonable to call them chain initiators. Thus, in essence, each of these compounds is activated by the catalyst to react with propylene oxide to form a hydroxylpropyl derivative. Thereafter, the reaction continues on the same basis, with the proton of the hydroxyl group reacting with further propylene oxide. This sequence is shown here with 1,5-pentanediol as the initiator. The hydroxyl... 

Polyether Polyols. Polyether polyols are addition products derived from cyclic ethers (Table 4). The alkylene oxide polymerization is usually initiated by alkali hydroxides, especially potassium hydroxide. In the base-catalyzed polymerization of propylene oxide, some rearrangement occurs to give allyl alcohol. Further reaction of allyl alcohol with propylene oxide produces a monofunctional alcohol. Therefore, polyether polyols derived from propylene oxide are not truly difunctional. By using zinc hexacyano cobaltate as catalyst, a more difunctional polyol is obtained (20). Olin has introduced the difunctional polyether polyols under the trade name POLY-L. Trichlorobutylene oxide-derived polyether polyols are useful as reactive fire retardants. Poly(tetramethylene glycol) (PTMG) is produced in the acid-catalyzed homopolymerization of tetrahydrofuran. Copolymers derived from tetrahydrofiiran and ethylene oxide are also produced. 

Figure 15.2 Reactions of bis(diisopropyI)-thiophosphoryI disulfide (DIPDIS) with ethylene-propylene-diene rubber (EPDM) and zinc oxide. (From Reference 32 with permission from John Wiley Sons.)...

A number of metal-catalyzed polymerizations have utilized CO2 as both a solvent and as a reagent in the reactions. Precipitation copolymerization of either propylene oxide (83) or cyclohexene oxide (84) with CO2 in SCCO2 has been catalyzed using heterogeneous zinc catalysts. Copolymerizations of CO2 and propylene oxide formed PCs with a molecular weight of about 10 g/mol and incorporation of CO2 at greater than 90% (eq. (7)). A small percentage of propylene carbonate by-product was also observed. 

The most important source of acetone is the Hock process for phenol production. In this process acetone is obtained as stoichiometric coupling product. If acetone needs to be produced deliberately, it can be obtained by oxidative dehydrogenation or dehydrogenation of isopropanol. Oxidative dehydrogenation proceeds at 400-600 °C at silver or copper contacts, direct dehydrogenation is carried out at 300-400 °C using zinc contacts. Alternatively, acetone can also be obtained by a Wacker-Hoechst oxidation of propylene. Acetone is used industrially as solvent. Moreover, the aldol condensate products of acetone (diacetone alcohol) are used as solvents. Acetone is also converted in an add catalyzed reaction with two moles of phenol for the synthesis of bisphenol A. Bisphenol A is an important feedstock for the production of epoxy resins and polycarbonates. 

The polymerization kinetics were studied in detail. It appeared that the rate of reaction decreased as the concentration of complex increased. This anomalous behavior was explained in terms of the ability of all the zinc atoms in the complex to form coordination complexes with propylene oxide monomer, but only the inner methoxyls were effective in opening the oxirane ring of monomer coordinated with the central zinc atom. In support of this explanation, it is noted that neither diethylzinc alone nor ethylzinc methoxide initiate propylene oxide polymerization under the conditions described here however, both will form complexes with propylene oxide, about two methyl oxiranes per zinc. Addition of either zinc alkyl to Tsuruta Catalyst/... 

As shown in Scheme 9, various organic compounds can act as a chiral initiator of asymmetric auto catalysis. 2-Methylpyrimidine-5-carbaldehyde 9 was subjected to the addition of z-Pr2Zn in the presence of chiral butan-2-ol, methyl mandelate and a carboxylic acid [74], When the chiral alcohol, (S)-butan-2-ol with ca. 0.1% ee was used as a chiral initiator of asymmetric autocatalysis, (S)-pyrimidyl alkanol 10 with 73% ee was obtained. In contrast, (,R)-butan-2-ol with 0.1% ee induced the production of (A)-10 with 76% ee. In the same manner, methyl mandelate (ca. 0.05% ee) and a chiral carboxylic acid (ca. 0.1% ee) can act as a chiral initiator of asymmetric autocatalysis, therefore the S- and IC enantiomers of methyl mandelate and carboxylic acid induce the formation of (R)- and (S)-alkanol 10, respectively. Chiral propylene oxide (2% ee) and styrene oxide (2% ee) also induce the imbalance of ee in initially forming the zinc alkoxide of the pyrimidyl alkanol in the addition reaction of z-Pr2Zn to pyrimidine-5-carbaldehyde 11 [75]. Further consecutive reactions enable the amplification of ee to produce the highly enantiomerically enriched alkanol 12 (up to 96% ee) with the corresponding... 

It may be mentioned that the use of ionic nucleophilic initiators, instead of zinc-based coordination catalysts, in order to promote propylene oxide/carbon dioxide copolymerisation, did not result in the formation of any copolymer but led to the cyclic carbonate, propylene carbonate [194,236,237]. Also, zinc-based coordination catalysts with non-condensed zinc atoms in their molecules (formed by the reaction of diethylzinc with a monoprotic compound such as... 

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