Trialkyl aluminum catalysts

The effect of a catalyst is important in cationic copolymerizations. Epoxides and /3-lactones form random copolymers only with trialkyl aluminum catalysts. Unusual sequence distributions were observed in the cationic copolymerization of epoxides or lactones using Lewis acids175-177) have been attributed to the di-... 

The anion of N-nitrosomethylethylamine (2.1-7) reacts with nitriles to form products of structure 2.1-8 in fair-to-good yield (Eq. 8). N-methyl-1,2,3-triazoles can be prepared by alkylation although both 1- and 2-methyl products are formed (Eq. 9). The reaction of benzonitrile with diazomethane in the presence of trialkyl-aluminum catalysts provides a modest yield of 2.1-9. ... 

In 1958, Natta tried to synthesize PA by bubbling acetylene gas through a titanium/trialkyl aluminum catalyst solution while stirring. One of the products in the reaction was a black, semicrystalline powder that was completely insoluble and unstable in the presence of air and water [4]. Although no analyses could be made, Natta assumed that he had made a high-molecular-weight, mostly trans, PA. Subsequently, PA was observed as a side product in the attempts to cyclotrimerize and cyclotetramerize acetylene [5]. 

Al—Ti Catalyst for cis-l,4-PoIyisoprene. Of the many catalysts that polymerize isoprene, four have attained commercial importance. One is a coordination catalyst based on an aluminum alkyl and a vanadium salt which produces /n j -l,4-polyisoprene. A second is a lithium alkyl which produces 90% i7j -l,4-polyisoprene. Very high (99%) i7j -l,4-polyisoprene is produced with coordination catalysts consisting of a combination of titanium tetrachloride, TiCl, plus a trialkyl aluminum, R Al, or a combination of TiCl with an alane (aluminum hydride derivative) (86—88). 

Chromium Oxide-Based Catalysts. Chromium oxide-based catalysts were originally developed by Phillips Petroleum Company for the manufacture of HDPE resins subsequendy, they have been modified for ethylene—a-olefin copolymerisation reactions (10). These catalysts use a mixed sihca—titania support containing from 2 to 20 wt % of Ti. After the deposition of chromium species onto the support, the catalyst is first oxidised by an oxygen—air mixture and then reduced at increased temperatures with carbon monoxide. The catalyst systems used for ethylene copolymerisation consist of sohd catalysts and co-catalysts, ie, triaLkylboron or trialkyl aluminum compounds. Ethylene—a-olefin copolymers produced with these catalysts have very broad molecular weight distributions, characterised by M.Jin the 12—35 and MER in the 80—200 range. 

The second type of solution polymerization concept uses mixtures of supercritical ethylene and molten PE as the medium for ethylene polymerization. Some reactors previously used for free-radical ethylene polymerization in supercritical ethylene at high pressure (see Olefin POLYMERS,LOW DENSITY polyethylene) were converted for the catalytic synthesis of LLDPE. Both stirred and tubular autoclaves operating at 30—200 MPa (4,500—30,000 psig) and 170—350°C can also be used for this purpose. Residence times in these reactors are short, from 1 to 5 minutes. Three types of catalysts are used in these processes. The first type includes pseudo-homogeneous Ziegler catalysts. In this case, all catalyst components are introduced into a reactor as hquids or solutions but form soHd catalysts when combined in the reactor. Examples of such catalysts include titanium tetrachloride as well as its mixtures with vanadium oxytrichloride and a trialkyl aluminum compound (53,54). The second type of catalysts are soHd Ziegler catalysts (55). Both of these catalysts produce compositionaHy nonuniform LLDPE resins. Exxon Chemical Company uses a third type of catalysts, metallocene catalysts, in a similar solution process to produce uniformly branched ethylene copolymers with 1-butene and 1-hexene called Exact resins (56). 

Molecular weights of poly(propylene oxide) polymers of greater than 100,000 are prepared from catalysts containing FeCl (40,41). The molecular weight of these polymers is gready increased by the addition of small amounts of organic isocyanates (42). Homopolymers of propylene oxide are also prepared by catalysis using diethylzinc—water (43), diphenylzinc—water (44), and trialkyl aluminum (45,46) systems. 

The discovery by Ziegler that ethylene and propylene can be polymerized with transition-metal salts reduced with trialkyl aluminum gave impetus to investigations of the polymerization of conjugated dienes (7—9). In 1955, synthetic polyisoprene (90—97% tij -l,4) was prepared using two new catalysts. A transition-metal catalyst was developed at B. E. Goodrich (10) and an alkaU metal catalyst was developed at the Ekestone Tke Rubber Co. (11). Both catalysts were used to prepare tij -l,4-polyisoprene on a commercial scale (9—19). 

Polyisoprenes of 94—98% as-1,4 content were obtained with lanthanum, cerium, praseodymium, neodymium, and other rare-earth metal ions (eg, LnCl ) with trialkyl aluminum (R3AI) (34). Also, a NdCl 2THF(C2H3)3A1 catalyst has been used to prepare 95% <7j -l,4-polyisoprene (35). <7j -l,4-Polyisoprene of 98% as-1,4 and 2% 3,4 content was obtained with organoalurninum—lanthariide catalysts, NdCl where L is an electron-donor ligand such as ethyl alcohol or butyl alcohol, or a long-chain alcohol, and is 1 to 4 (36). 

Amorphous (most likely atactic) 3,4-polyisoprene of 94—100% 3,4-microstmcture was prepared with a (C2H 3A1—Ti(0—/ -C Hy) catalyst (11). Crystalline 3,4-polyisoprene containing about 70% 3,4-units and about 30% i7j -l,4-microstmcture was prepared using a catalyst derived from iron acetyl acetonate, trialkyl aluminum, and an amine in benzene (37). However, this polyisoprene contained gel and was obtained in poor yield. Essentially gel-free crystallizable 3,4-polyisoprene of 70—85% 3,4-microstmcture with the remainder being cis-1,4 microstmcture was prepared in conversions of greater than 95% with a water-modified tri alkyl aluminum, ferric acetyl acetonate, and 1,10-phenanthroline catalyst (38). The 3,4-polyisoprene is stereoregular and beheved to be syndiotactic or isotactic. 

Effective catalysts have recently been developed for the addition of trialkyl-aluminum reagents to alkenes (carboalumination). 6 -(Pentamethylcyclopentadienyl) zirconium dimethylide activated by fra-(pentafluorophenyl)boron promotes the addition of trimethylaluminum to terminal alkenes.221... 

It can be seen that both the solvent and the catalyst affect the structure of the polymer produced. For example, the structure of the polyisoprene differs strongly with the alkali metal, even when used in the same solvent medium. Experiments with a typical organometallic complex catalyst, consisting of trialkyl-aluminum and titanium tetrachloride, show that the same initiator can lead to quite different structures in the products of polymerization of isoprene and of butadiene. 

It is known that the polymerization of ethylene by trialkyl aluminum is not a rapid reaction at normal pressures and temperatures. Ziegler, Gellert, Holzkamp, Wilke, Duck and Kroll (72) have found that ethylene was polymerized to higher trialkylaluminums only at elevated temperatures and pressures. Anionic hydride transfer commonly occured under these conditions. However, the addition of a transition metal halide such as titanium tetrachloride, the classical Ziegler catalyst, polymerized ethylene rapidly under mild conditions. 

There is considerable information that points to the cationic nature of the Ziegler ethylene polymerization. Tabata, Shibano, Sobue and Hara (76) have found that the polymerization of ethylene at —78° with cobalt —60 irradiation shows the characteristics of cationic polymerization. Roha, Kreider, Frederick and Beears (77) found that an active Ziegler catalyst for polyethylene from a non-reduced trialkyl-aluminum-titanium tetrachloride system requires an electrophilic com-... 

Fig. 5. Reactions with soluble titanocene catalysts, trialkyl-aluminum, and ethylene (56).

Low-molar-mass poly(butadiene) oils with 80%-97% cw-1,4 contents are produced with other Ziegler catalysts (for example, cobalt compounds with alkyl aluminum chlorides or nickel compounds with trialkyl aluminum and boron trifluoride-etherate). The products have few cross-links and dry as fast as wood oil and faster than linseed oil. Conversion of the poly (butadiene) oils with 20% maleic anhydride gives air-drying (air-hardening) alkyd resins. Modified poly (butadiene) oils stabilize erosion-endangered soils. Because of its low viscosity, the aqueous emulsion penetrates the surface soil layers. The surface crust is reinforced by an oxidative bonding process. Since no skin is formed on the soil crust, the aqueous absorption characteristics of the soil are retained. 

Later work by Ishida (1962) provided an explanation for the apparent contradiction. Briefly, the explanation is that the initiator is not really formed according to Eq. (25). When trialkyl-aluminum is used, the evidence which leads to this conclusion is as follows. If very dry acetaldehyde is used, little polymerization occurs. On the other hand, if water is reacted with the alkylalumi-num, a very active catalyst results. Since maximum activity is produced after reacting one mole of water with two moles of alkylaluminum [Eq. (26)], Ishida proposed that a dialumoxane, [(C2Hr,)AI]20, is the catalyst. In agreement with this work, Tani... 

High polymers. PolyCpropylene oxide) polymers with molecular weights of 100,000 or more can be prepared with a catalyst that consists of FeClj and approximately five equivalents of PO. The addition of small amounts of toluene 2,4- and 2,6-diisocyanates greatly increases the molecular weights of the polymers obtained. PO homopolymers can also be prepared with catalysts such as diethyl zinc and trialkyl aluminum compound. 

The liquid-phase industrial process for the dimerization of propylene is called the dimersol process. In this process, a Zeigler-type catalyst is generated in situ by the treatment of a nickel salt with trialkyl aluminum. The different isomers of C. alkenes that are formed can be explained by referring to Figure 7.1. A nickel hydride complex 7.1 initiates the dimerization reaction. Complexes 1.1 and 73 are formed by the insertion of the first propylene into the Ni-H bond in anti-Markovnikov and Markovnikov maimer, respectively. 

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