A-Olefin

Mashima K, Nakayama Y and Nakamura A 1997 Recent trends in polymerization of a-olefins catalyzed by organometallic complexes of early transition metals Adv. Polym. Sc/. 133 1-54... 

Ziegler found that adding certain metals or their compounds to the reaction mixture led to the formation of ethylene oligomers with 6-18 carbons but others promoted the for matron of very long carbon chains giving polyethylene Both were major discoveries The 6-18 carbon ethylene oligomers constitute a class of industrial organic chemicals known as linear a olefins that are produced at a rate of 3 X 10 pounds/year m the... 

One of the mam uses of the linear a olefins prepared by oligomerization of ethylene is in the preparation of linear low density polyethylene Linear low density polyethylene is a copoly mer produced when ethylene is polymerized in the presence of a linear a olefin such as 1 decene [H2C=CH(CH2)7CH3] 1 Decene replaces ethylene at random points in the growing polymer chain Can you deduce how the structure of linear low density polyethylene differs from a linear chain of CH2 units ... 

The linear a olefins described m Section 14 15 are starting materials for the preparation of a variety of aldehydes by reaction with carbon monoxide The process is called hydroformylation... 

The melting points of a series of poly(a-olefin) crystals were studied. All of the polymers were isotactic and had chain substituents of different bulkinesses. Table 4.2 lists some results. Use Eq. (4.5) as the basis for interpreting the trends in these data. 

Table 4.2 Values of T j, for Poly(a-olefin) Crystals in Which the Polymer has the Indicated Substituent (Results are Discussed in Example 4.1)...

Shell Higher Olefin Process) plant (16,17). C -C alcohols are also produced by this process. Ethylene is first oligomerized to linear, even carbon—number alpha olefins using a nickel complex catalyst. After separation of portions of the a-olefins for sale, others, particularly C g and higher, are catalyticaHy isomerized to internal olefins, which are then disproportionated over a catalyst to a broad mixture of linear internal olefins. The desired fraction is... 

Synthetic oils have been classified by ASTM into synthetic hydrocarbons, organic esters, others, and blends. Synthetic oils may contain the following compounds diaLkylben2enes, poly(a-olefins) polyisobutylene, cycloaUphatics, dibasic acid esters, polyol esters, phosphate esters, siUcate esters, polyglycols, polyphenyl ethers, siUcones, chlorofluorocarbon polymers, and perfluoroalkyl polyethers. 

Alkylated aromatic lubricants, phosphate esters, polyglycols, chlorotrifluoroethylene, siUcones, and siUcates are among other synthetics that came into production during much that same period (28,29). Polyphenyl ethers and perfluoroalkyl polyethers have followed as fluids with distinctive high temperature stabiUty. Although a range of these synthetic fluids find appHcations which employ their unique individual characteristics, total production of synthetics represent only on the order of 2% of the lubricant market. Poly(a-olefin)s, esters, polyglycols, and polybutenes represent the types of primary commercial interest. 

Although p oly (a-olefin) s (PAO) and esters are the prominent synthetic base stocks for automotive appfications, combinations of the two are becoming the choice in offering a balance of properties such as additive solubility, sludge control, and elastomer compatibility (34). 

Although synthetic lubrication oil production amounts to only about 2% of the total market, volume has been increasing rapidly (67). Growth rates of the order of 20% per year for poly( a-olefin)s, 10% for polybutenes, and 8% for esters (28) reflect increasing automotive use and these increases would accelerate if synthetics were adopted for factory fill of engines by automotive manufacturers. The estimated production of poly( a-olefin)s for lubricants appears to be approximately 100,000 m /yr, esters 75,000, poly(alkylene glycol)s 42,000, polybutenes 38,000, phosphates 20,000, and dialkyl benzene 18,000 (28,67). The higher costs reflected in Table 18 (18,28) have restricted the volume of siUcones, chlorotrifluoroethylene, perfluoroalkylpolyethers, and polyphenyl ethers. 

Density. The density (crystallinity) of catalyticaHy produced PE is primarily determined by the amount of comonomer ( a-olefin) in ethylene copolymer. This amount is easily controlled by varying the relative amounts of ethylene and the comonomer in a polymerization reactor. In contrast, the density of PE produced in free-radical processes is usually controlled by temperature. 

High density polyethylene (HDPE) is defined by ASTM D1248-84 as a product of ethylene polymerisation with a density of 0.940 g/cm or higher. This range includes both homopolymers of ethylene and its copolymers with small amounts of a-olefins. The first commercial processes for HDPE manufacture were developed in the early 1950s and utilised a variety of transition-metal polymerisation catalysts based on molybdenum (1), chromium (2,3), and titanium (4). Commercial production of HDPE was started in 1956 in the United States by Phillips Petroleum Company and in Europe by Hoechst (5). HDPE is one of the largest volume commodity plastics produced in the world, with a worldwide capacity in 1994 of over 14 x 10 t/yr and a 32% share of the total polyethylene production. 

The number of branches in HDPE resins is low, at most 5 to 10 branches per 1000 carbon atoms in the chain. Even ethylene homopolymers produced with some transition-metal based catalysts are slightly branched they contain 0.5—3 branches per 1000 carbon atoms. Most of these branches are short, methyl, ethyl, and -butyl (6—8), and their presence is often related to traces of a-olefins in ethylene. The branching degree is one of the important stmctural features of HDPE. Along with molecular weight, it influences most physical and mechanical properties of HDPE resins. 

The chemical iadustry manufactures a large variety of semicrystalline ethylene copolymers containing small amounts of a-olefins. These copolymers are produced ia catalytic polymerisation reactions and have densities lower than those of ethylene homopolymers known as high density polyethylene (HDPE). Ethylene copolymers produced ia catalytic polymerisation reactions are usually described as linear ethylene polymers, to distiaguish them from ethylene polymers containing long branches which are produced ia radical polymerisation reactions at high pressures (see Olefin POLYMERS, LOWDENSITY polyethylene). 

Densities and crystallinities of ethylene—a-olefin copolymers mosdy depend on their composition. The classification ia Table 1 is commonly used (ASTM D1248-48). VLDPE resias are usually further subdivided iato PE plastomers of low crystallinity, 10—20%, with densities ia the range of 0.915—0.900 g/cm, and completely amorphous PE elastomers with densities as low as 0.860 g/cm. ... 

Commercial production of PE resias with densities of 0.925 and 0.935 g/cm was started ia 1968 ia the United States by Phillips Petroleum Co. Over time, these resias, particularly LLDPE, became large volume commodity products. Their combiaed worldwide productioa ia 1994 reached 13 X 10 metric t/yr, accouatiag for some 30% market share of all PE resias ia the year 2000, LLDPE productioa is expected to iacrease by 50%. A aew type of LLDPE, compositioaaHy uniform ethylene—a-olefin copolymers produced with metallocene catalysts, was first introduced by Exxon Chemical Company in 1990. The initial production volume was 13,500 t/yr but its growth has been rapid indeed, in 1995 its combiaed production by several companies exceeded 800,000 tons. 

The large number of commodity and specialty resias collectively known as LLPDE are in fact made up of various resias, each different from the other in the type and content of a-olefin in the copolymer, compositional and branching uniformity, crystallinity and density, and molecular weight and molecular weight distribution (MWD). 

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