Olefin branching copolymers

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). 

Branch and bound techniques, discrete optimization via, 26 1023 Branched aliphatic solvents, 23 104 Branched alkylbenzene (BAB), 77 725 Branched copolymers, 7 610t Branched epoxies, 70 364 Branched olefins, 77 724, 726 Branched polycarbonates, 79 805 Branched polymers, 20 391 Branched primary alcohols, synthetic processes for, 2 2 7t Branching... 

Mechanical Properties. Mechanical characteristics of ethylene copolymers are functions of their structural characteristics, such as content and type of a-olefin, branching uniformity, molecular weight and width of molecular weight distribution (MWD), and orientation (see Table 5 for properties of films made from three grades of LLDPE). 

Styrene, which can be treated formally as an a-olefin branched in the 3-position, forms copolymers with ethylene and a-olefins (as well as with /i-olefins, involving isomerisation copolymerisation). Both heterogeneous Ziegler-Natta catalysts and a single-site metallocene catalyst promote the copolymerisation. 

Finally, examination of the volatile products of irradiation of branched polymers reveals the importance of loss of the side chains. For example, irradiation of branched copolymers of ethylene and a-olefins results in volatile products characteristic of both the frequency and structure of the side chain (59,60). In this work the authors also highlight the influence of radiation temperature and morphology of the irradiated semiciystalline polymer. 

Linear low density PE-LLD 0.910...0.925 short chain branches, copolymers with 1-olefins, 393...408 K... 

Some of the principles as well as problems involved in the melting of random copolymers are found in olefin type copolymers. The melting temperatures of a large number of random type ethylene copolymers, as determined by differential scanning calorimetry, are plotted as a function of the mole percent branch points in Fig. 5.11. The samples represented in this figure are either molecular weight and compositional fractions or those with a narrow composition distribution with a most probable molecular weight distribution.(74) These samples were crystallized and heated rapidly. In this set of data there are two different copolymers that contain ethyl... 

While previous studies containing precisely placed methyl- and ethyl-branched PE copolymers via ADMET are perfectly sequenced models of EP and EB materials, copolymers of ethylene with a-olefins are obtained in a statistically random fashion using Ziegler-Natta or metallocene chemistry. Although these materials can be obtained totally randomized, imperfections over the branch identity are usually incorporated into the PE backbone due to tile chain nature of this chemistry. Randomly branched copolymers with only one kind of branch identity can be created using ADMET, copolymerization followed by exhaustive hydrogenation of a methyl-branched a,(o-diene with an unbranched a,to-diene yields statistically random EP copolymers. " Randomness in tiie final material is assured since copolymerization of both diene monomers is carried out, and no electronically or sterically major... 

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). 

A lower a-olefin content is required in a uniformly branched ethylene copolymer to decrease its crystallinity and density to a given level. 

Physical Properties. LLDPE is a sernicrystaUine plastic whose chains contain long blocks of ethylene units that crystallize in the same fashion as paraffin waxes or HDPE. The degree of LLDPE crystallinity depends primarily on the a-olefin content in the copolymer (the branching degree of a resin) and is usually below 40—45%. The principal crystalline form of LLDPE is orthorhombic (the same as in HDPE) the cell parameters of nonbranched PE are a = 0.740 nm, b = 0.493 nm, and c (the direction of polymer chains) = 0.2534 nm. Introduction of branching into PE molecules expands the cell slightly thus a increases to 0.77 nm and b to around 0.50 nm. 

Content of Ot-Olefin. An increase in the a-olefin content of a copolymer results in a decrease of both crystallinity and density, accompanied by a significant reduction of the polymer mechanical modulus (stiffness). Eor example, the modulus values of ethylene—1-butene copolymers with a nonuniform compositional distribution decrease as shown in Table 2 (6). A similar dependence exists for ethylene—1-octene copolymers with uniform branching distribution (7), even though all such materials are, in general, much more elastic (see Table 2). An increase in the a-olefin content in the copolymers also results in a decrease of their tensile strength but a small increase in the elongation at break (8). These two dependencies, however, are not as pronounced as that for the resin modulus. 

Most Kaminsky catalysts contain only one type of active center. They produce ethylene—a-olefin copolymers with uniform compositional distributions and quite narrow MWDs which, at their limit, can be characterized by M.Jratios of about 2.0 and MFR of about 15. These features of the catalysts determine their first appHcations in the specialty resin area, to be used in the synthesis of either uniformly branched VLDPE resins or completely amorphous PE plastomers. Kaminsky catalysts have been gradually replacing Ziegler catalysts in the manufacture of certain commodity LLDPE products. They also faciUtate the copolymerization of ethylene with cycHc dienes such as cyclopentene and norhornene (33,34). These copolymers are compositionaHy uniform and can be used as LLDPE resins with special properties. Ethylene—norhornene copolymers are resistant to chemicals and heat, have high glass transitions, and very high transparency which makes them suitable for polymer optical fibers (34). 

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). 

In order to improve the physical properties of HDPE and LDPE, copolymers of ethylene and small amounts of other monomers such as higher olefins, ethyl acrylate, maleic anhydride, vinyl acetate, or acryUc acid are added to the polyethylene. Eor example, linear low density polyethylene (LLDPE), although linear, has a significant number of branches introduced by using comonomers such as 1-butene or 1-octene. The linearity provides strength, whereas branching provides toughness. 

Polyethylene, a thermoplastic, is the largest selling plastic material. LDPE is a branched polyethylene whose branches prevent close packing and gives low density. HDPE is polyethylene that has essentially no branching, so the molecules pack very well, which leads to high density and high crystallinity. LLDPE is actually a copolymer prepared at low temperature and low pressure from a mixture of ethylene and about 10% of a C4-C8 olefin. 

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