Ethylene/propylene copolymers copolymer chains

The cross-sectional area per chain in the hexagonal lattice of irradiated PE varies between 20.6 and 22.0 A. It is, thus, always greater than the cross-sectional area in the rotator phase in paraffins (19.5-20.0 A ), but on average somewhat smaller than that in constrained PE fibers above 7, /, (21.4-22.7 A ). An ethylene-propylene diene copolymer with approximately 64%, 32%, and 4% by weight of each component, respectively, was found to contain hexagonal crystals with a cross-sectional area per chain of 20.3 A". 

Since the excellent work of Moore and Watson (6, who cross-linked natural rubber with t-butylperoxide, most workers have assumed that physical cross-links contribute to the equilibrium elastic properties of cross-linked elastomers. This idea seems to be fully confirmed in work by Graessley and co-workers who used the Langley method on radiation cross-linked polybutadiene (.7) and ethylene-propylene copolymer (8) to study trapped entanglements. Two-network results on 1,2-polybutadiene (9.10) also indicate that the equilibrium elastic contribution from chain entangling at high degrees of cross-linking is quantitatively equal to the pseudoequilibrium rubber plateau modulus (1 1.) of the uncross-linked polymer. 

Methyl end groups resulting from main-chain scission in ethylene-propylene copolymers have observed by their characteristic 13C NMR resonance and determined quantitatively to give values of G(scission). 

Initiators such as BPO are used not only for the initiation of chain reaction polymerization, but also for the curing of polyesters and ethylene-propylene copolymers, and for the grafting of styrene on elastomeric polymer chains. 

Ethylene-propylene copolymers, and also polyisobutylene, are rubbers with saturated chains, which cannot be vulcanised with sulphur. They are, therefore. 

The block copolymers shown in both Table V and VI were hydrogenated. The B-lU block produced polyethylene and the polyisoprene block produced ethylene propylene alternating copolymer. The physical properties of this copolymer, composed of crystalline polyethylene block and a soft elastomeric segment made of an EPR block, is tabulated in Table VII. The data in this table illustrate the fact that a diblock of hydrogenated polybutadi ene-polyisoprene gave excellent physical properties. This is a further illustration of the new concept of soft chain interpenetrating the crystalli zable polyethylene chain via chain folding. 

Mean-square unperturbed dimensions and dipole moments are calculated for propylene-vinyl chloride copolymers by means of RIS theory. The calculations indicate that for these chain molecules is much more sensitive to chemical sequence distribution than is 0, a conclusion in agreement with results of previous studies of ethylene-propylene copolymers and styrene-substituted styrene copolymers. In the case of propylene-vinyl chloride chains, both 0 and are most strongly dependent on chemical sequence distribution in the case of copolymers which are significantly syndiotactic in stereochemical structure. 

RIS theory is used to predict values of the optical-configuration parameter Aa for ethylene - propylene copolymers as a function of chemical composition, chemical sequence distribution, and stereochemical structure of the propylene sequences. The calculations are based on information available for ethylene and propylene homopolymers, and on the model used to interpret the unperturbed dimensions of these copolymers. Values of Aa are generally found to decrease significantly with increase in the fraction of propene units, but to be relatively insensitive to chemical sequence distribution and stereochemical structure. Geometries and conformational energies are the same as those used for the interpretation of the unperturbed dimensions of these chains. The conformational energies used are E(q) = 0, EM 2.09, and E a>) = 0.37 kJ mol-1. 

The structure of ethylene-propylene copolymers shows that in the case of syndiospecific polymerization the steric control is due to the chirality of the asymmetric carbon of the last unit of the growing chain end.337... 

At room temperature, PE is a semi-crystalline plastomer (a plastic which on stretching shows elongation like an elastomer), but on heating crystallites melt and the polymer passes through an elastomeric phase. Similarly, by hindering the crystallisation of PE (that is, by incorporating new chain elements), amorphous curable rubbery materials like ethylene propylene copolymer (EPM), ethylene propylene diene terpolymer (EPDM), ethylene-vinyl acetate copolymer (EVA), chlorinated polyethylene (CM), and chlorosulphonated polyethylene (CSM) can be prepared. 

The same conclusion as in the case of propylene homopolymerisation has been drawn considering IR [396] and NMR [389,395] spectra of ethylene/propylene copolymers obtained with vanadium-based syndiospecific catalysts. The type of propylene insertion depends on the kind of last inserted monomer unit secondary insertion [scheme (40)] occurs more frequently when the last monomeric unit of the growing chain is propylene, while primary propylene insertion [scheme (39)] is more frequent when the last monomeric unit of the growing chain is ethylene [2]. The above explains the microstructure of ethylene/propylene copolymers obtained with vanadium-based Ziegler-Natta catalysts. These copolymers contain both m and r diads when the sequence of propylene units is interrupted by isolated ethylene units i.e. a propylene insertion after an ethylene insertion is substantially non-stereospecific [327,390,397], The existence of a steric interaction between the incoming monomer molecule and the last added monomer unit is also confirmed by the fact that the propagation rate for the secondary insertion of propylene in syndiospecific polymerisation is lower than for primary insertion in non-stereospecific polymerisation [398],... 

Many attempts have been made to synthesise ethylene/propylene block copolymers, referred to as polyallomers, with isospecific Ziegler-Natta catalysts. However, true block copolymers can hardly be synthesised. This is due to the short life of the growing polymer chains [68,241]. Therefore, only in a few cases, when the copolymers are synthesised by adding two comonomers sequentially and under very specific conditions in order to reduce chain transfer reactions, does unambiguous evidence for true block copolymer formation with isospecific catalysts exist [457]. 

Effect of Substrate. Again, polyethylene and ethylene-propylene copolymers are better substrates for block formation than polypropylene (Table XI). Polyethylene is better than polypropylene, and a polyethylene-polypropylene-polyethylene type of block polymer is better than polyethylene. This agrees with what has been found for AFR polymers containing methylvinylpyridine and acrylonitrile. It also supports our belief that AFR polymers are formed by the growing of a free radical polymer onto active ends of anionic polymer chains. If it were a random grafting reaction, it would be hard to explain why a propylene polymer with a more vulnerable tertiary hydrogen should give a lower... 

Toughened polypropylene may be prepared by block copolymerization in which ethylene monomer is added during the final stages of the polymerization of propylene (4). Thus, some polypropylene chains would contain an end block of rubbery ethylene-propylene copolymer. Alternatively, a blend of an elastomeric copolymer of ethylene and propylene (EPR or EPDM) with isotactic polypropylene (PP) can produce an impact-resistant polymer (5). 

Figure 1 Polymer enchainment patterns occurring in polyethylene (PE), ethylene-propylene copolymer (EP), and polypropylene (PP) chains (HDPE = crystalline high-density polyethylene, LLDPE — linear low-density polyethylene, LDPE = low-density polyethylene, EP rubber = elastomeric ethylene-propylene copolymer).

Copolymers of ethylene with a-olefins, such as the short-chain branched LLDPE (linear low-density polyethylene) impact materials or the EPD (ethylene-propylene-diene copolymer) rubbers represent major percentages of the total polyolefin production, due to their desirable mechanical properties. Solid-state MgCl2-supported Ziegler-Natta catalysts however, have unfavourable reactivity... 

Calculate the glass transition temperature, Tg for a noncrystalline ethylene-propylene random copolymer that contains 20 —CH3 groups per 100 main-chain carbons, knowing that it reduces the degree of crystallinity of the copolymer to 0%. 

As previously mentioned, the properties of olefm-CO copolymers depend strongly on the nature of the olefin employed. The glass transition temperature of 1-olefin-CO copolymers decreases from room temperature to nearly -60 °C upon increasing the chain length of the 1-olefin from propylene to 1-dodecene [33]. By contrast to polar ethylene-CO copolymers, copolymers with higher l-olefins display a hydrophobic character. For 1-olefin copolymerization, catalysts with entirely alkyl-substituted diphosphine hgands R2P-(CH2) -PR2 (R=alkyl, by comparison to R=Ph in dppp) such as 3 are particularly well-suited [48]. Efhylene-l-olefin-CO terpolymers and 1-olefin-CO copolymers can be prepared in aqueous polymerizations [43, 47, 48]. In the aforementioned copolymerization reactions, the polyketone was reported to precipitate during the reaction as a sohd [45, 47, 48, 50]. However, in the presence of an emulsifier such as sodium dodecyl sulfate (SDS) and under otherwise suitable conditions, stable polymer latexes can be obtained. 

NOESY has also been used to elucidate the chain conformation of poly(styrene-a/ -MMA).220,221 2D INADEQUATE has been applied to studies of monomer sequence distribution in ethylene-propylene copolymer.223 Additivity rules for the 13C chemical shifts of ethylene-propylene copolymer were devised for configurational sequences as well as substituent effects.226... 

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