Olefinic copolymers Butene-propylene

It has been proposed to improve the heat sealability of TPX by the addition of a propylene-a-olefin copolymer. Satisfactory results have been achieved by melt mixing a TPX polymer with an 1-butene polymer and a propylene polymer (23). 

Ionic copolymers are composed from an a-olefin with an olefin content of 80 mol-% and an ethylenically unsaturated carboxylic acid (6). Suitable olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, etc. 

Introduction of metallocenes in state-of-the-art technologies gives access to new copolymers of ethylene and 1-olefins such as propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene with narrow molecular mass distributions and uniform copolymer compositions. On this basis it is possible to synthesize polyolefins with well-balanced properties. These metallocene/methylalumoxane... 

These catalyst systems also copolymerize C2H4 with long-chain a-olefins, e.g., propylene, 1-butene, and 1-hexene. Through variations in the monomer behavior, the desired proportion of olefin/ethylene in the copolymer can be regulated. By incorporating... 

Galimberti and co-workers synthesized ethylene/ propylene/4-iodo-l-butene terpolymers with a V(acac)3/AlEt2X catalyst (X = Cl, I). The copolymers prepared were amorphous, having at least 35 wt % propylene content, and possessed a bimodal molecular weight distribution of high polymer (MW > 500 000) and oligomers. The preparation of crystalline copolymers of propylene with linear ft>-halo-olefins using TiCla/EtsAl has also been reported by Hoechst. ... 

Olefin Copolymers Molded EEA (ethylene ethyl acrylate) EVA (ethylene vinyl acetate) Ethylene butene Propylene—ethylene ionomer D35 (Shore) D36 (Shore) D65 (Shore) D60 (Shore)... 

Several peaks arising from different pentad and hexad comonomer sequences have been observed n the C-NMR spectrum of stereoregular 1-butene-propylene copolymers. The paper by Aoki and co-workers [54] demonstrated that the analytical method based on the two-dimensional (2D)-INADEQUATE spectrum and the chemical shift calculation via the y-effect is very powerful for the assignment of C-NMR spectra of higher a-olefin copolymers. A stereoregular 1-butene-propylene copolymer is a suitable example because reliable assignments have been proposed by a reaction probability model [55]. 

Using benzene solvent and a variety of initiators, Frank " described the preparation and properties of a-olefin-MA copolymers from propylene, 1-butene, isobutene, cis- and m 5-2-butene, 2-methyl-l-pentene, 2,4,4-trimethyl-1-pentene, 1-hexene, and 1-octene. In order to characterize the materials, the [r/]-Mvv relationship was elucidated for the polymers ... 

Some data have been published on the copolymers of propylene with different linear high olefins 33,40). The main method of analysis is based on the 720 cm band absorbance in the IR spectra (calibration with homopolymer blends). For propylene-butene-1-octene-l copolymers the dependance is (33) ... 

Catalysts which are isospecific for the polymerization of propylene, butene-1, etc., can also be used for the preparation of copolymers of these olefins with ethylene and with each other. There is much evidence to indicate that the chiral specificity of the catalyst is retained during these reactions [72-76], Thus, the spectra of ethylene(e)-propylene(P) copolymers prepared with an isospecific catalyst system are much simpler than those prepared with a nonspecific catalyst [75]. Studies on copolymers of propylene with c-enriched ethylene prepared with an isospecific catalyst indicate that the propylene-ethylene-propylene triads have a single type of configuration, which is probably meso. This is indicated by the fact that only two resonances are observed for ethylene units in P-E-P triads. Furthermore, there is no evidence for the presence of ethylene units flanked by two tertiary carbon atoms (due to inversions of propylene units) in the copolymers. In contrast, copolymers prepared from nonspecific or syndiospecific catalysts have been shown to contain ethylene units centered in both meso- and racemic- PEP... 

Aoki and co-workers [46] demonstrated that spectral analysis based on the 2D-INADEQUATE spectrum and the chemical shift calculation via the y-effect is very useful for C-NMR chemical shift assignments of higher a-olefin copolymers. The successful result of this spectral analysis for a stereoregular 1-hutene-propylene copolymer confirms the reliability of this method. Eurther, the conformational states of the side chain in the 1 -butene unit is evaluated through the chemical shift calculation by considering the side-chain conformation. Therefore, this method is applicable to the analysis of the C-NMR spectrum and of the side-chain conformation in various olefin homo- and co-polymers. 

Sequencing studies have also been conducted on the following olefin copolymers ethylene terephthalate [69-72], ethylene-a-olefin [73], ethylene-a-methylstyrene [74], ethylene-decene-1 [75], ethylene-butene [33], ethylene-propylene diene [76], miscellaneous ethylene copolymers [49] and ethylene-acrylonitrile [77]. 

The principal polyolefins are low-density polyethylene (ldpe), high-density polyethylene (hope), linear low-density polyethylene (lldpe), polypropylene (PP), polyisobutylene (PIB), poly-1-butene (PB), copolymers of ethylene and propylene (EP), and proprietary copolymers of ethylene and alpha olefins. Since all these polymers are aliphatic hydrocarbons, the amorphous polymers are soluble in aliphatic hydrocarbon solvents with similar solubility parameters. Like other alkanes, they are resistant to attack by most ionic and most polar chemicals their usual reactions are limited to combustion, chemical oxidation, chlorination, nitration, and free-radical reactions. 

Copolymerisations of propylene [68,458-460] and 1-butene [47] with higher a-olefins have also been carried out in order to obtain copolymers offering a range of properties not available from the homopolymers alone. As regards the copolymerisability of a-olefins, which decreases with increasing size of the alkyl substituent at the double bond, it results mainly from steric effects [458]. 

Preferred olefins in the polymerisation are one or more of ethylene, propylene, 1-butene, 2-butene, 1-hexene, 1-octene, 1-pentene, 1-tetradecene, norbornene and cyclopentene, with ethylene, propylene and cyclopentene. Other monomers that may be used with these catalysts (when it is a Pd(II) complex) to form copolymers with olefins and selected cycloolefins are carbon monoxide (CO) and vinyl ketones of the general formula H2C=CHC(0)R. Carbon monoxide forms alternating copolymers with the various olefins and cycloolefins. 

The most important monomers for the production of polyolefins, in terms of industrial capacity, are ethylene, propylene and butene, followed by isobutene and 4-methyl-1-pentene. Higher a-olefins, such as 1-hexene, and cyclic monomers, such as norbornene, are used together with the monomers mentioned above, to produce copolymer materials. Another monomer with wide application in the polymer industry is styrene. The main sources presently used and conceivably usable for olefin monomer production are petroleum (see also Chapters 1 and 3), natural gas (largely methane plus some ethane, etc.), coal (a composite of polymerized and cross-linked hydrocarbons containing many impurities), biomass (organic wastes from plants or animals), and vegetable oils (see Chapter 3). 

Random copolymers of ethylene and ct-olefins (1-alkenes) can be obtained with Ziegler-Natta catalysts, the most important being those of ethylene and 1-butene (LLDPE) and ethylene with propylene (EPM or EPR and EPDM). Representative reactivity ratios are presented in Table 9.7. It is seen from these values that ethylene is much more reactive than higher alkenes, and the ratios vary with the nature and physical state of the catalyst. In most Instances, riV2 is close to unity. Heterogeneous Ziegler-... 

Copolymers have also been prepared using mixtures of olefins with sulfur dioxide. Olefin pairs studied were butene with propylene [22-22b], butene with pentene [13], butene with isobutene [13b], butene with acrylonitrile [13,23], butene with vinyl acetate [24], butene with methacrylate esters [25], butene with acrylic esters [25], and butene with butadiene [24]. 

Vinyl acetate in the presence of other olefins reacts with sulfur dioxide to give copolymers [24]. For example 20-30% vinyl acetate in the presence of propylene or butene reacts with sulfur dioxide. 

Many different block copolymers of olefins, like ethylene with propylene and ethylene with butene-1, are manufactured. Use of the anionic coordination catalysts enables variations in... 

Norbomene can be copolymerized with olefins such as ethylene, propylene, 1-butene, and longer-chain a-olefins using early and late transition metal catalysts. The resultant copolymer properties depend on different parameters, such as comonomer content and distribution throughout the polymer chain, as well as the conformational orientation of the comonomer units. The microstmcture of the copolymer can be controlled by the appropriate choice of reaction conditions and catalyst stmcture. The most powerful method to determine copolymer microstmcture is NMR spectroscopy. In the past years, much progress has been achieved in making peak assignments for olefin-norbornene copolymers. - ... 

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