Polyolefins 4- substituted

Because of the high melt viscosity of polyolefins, normal spinning melt temperatures are 240—310°C, which is 80—150°C above the crystalline melting point. Because of the high melt temperatures used for polyolefin fiber spinning, thermal stabilizers such as substituted hindered phenols are added. In the presence of pigments, the melt temperature must be carefully controlled to prevent color degradation and to obtain uniform color dispersion. 

Polyolefins such as polyethylene and polypropylene contain only C—C and C—H bonds and may be considered as high molecular weight paraffins. Like the simpler paraffins they are somewhat inert and their major chemical reaction is substitution, e.g. halogenation. In addition the branched polyethylenes and the higher polyolefins contain tertiary carbon atoms which are reactive sites for oxidation. Because of this it is necessary to add antioxidants to stabilise the polymers against oxidation Some polyolefins may be cross-linked by peroxides. 

The predictable stereochemistry of the ring closure of substituted 5-hexenyllithiums, coupled with the ease with which the product organolithium may be functionalized, permits rational design of synthetic routes to polycyclic systems by sequential anionic cyclizations of polyolefinic alkyllithiums.12 The preparation of stereoisomerically pure e do-2-substituted bicyclo[2.2.1]heptanes is illustrative of this approach to polycyclic systems.12... 

Data concerning the chain conformations of isotactic polymers are reported in Table 2.1. In all the observed cases the torsion angles do not deviate more than 20° from the staggered (60° and 180°) values and the number of monomeric units per turn MIN ranges between 3 and 4. Chains of 3-substituted polyolefins, like poly(3-methyl-l-butene), assume a 4/1 helical conformation (T G )4,45,46 while 4-substituted polyolefins, like poly(4-methyl-1-pentene), have less distorted helices with 7/2 symmetry (T G )3.5-39 When the substituent on the side group is far from the chain atoms, as in poly(5-methyl-1-hexene), the polymer crystallizes again with a threefold helical conformation (Table 2.1). Models of the chain conformations found for the polymorphic forms of various isotactic polymers are reported in Figure 2.11. 

Similarly large anisotropies were later reported for highly emissive blends of alkoxy-substituted bis(phenylethynyl)benzene derivatives and polyolefins such as linear low-density polyethylene (LLDPE) and isotactic polypropylene (z-PP) [8,9]. The latter systems reach high levels of anisotropy at very low draw ratios, which is advantageous from a processing point of view. 

ARA Palmans, M Eglin, A Montali, C Weder, and P Smith, Tensile orientation behavior of alkoxy-substituted BA(phenylethynyl)benzene derivatives in polyolefin blend films, Chem. Mater., 12 472-480, 2000. 

Fig. 7.10. (a) Ionization energies of certain classes of organic molecules as a function of their molecular weight, and (b) relative sensitivities for (O) alkylbenzenes, ( ) polyolefines, and ( ) substituted naphthalenes in chlorobenzene CE-CI. Adapted from Ref [51] by permission. American Chemical Society, 1983. 

Shaw selected a combination of polyolefin resins as the base polymer of choice for its substitute, EcoWorx . Due to the low toxicity of its feedstocks, superior adhesion properties, dimensional stability, and its ability to be recycled, EcoWorx meets all of the design criteria necessary to satisfy the needs of the marketplace from a performance, health, and environmental standpoint. Research also indicated that the post-consumer carpet tile had a positive economic value at the end of its useful life. The cost of collection, transportation, elutriation, and return to manufacturing processes is less than the cost of using virgin raw materials. This is a truly recyclable (or Cradle to Cradle) product and is a good example of how substitution through innovation can make economic as well as environmental sense. ... 

Harden s (27) market survey of the growth of polyolefin foams production and sales shows that 114 x 10 kg of PE was used to make PE foam in 2001. The growth rate for the next 6 years was predicted as 5-6% per year, due to recovery in the US economy and to penetration of the automotive sector. In North America, 50% of the demand was for uncrosslinked foam, 24% for crosslinked PE foams, 15% for EPP, 6% for PP foams, 3% for EVA foams and 2% for polyethylene bead (EPE) foam. As protective packaging is the largest PE foam use sector, PE foam competes with a number of other packaging materials. Substitution of bead foam products (EPP, EPE, ARCEL copolymer) by extruded non-crosslinked PE foams, produced by the metallocene process was expected on the grounds of reduced costs. Compared with EPS foams the polyolefin foams have a lower yield stress for a given density. Compared with PU foams, the upper use temperature of polyolefin foams tends to be lower. Eor both these reasons, these foams are likely to coexist. 

Most general purpose linear polymers, such as polyolefins, PS, PVC, and polymethyl methacrylate (PMMA), are not suitable for use at temperatures above 100 °C. PMMA and other polymers of 1,1-substituted vinyl monomers, such as poly-a-methylstyrene, decompose almost quantitatively to their monomers at elevated temperatures. However, the Tg and Tm values of these polymers are greater than those of polymers from 1-substituted vinyl monomers. For example, the Tg values of polymethyl acrylate (PMA) and PMMA are 276 and 381 K, respectively. 

Thermal and Oxidative Stability. In general, polyolefins undergo thermal transitions at much lower temperatures than condensation polymers thus, the thermal and oxidative stability of polyolefin fibers are comparatively poor. Preferred stabilizers are highly substituted phenols such as Cyanox 1790 and lrganox 1010, or phosphites such as Ultranox 626 and Irgafos 168. 

Substitute for Conventional Vulcanized Rubbers, For this application, the products are processed by techniques and equipment developed for conventional thermoplastics, ie, injection molding, extrusion, etc. The S—B—S and S—EB—S polymers are preferred (small amounts of S—EP—S are also used). To obtain a satisfactory balance of properties, they must be compounded with oils, fillers, or other polymers compounding reduces costs. Compounding ingredients and their effects on properties are given in Table 8. Oils with high aromatic content should be avoided because they plasticize the polystyrene domains. Polystyrene is often used as an ingredient in S—B—S-based compounds it makes the products harder and improves their processibility. In S—EB—S-based compounds, crystalline polyolefins such as polypropylene and polyethylene are preferred. Some work has been reported on blends of liquid polysiloxanes with S—EB—S block copolymers. The products are primarily intended for medical and pharmaceutical-type applications and hardnesses as low as 5 on the Shore A scale have been reported (53). 

No equivalent data seem available for oxacyclobutane itself but a number of 3,3-substituted derivatives have been documented (17,30) and show clearly the importance of symmetry for crystallinity and the marked increase in the melting point produced by polar substituents. The melting points of the simpler ether polymers are somewhat lower than those of the corresponding polyolefins, presumably because of the greater flexibility of the polyether chain coupled with low van der Waal s forces. They must be determined primarily by the ability of the chains to fit into a lattice, i. e. by the shape of the chains, so there seems no reason... 

Tertiary phosphine groups with long alkyl chains bound directly to phosphorus or substituted at the para position of triphenylphosphine give rise to a range of interesting and potentially useful complexes. In particular these may be used to prepare polyolefin hydrogenation catalysts based on platinum(II) and palladium(II) complexes that are both more active and more selective towards reduction to monoolefins than previous catalysts based on these systems. The platinum(II) complexes are better than the palladium(II) complexes. Additionally the new phosphines are more effective than triphenylphosphine in promoting the oxidative addition of methyl iodide to trans- [Rh(PR3)2Cl(CO)]. 

Similar, and even more stringent, limitations apply to olefin polymers. In general it is not possible to synthesize polyolefins with more than two alkyl substituents per two carbon atoms. With heavier substitution the polymer becomes unstable relative to the monomer. 

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