Crystalline domain polypropylene

The properties of elastomeric materials are also greatly iafluenced by the presence of strong interchain, ie, iatermolecular, forces which can result ia the formation of crystalline domains. Thus the elastomeric properties are those of an amorphous material having weak interchain iateractions and hence no crystallisation. At the other extreme of polymer properties are fiber-forming polymers, such as nylon, which when properly oriented lead to the formation of permanent, crystalline fibers. In between these two extremes is a whole range of polymers, from purely amorphous elastomers to partially crystalline plastics, such as polyethylene, polypropylene, polycarbonates, etc. 

Isotactic polypropylene is a rather stiff and tough solid material with a melting point of 164°C. Closely packed, CHs-studded helices (Figure 17), rigidly interwoven in crystalline domains (Figure 18), account for the mechanical and thermal resistance of isotactic polymers. Syndiotactic polypropylene has a related crystalline structure, but atactic polymers are amorphous and form oily or waxy materials depending on chain lengths. 

Rubbery behavior—large, reversible extensibility—implies an absence of crystallinity, and this is usually the case for undeformed elastomers. However, small extents of crystallization may be present at ambient temperature in some elastomers, including EPDM with high ethylene content, epichlorohydrin rubber, and polypropylene oxide. The crystallites in these materials can act as reinforcing agents. Many thermoplastic elastomers have crystalline domains that function as reversible crosslinks (Rzymski and Radusch, 2005 Bhowmick and Stephens, 2001). 

In the above process, the formation of crystalline domains involves consecutive insertions from one of the lateral coordination sites of the catalyst so as to give rise to isotactic sequences, whereas consecutive insertions at the other site (2) give rise to atactic amorphous sequences. Interconversion between these two states must occur within the lifetime of a given polymer chain in order to generate a physically cross-linked network and is believed to occur via occasional isomerizations of the polymer chains (i.e., interconversion at the metal center). Preparation of an oscillating catalyst that yields an elastomeric polypropylene was also reported by others [441]. 

Crystalline polyolefins as polypropylene (PP) with high tacticity and copolymers of propylene with ethylene and/or higher a-olefins containing sufficiently long isotactic PP blocks can only be dissolved under conditions (solvent/temperature) which cause complete melting of the crystalline domains. Therefore, SEC of PP and crystalline copolymers of propylene must be carried out at elevated temperatures which requires the special equipment of high-temperature SEC (HT-SEC) which is commercially available from several sources, e.g. Millipore-Waters Corp. (Milford, MA, USA) and Polymer Laboratories Ltd (Church Stretton, Shropshire, UK). 

Chain Packing and Crystal Structures. The chain packing and the suhmolecular arrangement of repeat units and pendant side groups of macromolecules in crystalline domains of polymers can be visualized using contact mode SFM. The resolution is in most cases not true resolution, since the area of the contact area (1 — few nm ) exceeds the molecular scale and must be considered lattice resolution instead. The first example of molecularly resolved structures of a polymer dates back to 1988, when Marti and co-workers reported on an SFM study on a polydiacetylene film (128). Examples for resolved chain packing and polymer crystal structure determination at the surface of semicrystalline polymers include poly(tetrafiuoroethylene) (PTFE) (129,130), polyethylene (PE) (131-133), polypropylene (PP) (134,135), poly(ethylene oxide) (PEO) (136), aramids (137,138), and poly(oxy methylene) (POM) (139). 

FIGURE 9.21 The time-dependent development of crystalline domains in a dip coated film of polypropylene having 36% mmmm prepared with 9a/MAO (sample A36) can be tracked by obtaining TM-SFM phase shift images at room temperature after (a) 0 min, (b) 120 min, and (c) 280 min. 

The thermoplastic polyolefin rubbers (TPOs) are physical blends of ethylene-propylene rubber with polypropylene. A form of cross-linking would appear to be provided by crystalline domains based on the polypropylene component. It would seem reasonable to presume, that in order to effectively link a rubbery matrix based on EPR with the crystalline domains based on polypropylene, that there should be some co-crystallization of regular polypropylene segments in the EPR with the polypropylene. Such linkages would then provide a means of obtaining a rubbery network linked by polypropylene crystalline structures. 

EPR random copolymers are inherently thermoplastic and rubbery in nature but to give them useful levels of strength, creep resistance, heat resistance, and solvent resistance, they are commonly blended, or block or graft copolymerized, with crystalline polyolefins, particularly polypropylene, which on cooling separate as crystalline domains and act as thermoplastic crosslinks and reinforcing fillers. ... 

Thermoplastic IPN s may also contain a chemically crosslinked component, but the requirement is that it not be the continuous phase in the system. For example, semi-crystalline isotactic polypropylene can be combined with EPDM which is either incompletely crosslinked, or forms cylindrical domains. ... 

The data from this table illustrate the semicompatibility of the phase between isotactic polypropylene and the high density polyethylene with block copolymer without gross interference in the domain structure or the crystalline phases that exist in these TPR s. 

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). 

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