Polyolefin blend elastomers

Thermoplastic polyolefin elastomer/ polyolefin blend elastomer Thermoplastic vulcanizate elastomer TPV TPR, Santo-prene, Geolast, Vyram, Nex-prene, Alcryn... 

A route to compatibility involving ionomers has been described recently by Eisenberg and coworkers [250-252]. The use of ionic interactions between different polymer chains to produce new materials has gained tremendous importance. Choudhury et al. [60] reported compatibilization of NR-polyolefin blends with the use of ionomers (S-EPDM). Blending with thermoplastics and elastomers could enhance the properties of MPR. The compatibility of copolyester TPE, TPU, flexible PVC, with MPR in aU proportions, enables one to blend any combination of these plastics with MPR to cost performance balance. Myrick has reported on the effect of blending MPR with various combinations and proportions of these plastics and provided a general guideline for property enhancement [253]. 

Roy Choudhury N., De P.P., and Bhowmick A.K., Thermoplastic elastomeric natural rubber-polyolefin blends. Thermoplastic Elastomers from Rubber Plastic Blend (De S.K. and Bhowmick A.K., eds.), Ellis Horwood, London, 1990, 11. 

Roy Choudhury N. and Bhowmick A.K., Strength of thermoplastic elastomers from rubber-polyolefin blend, J. Mat. Sci., 25, 161, 1990. 

Kresge E.N., Polyolefin thermoplastic elastomer blends. Rubber Chem. TechnoL, 64, 469, 1991. 

In addition to the polyolefin blends designed for thermoplastic elastomer applications, a great deal of interest also has centered on other kinds of blends of polyolefins as has been reviewed recently (see chapter 21 of Ref. 10 by Plochocki). In a recent paper (84), we showed that blends involving polypropylene-high density polyethylene-low density polyethylene in various proportions and combinations exhibit additivity of tensile strength however, there are serious losses in ductility in some cases such that the blends are less ductile than either pure component. It is interesting to note, however, that these losses in ductility can largely be restored by addition of rather small amounts of an amorphous ethylene-propylene rubber (84). 

Most polyolefin blends to be injection molded are based on elastomer-modified PP (the elastomer is mainly EPDM). The elastomer can be mechanically incorporated, such as in Oleflex TPO. However, there is a growing number of PP/EPDM blends prepared directly in the reactor the rubber modifier is incorporated during PP polymerization (i.e., Kelburon ). The blends are often used in... 

There are two classes of polyolefin blends elastomeric polyolefin blends also called polyolefin elastomers (POE) and nonelastomeric polyolefin blends. Elastomeric polyolefin blends are a subclass of thermoplastic elastomers (TPEs). In general, TPEs are rubbery materials that are processable as thermoplastics but exhibit properties similar to those of vulcanized rubbers at usage temperatures (19). In TPEs, the rubbery components may constitute the major phase. However, TPEs include many other base resins, which are not polyolefins, such as polyurethanes, copolyamides, copolyesters, styrenics, and so on. TPEs are now the third largest synthetic elastomer in total volume produced worldwide after styrene-butadiene rubber (SBR) and butadiene mbber (BR). 

Two important types of elastomeric polyolefin blends are reactor-made iPP/ EPR blends and postreactor blend iPP/EPDM. The latter is called thermoplastic vulcanizates (TPVs), produced by dynamic vulcanization of blends containing a thermoplastic and an elastomer. To make iPP/EPDM TPV, the two polymers PP and EPDM are mixed with curatives, such as peroxides, phenolic resins, or sulfur with accelerators, and dynamically cured in an extmder resulting in a blend consisting of micrometer-sized elastomer particles dispersed in the PP matrix (20-24). Paraffinic oils are added in the melt mixing process for viscosity control and cost. In iPP/ EPDM TPV, the crystalline iPP resin is normally the minor phase. Recently, polyolefin plastomers have been added to the class of elastomeric polyolefin blends. Polyolefin plastomers are ultralow molecular weight linear low density polyethylenes (ULMW-LLDPE). Nonelastomeric polyolefin blends are blends of polyolefins with mostly nonpolyolefin (other thermoplastic) matrices as mentioned earlier. 

The choice of date range is arbitrary. The number of journal articles for each year was obtained from a search of electronic version of English-based polymer and polymer-related journals using the keywords polyolefin and blends. Within polyolefin keyword, the subkeywords used in the search were polyethylene (PE, LLDPE, LDPE, HDPE, UHMWPE, PE, etc.), polypropylene (PP, iPP, sPP, aPP, etc.), polybutene-1, poly-4-methylpentene-l, ethylene-diene monomer, ethylene-propylene-diene terpolymer, ethylene propylene rubber, thermoplastic olefins, natural rubber (NR), polybutadiene, polyisobutylene (PIB), polyisoprene, and polyolefin elastomer. For the polyolefin blends patent search, polymer indexing codes and manual codes were used to search for the patents in Derwent World Patent Index based on the above keywords listed in the search strategy. 

The fourth trend is spurred by environmental sustainability concerns and the need for increased recyclability and reuse of polyolefin blends. In this regard, there is increasing replacement of PVC by polyolefin-polyolefin blends. There is also an increase in recyclability of EPDM mbber vulcanizates since EPDM is the fastest growing elastomer among synthetic rubber and the most used of nontire rubbers. Also, cryogenically ground rubber tires are being used as fillers for polyolefin blends such as LLDPE/HDPE. 

There have been extensive applications of isotactic polypropylene (iPP)/EPM blends. These were used to produce rubber toughened polypropylene blends and subsequently polyolefin thermoplastic elastomers (88,89). Most commercial EPMs contain more than 50 mol% of ethylene, and these are elastomers. The solubility parameter of EPM should be intermediate to those of polyethylene and polypropylene dependent on ethylene content. Thus, it is often used to compatibilize PE/PP blends (90,91). 

In order to improve properties and compatibility of PP/EPDM blends, ternary blends and composites are sometimes prepared from the PP/EPDM blends. For instance, Sanchez et al. (10) prepared ternary blends of PP, high density polyethylene and EPDM with several blending ratios and investigated the melt rheological behaviors. They discussed the effect of the shear rate on the viscosity and flow curve in terms of the exponent of low power for a non-Newtonian liquid. They showed that addition of an elastomer to the polyolefin blends changes the shape of the viscosity-composition curve, and they discussed it in terms of the possible morphology of the blend. Similar works have been also reported by Ha et al. (11,12). 

During the past three decades a few groups of materials have been developed that could be considered as being in this category. Designated as thermoplastic elastomers, they include (1) styrene-diene-styrene triblock copolymers (2) thermoplastic polyester elastomers and thermoplastic polyurethane elastomers and (3) thermoplastic polyolefin rubbers (polyolefin blends). 

Thermoplastic elastomers contain sequences of hard and soft repeating units in the polymer chain. Elastic recovery occurs when the hard segments act to pull back the more soft and rubbery segments. Cross-linking is not required. The six generic classes of TPEs are, in order of increasing cost and performance, styrene block copolymers, polyolefin blends, elastomeric alloys, thermoplastic urethanes, thermoplastic copolyesters, and thermoplastic polyamides. 

Duroplastics are classified as shown in Fig. 7. The chenucal crosslinking reaction takes place in the molding tool (usually heated). Table 4 describes, based on the example of polyolefin blends, their advantages over thermoplastics and elastomers. 

Blending within the family of polyolefins has, however, been more common (Plochocki 1978). Although they are usually immiscible with each other, there exists some degree of mutual compatibility between them. The similarity of their hydrocarbon backbones and the closeness of their solubility parameters, although not adequate for miscibility, account for a relatively low degree of interfacial tension. For example, the solubility parameters of polyethylene, polyisobutylene, ethylene-propylene rubber, and polypropylene are estimated to be 16.0,16.4,16.5, and 17.0 cm respectively, all very close to each other (VanKrevelen 1990). Similarly, the interfacial tension coefficients between PE or PP and EP-elastomers are quite small (typically ca. 0.1 MN/m) (Shih 1990 Wu 1989). Hence, polyolefin blends have been made since the early days of polyolefin commercialization via a simple melt mixing, without a compatibUizer. 

Polyolefine blends are group of versatile materials, which properties can be tailored to specific applications already at the stage of compounding and further processing. Our previous papers on elastomer/plastomer blends were devoted to phenomenon of co crystallization in isotactic poly-propylene/ethylene-propylene-diene rubber (iPP/EPDM) [1] or surface segregation in low-density polyethylene/ethylene-propylene-diene rubber (LDPE/EPDM) [2, 3] systems. Composition and structure of the materials were related to their properties. Recently, we have described the influence... 

Rubber matrices have commonly been used as a second phase to improve the toughness of brittle thermoplastic materials, such as polypropylene and polyethylene. These systems, commonly referred to as polyolefin thermoplastic elastomers (TPOs), are a special class of thermoplastic elastomers that combine the processing characteristic of plastics at elevated temperatures with the physical properties of conventional elastomers at service temperature, playing an increasingly important role in the polymer material industry. Polyolefin blends attract additional interest due to the possibility of recycling plastic wastes, avoiding the complex and expensive processes of separation of the different components. 

M. Ono, K. Nakajima, T. Nishi, Nano-physical properties in polyolefin and elastomer blend consisting of different elastomer morphologies. Polymer Preprints, Japan 55 (2) (2006) 3598. 

Only two classes of polypropylene (PP) blends have achieved commercial success blends wiA polyolefins and with polyamides (PA). With PP/polyolefin blends, the goal is either to improve the impact resistance of the base resin (impact-modified PPs) or to produce thermoplastic elastomers (d)mamically vulcanized blends). PA/PP blends aim at bridging the property gap between the two pol5oners. Therefore, sigitificant information on processing is available only for these two families of blends. 

Lamellas of crystalline phase of the surface layer of polyolefin blends studied are thicker than present in the surface layer of their components, what suggests cocrystallization of ethylene monomer unit from EPDM. Linear LDPE facilitates the phenomenon, especially when takes place in amorphous elastomer matrix. Branched plastomer recrystallizes to the same lamellar liiickness, no matter the structure of elastomer matrix. 

---