Ethylene copolymers properties

Properties ethylene-propylene resin Poly(vinylidene fluoride) Unfilled Glass-fiber- reinforced ethylene copolymer Cellulose- filled Glass-fiber- reinforced... 

Copolymeis of ethylene [74-85-1] and tetiafluoioethylene [116-14-3] (ETFE) have been alaboiatory curiosity for more than 40 years. These polymers were studied in connection with a search for a melt-fabricable PTFE resin (1 5) interest in them fell with the discovery of TFE—HFP (FEP) copolymers (6). In the 1960s, however, it became evident that a melt-fabricable fluorocarbon resin was needed with higher strength and stiffness than those of PTFE resins. Earlier studies indicated that TFE—ethylene copolymers [11939-51 -6] might have the right combination of properties. Subsequent research efforts (7) led to the introduction of modified ethylene—tetrafluoroethylene polymer [25038-71-5] (Tefzel) by E. I. du Pont de Nemours Co., Inc, in 1970. 

Within the scope of the original definition, a very wide variety of ionomers can be obtained by the introduction of acidic groups at molar concentrations below 10% into the important addition polymer families, followed by partial neutralization with metal cations or amines. Extensive studies have been reported, and useful reviews of the polymers have appeared (3—8). Despite the broad scope of the field and the unusual property combinations obtainable, commercial exploitation has been confined mainly to the original family based on ethylene copolymers. The reasons for this situation have been discussed (9). Within certain industries, such as flexible packaging, the word ionomer is understood to mean a copolymer of ethylene with methacrylic or acryhc acid, partly neutralized with sodium or zinc. 

EinaHy, in 1976, Kaminsky and Sinn in Germany discovered a new family of catalysts for ethylene polymerization. These catalysts (ie, Kaminsky catalysts) contain two components a metallocene complex, usually a zkconocene, and an organoaluminum compound, methylaluminoxane (8,9). These catalysts and thek various later modifications enable the synthesis of ethylene copolymers with a high degree of branching uniformity. Formally classified as MDPE, LLDPE, or VLDPE, the resins thus produced have a number of properties that set them apart from common PE resins in terms of performance... 

The compositional distribution of ethylene copolymers represents relative contributions of macromolecules with different comonomer contents to a given resin. Compositional distributions of PE resins, however, are measured either by temperature-rising elution fractionation (tref) or, semiquantitatively, by differential scanning calorimetry (dsc). Table 2 shows some correlations between the commercially used PE characterization parameters and the stmctural properties of ethylene polymers used in polymer chemistry. 

Mechanical Properties. Mechanical characteristics of ethylene copolymers are functions of their stmctural characteristics. 

Random insertion of ethylene as comonomer and, in some cases, butene as termonomer, enhances clarity and depresses the polymer melting point and stiffness. Propylene—butene copolymers are also available (47). Consequendy, these polymers are used in apphcations where clarity is essential and as a sealant layer in polypropylene films. The impact resistance of these polymers is sligbdy superior to propylene homopolymers, especially at refrigeration temperatures, but still vastiy inferior to that of heterophasic copolymers. Properties of these polymers are shown in Table 4. 

Vinyl Acetate—Ethylene Copolymers. In these random copolymers, the ratio of ethylene to vinyl acetate (EVA) is varied from 30—60%. As the vinyl acetate content increases, the oil and heat resistance increases. With higher ethylene content the physical strength, tensile, and tear increases. The polymers are cured with peroxide. The main properties of these elastomers include heat resistance, moderate oil and solvent resistance, low compression set, good weather resistance, high damping, exceUent o2one resistance, and they can be easily colored (see Vinyl polymers, poly(VINYL acetate)). 

A. Akimoto and A. Yano, Production of ethylene copolymers with metallocene catalysts at high pressure and its properties, MetCon 94 Proceedings, USA, May 1994. 

Norbornene-ethene copolymer, 16 113 Norbornene-ethylene copolymers, 20 433 physical properties of, 20 420-422 Norbornenodiazetine derivatives, 13 306 Nordel IP (metallocene), 7 637 Nordihydroguaiaretic acid, antioxidant useful in cosmetics, 7 830t Nordstrandite, 2 421, 425 activation, 2 394 classification, 2 422 decomposition sequence, 2 392 from gelatinous boehmite, 2 427 structural properties of, 2 423t NO-reduction reactions, TWC catalyst, 10 49... 

Cyclopentadienyl ligands have become extremely important in catalysis for metal such as Ti, Zr, and Hf (Chapter 10) and in academic studies of related elements such as Ta. Ethylene polymerisation with the use of CpiTiCE (alkylated with aluminium alkyl compounds) has been known for many decades, but the intensive interest in derivatives of these compounds started in the early 1980 s following the discovery of MAO (methaluminoxane - see chapter 10) which boosted metallocene catalyst activities by several orders of magnitude. Commercial interest focussed on ethylene copolymers (LLDPE where more homogeneous comonomer incorporation resulted in greatly improved copolymer properties) and in enantiospecific polymerisations for propene, styrene, etc. 

Another way to recover the catalyst from the dormant site is the copolymerisation of ethene, but this is slower and less attractive than the use of hydrogen. Furthermore the use of ethylene inevitably results in the formation of propylene-ethylene copolymers with all the consequent effects on polymer properties. 

A review is presented of the nitrogen autoclave process for the manufacture of crosslinked polyolefin foams. Process and product developments over the last few years are summarised and future possibilities are described. Process developments include use of higher temperatures and pressures to produce foams having densities as low as 10 kg/cub.m. Product developments include foams based on HDPE/LDPE blends, propylene copolymers and metallocene-catalysed ethylene copolymers. The structure and properties of these foams are compared with those of foams produced by alternative processes. 5 refs. 

Polycarbonate is blended with a number of polymers including PET, PBT, acrylonitrile-butadiene-styrene terpolymer (ABS) rubber, and styrene-maleic anhydride (SMA) copolymer. The blends have lower costs compared to polycarbonate and, in addition, show some property improvement. PET and PBT impart better chemical resistance and processability, ABS imparts improved processability, and SMA imparts better retention of properties on aging at high temperature. Poly(phenylene oxide) blended with high-impact polystyrene (HIPS) (polybutadiene-gra/f-polystyrene) has improved toughness and processability. The impact strength of polyamides is improved by blending with an ethylene copolymer or ABS rubber. 

For the sake of brevity detailed tables of all tests performed are shown for duPont ionomer resins only (Tables II, III, IV, VI to X). The other ethylene copolymers were similarly treated and evaluated. The effects of increasing radiation dosages on certain physical properties of selected duPont ionomers are shown graphically in Figures 1, 2, and 3. 

Low density poly(ethylene) (LDPE) may have unsatisfactory heat seal properties, as they often do not provide sufficient adhesion between the sealing layers to result in a good adhesive seal for a package. Efforts to improve the heat seal characteristics of LDPE by blending them with other materials, such as ethylene copolymers with methacrylic acid or acrylic acid, have not had universal success. 

Each set of experiments was carried out under the same reaction condition except using different comonomers, i.e. p-methylstyrene, o-methylstyrene, m-methylstyrene and styrene, respectively. The compositions of copolymers were determined by H NMR spectra, and the thermal properties (melting point and crystallinity) were obtained by DSC measurements. Overall, all comonomers show no retardation to the catalyst activity. In fact, the significantly higher catalyst activities were observed in all copolymerization reactions (runs 2-5), comparing with that of ethylene homopolymerization (run 1). Within each set (runs 2-5 and 6-9) of comparative experiments, p-methylstyrene consistently shows better incorporation than the rest of comonomers, i.e. o-methylstyrene, m-methylstyrene and styrene. Both catalysts with constrained mono- and di-cyclopentadienyl ligands are very effective to incorporate p-methylstyrene into polyethylene backbone. In runs 2 and 6, more than 80 % of p-methylstyrene were converted to copolymer within one hour under constant (- 45 psi) ethylene pressure. On the other hand, only less than half of styrenes (runs 5 and 9) were incorporated into ethylene copolymers under the same reaction conditions. The significantly... 

Despite tlte broad scope of the held and the unusual property combinations obtainable, commercial exploitation has been confined mainly to the original family based on ethylene copolymers. Within certain industries, such as llexihle packaging, the word ionomer is understood to mean a copolymer of ethylene with methacrylic or acrylic acid, partly neutralized with sodium or zinc. 

Four olefins are used in industry to manufacture ethylene copolymers 1-butene, 1-hexene, 4-methyl-1-pentene. and 1-octene. Copolymers containing 1-butene account for approximately 40% of all LLDPE resins manufactured worldwide, 1-hexene copolymers for 35%, 1-octene copolymers for about 20%, and 4-mcthyl-l-pcntcnc copolymers for the rest. The type of o-olcliit exerts a significant influence oil tlie copolymer properties. 

Mechanical Properties. Mechanical characteristics of ethylene copolymers are functions of their structural characteristics, such as content and type of a-olefin, branching uniformity, molecular weight and width of molecular weight distribution (MWD), and orientation (see Table 5 for properties of films made from three grades of LLDPE). 

Random ethylene copolymers with small amounts (4-10 wt-%) of 7-olefins, e.g. 1-butene, 1-hexene, 1-octene and 4-methyl- 1-pentene, are referred to as linear low-density polyethylene, which is a commercially relevant class of polyolefins. Such copolymers are prepared by essentially the same catalysts used for the synthesis of high-density polyethylene [241]. Small amounts of a-olefin units incorporated in an ethylene copolymer have the effect of producing side chains at points where the 7-olefin is inserted into the linear polyethylene backbone. Thus, the copolymerisation produces short alkyl branches, which disrupt the crystallinity of high-density polyethylene and lower the density of the polymer so that it simulates many of the properties of low-density polyethylene manufactured by high-pressure radical polymerisation of ethylene [448] (Figure 2.3). 

Physical properties are related to ester-segment structure and concentration in thermoplastic polyether-ester elastomers prepared hy melt transesterification of poly(tetra-methylene ether) glycol with various diols and aromatic diesters. Diols used were 1,4-benzenedimethanol, 1,4-cyclo-hexanedimethanol, and the linear, aliphatic a,m-diols from ethylene glycol to 1,10-decane-diol. Esters used were terephthalate, isophthalate, 4,4 -biphenyldicarboxylate, 2,6-naphthalenedicarboxylate, and m-terphenyl-4,4"-dicarboxyl-ate. Ester-segment structure was found to affect many copolymer properties including ease of synthesis, molecular weight obtained, crystallization rate, elastic recovery, and tensile and tear strengths. 

Ethylene copolymers were compared with liquid plasticisers for use as additives to improve the flexibility of poly(vinyl chloride) (PVC) for electrical cable insulation applications. The PVCs were assessed by determining smoke generation, flammability, tensile properties and the low temperature brittle point. The ethylene copolymers gave similar peak heat release rates, but the peak smoke and the total smoke generation were lower. They also gave similar or increased strength, similar elongation and flexural modulus, and lower brittle point temperatures. 4 refs. 

A family of ADMET model copolymers were synthesized and used to study the effects of regular microstructure on polymer properties, in particular functionahzed polyethylenes. The structure-property relationships of various ethylene copolymers can be clarified using these model systems. This is illustrated in Fig. 3 by the relationship of to functional group size. Future studies on these and similar systems should lead to fundamental discoveries concerning the class of materials known as polyethylenes and their physical properties. 

Recent developments in ADMET polymerization and its use in materials preparation have been presented. Due to the mild nature of the polymerization and the ease of monomer synthesis, ADMET polymers have been incorporated into various materials and functionaUzed hydrocarbon polymers. Modeling industrial polymers has proven successful, and continues to be appUed in order to study polyethylene structure-property relationships. Ethylene copolymers have also been modeled with a wide range of comonomer contents and absolutely no branching. Increased metathesis catalyst activity and functional group tolerance has allowed polymer chemists to incorporate amino acids, peptides, and various chiral materials into metathesis polymers. Sihcon incorporation into hydrocarbon-based polymers has been achieved, and work continues toward the application of latent reactive ADMET polymers in low-temperature resistant coatings. 

Ethylene may be copolymerised with vinyl acetate to make ethyl-vinyl acetate, offering high seal integrity and clarity for frozen food applications where a high degree of toughness is required. Ethylene copolymers with other olefins such as propylene, 1-hexene and 1-octene allow a range of properties to be achieved. Linear low density polyethylene (LLDPE) has a... 

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