Terpolymers monoxide

Quantum, by contrast, converted an ethylene—carbon monoxide polymer into a polyester-containing terpolymer by treatment with acidic hydrogen peroxide, the Baeyer-Villiger reaction (eq. 11). Depending on the degree of conversion to polyester, the polymer is totally or partially degraded by a biological mechanism. 

Aliphatic polyketones are made from the reaction of olefin monomers and carbon monoxide using a variety of catalysts. Shell commercialized a terpolymer of carbon monoxide, ethylene, and a small amount of propylene in 1996 under the trade name Carilon (structure 4.79). They have a useful range between the Tg (15°C) and (200°C) that corresponds to the general useful range of temperatures for most industrial applications. The presence of polar groups causes the materials to be tough, with the starting materials readily available. 

New terpolymers of vinyl acetate with ethylene and carbon monoxide have been prepared and their uses as additives to improve the curing and flexibility of coating resins, eg, nitrocellulose, asphalt, phenolics, and polystyrene, have been described (130—132). Vinyl acetate and vinylidene cyanide form highly alternating copolymers. 

The compatibility of blends of poly (vinyl chloride) (PVC) and a terpolymer (TP) of ethylene, vinyl acetate, and carbon monoxide was investigated by dynamic mechanical, dielectric, and calorimetric studies. Each technique showed a single glass transition and that transition temperature, as defined by the initial rise in E" at 110 Hz, c" at 100 Hz, and Cp at 20°C/min, agreed to within 5°C. PVC acted as a polymeric diluent which lowered the crystallization temperature, Tc, of the terpolymer such that Tc decreased with increasing PVC content while Tg increased. In this manner, terpolymer crystallization is inhibited in blends whose value of (Tc — Tg) was negative. Thus, all blends which contained 60% or more PVC showed little or no crystallinity unless solvent was added. 

TVy blending with any one of a multitude of additives, PVC can be transformed into a broad spectrum of resins ranging from highly plasticized to impact resistant. The use of polymeric plasticizers has attracted a great deal of attention because they provide superior permanence in physical properties over their low molecular weight counterparts. Recently a terpolymer of ethylene, vinyl acetate, and carbon monoxide was reported to be miscible with PVC (1,2). The system is of interest because blends of PVC and ethylene-vinyl acetate copolymers range from incompatible to miscible, depending on the content of vinyl acetate in the copolymer (3,4,5). We have therefore undertaken x-ray,... 

The fluorination of the inner surface of intravenous tubing, using atmospheric pressure plasma glow (APG), has been evaluated to enhance biocompatibility and suppress plasticiser migration (273). The effect of plasma treatment on the migration of DOA, and an EVA-carbon monoxide terpolymer as partial or complete replacement, into isooctane solution has given positive results (231). A closed system microwave plasma reactor was used to react imidazole molecules to PVC surfaces with the claim that the resulting PVC was useful as an implant for biomedical applications, on the basis of spectroscopic studies (368). 

The new family of thermoplastic, perfectly alternating olefin/carbon monoxide polymers provides a superior balance of performance properties not found in other commercial materials. The first commercial polymer will be an ethyl-ene/propene/CO terpolymer which will be marketed by Shell under the trade-name Carilon . 

The copolymerization of alkenes with carbon monoxide has attracted the attention of chemists for many years [1]. Following the commerciahzation of Carilon, an alternating olefin carbon monoxide terpolymer based on ethene and small amounts (5-10%) of propene (Scheme 8.1, 1), by Shell [2, 3] in the 1990s interest in the identification of new and more active catalysts and of the stereochemical characteristics of the reaction has grown. 

Aliphatic polyketones based on carbon monoxide and ethylene are called PK copolymer, while the first commercialised grades based on carbon monoxide, ethylene and a small amount of propylene are called PK terpolymer. 

The first commercial blend of this type is Cylon . Here PVC is the matrix, and PA (that melts below 215°C ) the dispersed phase. The two resins were compatibilized using the well known PVC plasticizer — Elvaloy (a terpolymer of ethylene, carbon monoxide and acrylics). These soft to semi-rigid alloys were commercialized for wire coating, automotive applications and blow molding [Grande, 1997 Hofmann, 1998]. They are flame, abrasion and chemicals resistant, easy to process, and tough. 

In a typical formulation, an ethylene-n-butyl-acrylate-carbon monoxide (60/30/10) terpolymer (60 wt%) is melt compounded with plasticized PVC (40 wt%) in a twin-screw extruder and the ethylene terpolymer dispersion cured in situ during the mixing by catalytic amounts of a suitable peroxide (0.3%) and a bismaleimide crosslink promoter (0.2%). The extruded pellets of the elastomeric blend can be used in conventional melt fabrication processes such as profile extrusion, extrusion coating, milling and calendering of sheets, injection and/or compression molding. 

Earlier references to these terpolymers (SOa/olefin/caibon monoxide) are known. For example, U.S. Patent 2,634,254 discloses the terpolymer prepared by polymerization in the presence of a free radical catalyst such as an azo compound. Also, U.S. Patent 4,251,340 discloses similar terpolymers prepared using irradiation as the initiator. These terpolymers are generally high melting (m.p. about 280°C) and show good structural durability for high temperature applications. 

Terpolymer of cw,cw-l,5-cyclooctadiene-carbon monoxide-sulfur dioxide [76]. 

The copolymerization of ethylene and carbon monoxide to give alternating copolymers has attracted considerable interest in both academia and industry over recent decades [1, 2]. Attention was focused on aliphatic polyketones such as poly(3-oxotrimethylene) (1) because of the low cost and plentiful availability of the simple monomers. The new family of thermoplastic, perfectly alternating olefin/ carbon monoxide polymers commercialized by Shell provides a superior balance of performance properties not found in other commercial materials the an ethylene/ propene/CO terpolymer is marketed by Shell imder the tradename Carilon . About the history of polyketones see Refs. [3-11],... 

PRI Privalko, V.P., Korskanov, V.V., Privalko, E.G., Dolgoshey, V.I., Huhn, W., and Rieger, B., Thermodynamic properties and thermoelastic behavior of the alternating terpolymers of ethene, propene, and caibon monoxide in the melt state, J. Macromol. Sci.-Phys. B, 40, 83, 2001. 

Ethylene-vinyl acetate (EVA) polymers (containing 65%-70% by weight of vinyl acetate) are of industrial interest as high-molecular weight plasticizers for PVC, mainly because of their low cost. A polymeric plasticizer PB-3041 available from Du Pont allows the preparation of a highly permanent plasticized PVC formulation. It is believed to be a terpolymer of ethylene, vinyl, acetate, and carbon monoxide. Also, butylene terephthalate-tetrahydrofuran block copolymers, with the trade name of Hytrel (Du Pont), are used as excellent permanent plasticizers of PVC. 

Ethylene vinyl acetate carbon monoxide terpolymer 19.4... 

The method of preparing superparamagnetic particles developed by Charmot [109] uses hydrophobic non-porous polystyrene seed particles of narrow size distribution. A seeded polymerization is carried out to increase the particle size (1.35 pm) and a terpolymer is formed around the seed particles by a dispersion polymerization of styrene, DVB and 4-vinylpyridine in toluene. The toluene containing cobalt precursor swells the latex particles, which results in a homogeneous distribution of the metal precursor. A thermolysis reaction is conducted in the presence of 4-vinylpyridine, and the release of carbon monoxide indicates the decomposition of the metal salt into cobalt. The main problem of this method is the particle surface deformation during the evolution of carbon monoxide. The amount of crosslinker, however, cannot be reduced below a certain level without significantly modifying the properties of the particles. 

Poly (ethylene-chlorotrifluoroethylene). See Ethylene/chlorotrifluoroethylene copolymer Poly (ethylene-co-acrylic acid). See Ethylene/acrylic acid copolymer Poly (ethylene-co-1-butene). See Ethylene/butene-1 copolymer Poly (ethylene-co-butyl acrylate). See Ethylene/butyl acrylate copolymer Poly (ethylene-co-carbon monoxide). See Ethylene/carbon monoxide copolymer Poly (ethylene-co-ethyl acrylate). See Ethylene/ethyl acrylate copolymer Poly (ethylene-co-methacrylic acid). See Ethylene/methacrylic acid copolymer Poly (ethylene-co-methyl acrylate). See Ethylene/methyl acrylate copolymer Poly (ethylene-co-methyl acrylate-co-acrylic acid). See Ethylene/methyl acrylate/acrylic acid terpolymer... 

One copolymer of ethylene and carbon monoxide are available commercially. The material offered under the trade name of CarilOTi is actually a terpolymer, because it contains a small quantity of propylene. It is reported [98] that use of a palladium catalyst permits formation of perfectly alternating interpolymer. The product is reported to be a tough, chemical resistant material. 

While the polyketone terpolymer derived from carbon monoxide, ethylene, and propylene is economical with some attractive properties, such as heat, chemical, permeation, and abrasion resistance, it suffers from low-impact strength. One cost-effective approach to overcoming this shortcoming and upgrading its performance profile for automotive applications such as wheel covers, wheel caps, fuel filter necks, fuel tanks, fuel tubes, center fascias, door handles, roof rack covers, gears, junction boxes, connectors, and seat backs, as well as electric/electronic components and durable household items involves blending with polyamides including a rubber modification (Lee et al. 2013). 

COPO Poly(carbon monoxide-co-polyolefin), a linear, alternating terpolymer CORI Corotating, fully intermeshing TSE Cp Cyclopentadienyl Cp=CsH5 Cyclopentadienyl anion ... 

However, more recently, the ethylene-vinyl acetate-carbon monoxide (E-VA-CO) terpolymers (Tg = —32 °C), offering a more complete miscibility with PVC, because of the polar keto groups in the terpolymer structure, have replaced the EVA copolymers for fiexibilizing the PVC. The E-VA-CO/PVC blends exhibit a single Tg behavior, indicating the complete miscibility (McConnell et al. 2004). Thus, the E-VA-CO terpolymer is more effective as a miscible, polymeric plasticizer for effectively lowering the Tg of PVC to make it more fiexible. 

Hence, commercial E-VA-CO terpolymers (Elvalloy 741 and 742, DuPont) are now the more preferred and more commonly used flexibilizing modifiers in PVC blends. For an even better low-temperature flexibility in PVC blends, ethylene-n-butyl acrylate-carbon monoxide (E-BA-CO) (Evalloy HP, Dupont) is used. The advantage of E-BA-CO terpolymer is its lower Tg (—52 °C). PVC/E-VA-CO blends and PVC/E-BA-CO blends are particularly used in roofing membrane and geomembrane application. 

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