Aliphatic polyketones

Property Units Aliphatic polyketone Acetal Nylon 66 conditioned... 

Aliphatic iodine derivatives, 14 376 Aliphatic ketones, 14 563, 571, 581-585 reactions of, 16 331-332 Aliphatic monothiopolyesters, 23 739 Aliphatic nitration, 12 187 Aliphatic peroxyacids, 13 464 Aliphatic peroxycarboxylic acids, 18 463 Aliphatic phosphines, 19 60 Aliphatic polyamides (PA), 10 207-210 19 713, 739. See also Aromatic polyamides PA entries producers of, 10 210 properties of, 10 208, 209t Aliphatic polycarbonates, 24 703 preparation of, 19 798 Aliphatic polyketones (PK), 10 197 costs of, 10 222 properties of, 10 198t Aliphatic poly(monosulfide)s, 23 702-704 Aliphatic polyphosphonate dyes, 9 480 Aliphatic poly(polysulfide)s, 23 711 Aliphatic polysulfides, 23 734 Aliphatic polysulfoxides, 23 733 miscibility of, 23 735 Aliphatic polyurea preparation, carbonyl sulfide in, 23 625... 

Launching new polymers of medium-range performance is a difficult operation economically, as proved by the case of the aliphatic polyketones. New polymer families are rarely marketed but there are some examples where they provide improved processing performances, which is a particularly needed property to satisfy economic requirements. Modification of existing polymers is also an interesting route. Let us quote some examples ... 

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. 

The copolymerization of ethylene and carbon monoxide to give alternating copolymers has attracted considerable interest in both academia and industry over recent decades [1], Attention was focused on aliphatic polyketones such as poly(3-oxotrimethylene), (Structure 1) because of the low cost and plentiful availability of the simple monomers, ethylene and carbon monoxide. 

Also, the carbonyl group can be derivatized to a variety of interesting new materials. Significant advances in technological synthesis and processing made by Shell over the past decade have now moved aliphatic polyketones to commercial reality [2]. 

Aliphatic polyketone based on carbon monoxide, ethylene and a small amount of propylene, commercialised by Shell under the trademark CARILON Polymer (PK-EP), see Chapter 9. 

Chapter nine shows how the different TA techniques focussed on one product, contribute to the characterisation of a new polymeric system aliphatic polyketone. This polyketone is a perfectly alternating copolymer from carbon monoxide and ethylene (PK copolymer). The key-properties of this new polymeric system were calculated as an example. 

A unique catalyst invention at the Shell Research Laboratories in Amsterdam in 1982 [l, 2, 3] made it possible to polymerise carbon monoxide and alpha-olefins such as ethylene into linear, perfectly alternating structures. This led directly to the development of a new class of thermoplastic polymers known as aliphatic polyketones (PK), which Shell is commercialising under the trademark CARILON. 

Constitutive equation Continuous mixers Continuum mechanies Convergence Convergent flow Convergent-divergent flow (e-d) COPO (Aliphatic Polyketone)... 

Carilon Shell Chemical s trade name for its semicrystalline aliphatic polyketone plastics. 

Flame retardancy for electrical and electronic appliances and wiring has been discussed by various workers including Dawson and Landry [14] and Canand and co-workers [15]. Porro [16] investigated the electrical properties of filled and unfilled aliphatic polyketones [15]. Flame-retardant thermoplastic elastomers have been discnssed by... 

The determination of refractory elements with volatilities lower than the temperature needed for the sample matrix volatilization represent the optimum situation, in which complete removal of the matrix can be achieved prior to analyte vaporization. An example to illustrate this kind of application is the determination of Pd (showing a quite low volatility), present as a catalyst residue in a solid aliphatic polyketone [22]. In this application, the bulk of the matrix was removed almost completely at 800°C without any palladium losses, allowing analyte vaporization free from sample matrix covaporization at 2000 C. 

Aliphatic polyketone (Carilon ) Pd Solid sampling AS,SA Ir and At2 used as internal standards [22]... 

Pri ce. The price of a thermoplastic resin is basically determined by the cost of preparation, which in turn strongly depends on the cost of reagents (monomers, catalysts, etc), the complexity of the manufacturing process, and the dimension of production plants. Aliphatic polyketones, for instance, are made from very cheap raw molecules as ethylene, propylene, and CO their cost is determined by the need for expensive catalysts, based on Pd complexes, and the relatively complex production plant. On the other hand, PEN, which can easily be prepared in the same reactors used for PET, suffers from the difficult availability of its basic monomer dimethyl 2,6-naphthalene dicarboxylate. Most engineering polymers contain aromatic monomers, which are difficult to synthesize and polymerize, with slow and sophisticated mechanisms (condensation, substitution, oxidative coupling). 

Fig. 27. Scanning electron composite micrograph of fatigue-induced fracture surface in aliphatic polyketone terpolsmier (A) initiation site and subcritical crack growth, (B) critical radius, and (C) texture associated with remaining ligaments (114).

Fig. 28. Scanning electron micrograph of damage occurring below crack surface in an aliphatic polyketone polymer (Ref 114). Note that the highest density of crazes occurs near the crack surface.

Fig. 29. Scanning electron micrographs of crack tip in plane strain (above) and plane stress (below) conditions for an aliphatic polyketone terpolymer (114).

Aliphatic polyketones described here are a family of semicrystalline thermoplastics obtained by co- or terpolymerization of CO and ethene and/or higher a-olefins. Main emphasis will be on CO/ethene/propene-based terpol5uners [PK-EP]. These polymers can be produced with a wide range of compositions and molecular weights. Various aspects of polyketone catalysis, the pol5mierization process, the types and properties of polyketones, and their applications are reviewed. A number of reviews on polyketones have appeared in recent years (1-5). 

Since this finding, a large variety of transition-metal-based catalysts have been reported for the production of perfectly alternating aliphatic polyketones (17-27). Particularly suitable systems include palladium(II)- or nickel(II)-based complexes modified with a neutral or anionic bidentate chelating ligand and weakly coordinating anions X (such as OTs, OTf, TEA, BF4 and tetra-arylborates) (2,3,13). 

Polyketone catalysis can be carried out in a wide variety of solvents, including water [using sulfonated ligands (75-79)], aprotic solvents [in which alumox-anes can be used as cocatalysts (80,81)], and even in solvent-free systems (62,82). However, methanol remains the solvent of choice for industrial polyketone production. Aliphatic polyketones can also be manufactured in a gas-phase process (83,84). 

The production of aliphatic polyketones at larger scale started in the market development unit (MDU production capacity 500 t/a) in Moerdijk, the Netherlands, in 1986 at Shell. The first commercial plant (capacity 7 kt/a) for the production of aliphatic polyketones came on stream in Carrington, U.K, in 1996. Production is carried out in a batch slurry process, by terpolymerization of CO, ethene, and propene in methanol at 70-90°C and 40-60 bar. The catalyst Pd(bdompp)(TFA)2 (2) is suitably prepared in acetone by mixing palladium acetate. 

A similar aliphatic polyketone product, Ketonex , has been produced at pilot-plant scale by BP in Grangemouth, Scotland (120,121). Production was presumably carried out in a continuous slurry process. 

Table 5, Overview of Various Types of Aliphatic Polyketones... 

Filled and Reinforced Aliphatic Polyketone Compounds. Aliphatic... 

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