Temperature ethylene-carbon monoxide copolymers

For photolysis of the ethylene—carbon monoxide copolymer in solution, the AH-6 lamp and a 20-mm. path-length quartz cell were used. The cell was filled with the solvent, pure n-heptane, and the intensity of the lamp was measured at the experimental temperature. Freeze-dried polymer was then added to make a 2% solution, which absorbed about 25% of the light. The polymer was dissolved, and the solution was mixed by a dry nitrogen stream, which also flushed out any air dissolved in the solvent. The light beam was then allowed to enter the cell, and the photolysis commenced the intensity of the emergent beam was monitored by the photomultiplier tube and the recorder. At the end of the photolysis the cell was filled with pure solvent, and the intensity of the lamp was measured again. The polymer was recovered from solution by evaporating the heptane it was then dissolved in benzene and freeze-dried. 

The 1% ethylene-carbon monoxide copolymer was also irradiated in the solid phase (thin film). Compression-molded films were fixed on plates which fitted into the Perkin Elmer 521 infrared spectrophotometer. An infrared spectrum of the polymer could thus be obtained after each period of photolysis without disturbing the film. For photolyses at room temperature and above the plates were mounted in a solid brass cell through which a stream of inert gas could be passed while the cell was being heated. 

Fig. 5.23 Plot of melting temperature against CO concentration for alternating ethylene-carbon monoxide copolymers. (Adapted from Colombo, et al (158))...

A classic example of an alternating-type copolymer is found in the ethylene-carbon monoxide copolymer [34-39]. This copolymer is polymorphic. The a form is stable at low temperature and transforms to the P form at 140 °C. The melting temperature of this form is about 255 °C. This temperature is much greater than that for linear polyethylene or any of its random copolymers. This again is the result of a crystal structure different from that of polyethylene that accompanies the high extent of alternation. 

It is generally believed that ethylene-carbon monoxide copolymers because of their internal ketone group, degrade mainly by Norrish Type II chain scission reactions when subjected to ultraviolet radiation in the 290 nm region. The reaction has been found to be generally independent of temperature [3]. 

Chromium Oxide-Based Catalysts. Chromium oxide-based catalysts were originally developed by Phillips Petroleum Company for the manufacture of HDPE resins subsequendy, they have been modified for ethylene—a-olefin copolymerisation reactions (10). These catalysts use a mixed sihca—titania support containing from 2 to 20 wt % of Ti. After the deposition of chromium species onto the support, the catalyst is first oxidised by an oxygen—air mixture and then reduced at increased temperatures with carbon monoxide. The catalyst systems used for ethylene copolymerisation consist of sohd catalysts and co-catalysts, ie, triaLkylboron or trialkyl aluminum compounds. Ethylene—a-olefin copolymers produced with these catalysts have very broad molecular weight distributions, characterised by M.Jin the 12—35 and MER in the 80—200 range. 

In the case of ethylene/carbon monoxide copolymerisation with nickel- and palladium-based catalysts, a strictly alternating high molecular weight copolymer is formed (average molecular weight in the range 10 x 103 100 x 103).When more developed catalysts are used, the copolymerisation conditions can be mild a temperature of 25 °C combined with a pressure of ca 20 atm. The obtained copolymer, poly(ethylene-c// -carbon monoxide), poly(l-oxytrimethylene)... 

This is the case, for example, in the copolymerization of carbon monoxide and ethylene where the CO will not add to itself but does copolymerize with the olefin monomer. General theoretical treatments have been developed for such cases, taking into account temperature and penultimate effects. Again, the superiority of these more complicated theories over the simpler copolymer model is not proved for all systems to which they have been applied. 

It is well-known that the occurrence of chain defects, in the form of for example small methylene sidegroups, could reduce this Tm-value [4J. This offered the possibility to reduce the relative high processing temperature of PK copolymers. The effect of addition of small amounts of propylene to the carbon monoxide/ ethylene mixture on the Tm-value is shown in Figure 9.1. A nearly linear decrease of the Tm-value as a function of the weight percentage of C3 was found for propylene concentrations between 0 and about 15 %wt. i.e. for the Tm-value holds ... 

The copolymer between ethylene and carbon monoxide has been known since the early 1940s. In 1941 this copolymer was produced at Bayer in a high-temperature, high-pressure process (230 °C, 200 atm). Roughly 10 years later, this polymer was produced through... 

Fig. 5.24 Plot of reciprocal melting temperature against In X, the fraction of crystal-lizable units, for the temating copolymers of ethylene and carbon monoxide. (From Starkweather (163))...

Absent from Table 10 are the comonomers carbon monoxide, carbon dioxide, and sulfur dioxide. These comonomers are not included because their copol mieiization does not obey the normal copolymer model illustrated by reactions (vix—xvii) and hence cannot be described by kinetic parameters which take into account only these reactions. For example. Furrow (/28) has i own that caibon dioxide will react with growing polyethylene chains in a free-radical reaction, but that it terminates the chains giving carboxylic acids. It does not copolymerize in the usual sense (which would give polyesters). Carbon monoxide and sulfur dioxide appear not to obey the normal cppol3nner curve of feed composition versus polymer composition and it has been reported that these materials form a complex with ethylene whidi is more reactive than free CO or SOg, perhaps a 1 1 complex. Copolymerization of both CO and SO is further complicated by a ceiling temperature effect. Cppolymerization has been carried out with ethylene and these monomers, however, and poly-ketones and pol3Tsufones are the resultant products. 

Figure 21 Melting temperature-composition relation for alternating copolymer of ethylene and carbon monoxide ...

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