Pressure effects radical copolymerization

Historically, high-pressure free radical copolymerization has been used to produce highly branched, ill-defined copolymers of ethylene and various polar monomers. Although these materials are in production and extensively used throughout the world, the controlled incorporation of polar functionality coupled with linear polymer structure is still desired to improve material properties. Recent focus in this area has led to the development of new transition metal catalysts for ethylene copolymerization however, due to the electro-philicity of the metal centers in these catalysts, polar functional groups often coordinate with the metal center, effectively poisoning the catalyst. There has b een some success, but comonomer incorporation is hard to control, leading to end-functionalized, branched polyethylenes [44, 46]. These results are undesirable due to low incorporation of polar monomer into the polymer as well... 

Tphis paper is concerned with the effect of ionizing radiation on the physical and mechanical properties of copolymers of ethylene with alkyl acrylates, such as ethyl acrylate, butyl acrylate, and 2-ethvlhexyl acrylate (J, 2, 3). These polymers are made by the free radical copolymerization of ethylene under high pressure with alkyl esters of acrylic acid (9). They are more flexible than polyethylene and because of the polar nature of the comonomer, they are more compatible with fillers and with other polymers than is polyethylene. 

Several authors have examined the pressure effect upon the reactivity of radicals in copolymerization and it is claimed that the direction as well as the magnitude of the pressure effect on the reactivity ratios for some copolymerizations can be predicted by making use of the Q e scheme. Other workers have examined the influence of the solvent in radical copolymerizations. In particular the solvation of radicals and the use of solvation for controlling... 

A significant fraction, more than 25%, of the low-density polyethylene (LDPE) (Sec. 3-14a) produced by radical polymerization consists of various copolymers of ethylene. LDPE has come under increasing economic pressure in recent years because of a combination of factors [Doak, 1986]. High-density polyethylene (HDPE) has displaced LDPE in applications such as blow-molded bottles and thin films where the increased strength of HDPE is preferred over the clarity of LDPE. Linear low-density polyethylene (LLDPE) (Sec. 8-1 lc) competes effectively with LDPE in terms of both cost and properties. New producers of ethylene have entered the LDPE market because of a lack of alternatives for their feedstocks. Many LDPE producers use copolymerization as a strategy to obtain products more resistant to displacement by HDPE and LLDPE. 

Another aspect of free radical polymerizations under pressure which has been recently studied is the effect of pressure on comonomer reactivity ratios (5). In two copolymerization systems—styrene-acrylonitrile and methyl methacrylate-acrylonitrile—it was found that the product of the reactivity ratios, rif2, approaches unity as the pressure is increased. The monomer-polymer composition curves for these two copolymerizations at 1 and 1000 atm. are illustrated in Figures 1 and 2. The effect of pressure on the individual reactivity ratios and on the fit2 product is given in Table II. 

The effectiveness of a modifier depends on its chemical structure, concentration, temperature, and pressure. A concentration-independent measure for its effectiveness is the chain transfer constant, defined as the ratio of kinetic coefficients for the transfer reaction to this substance and radical chain propagation reaction. Usually the effectiveness of chain transfer agents is increased with rising temperature and reduced pressure. The chain transfer constant of modifiers falls from aldehydes, which are more effective than ketones or esters, to hydrocarbons. Unsaturated hydrocarbons typically have higher transfer constants than saturated hydrocarbons and a strong effect on polymer density must be considered because of the ability to copolymerize that give a higher frequency of short-chain branches in the polymer. 

---