Ethylene copolymers, radiation

Temperature dependence (related to the temperature dependence of the conformational structure and the morphology of polymers) of the radiation effect on various fluoropolymers e.g., poly (tetrafluoroethylene-co-hexafluoropropylene), poly(tetrafluoroethylene-co-perfluoroalkylvinylether), and poly(tetrafluoroethylene-co-ethylene) copolymers has been reported by Tabata [419]. Hill et al. [420] have investigated the effect of environment and temperature on the radiolysis of FEP. While the irradiation is carried out at temperatures above the glass transition temperature of FEP, cross-linking reactions predominate over chain scission or degradation. Forsythe et al. [421]... 

Table II shows the effect of various doses of electron irradiation on the solubility of ethylene-ethylacrylate copolymer. Extraction with boiling toluene for 64 hours revealed extensive crosslinking after absorption of a 5-megarep dose of radiation. Copolymers of ethylene with isobutyl acrylate and 2-ethylhexyl acrylate were examined briefly. A 29 wt.% isobutyl acrylate-ethylene copolymer of melt index 1.3 decigrams per minute was crosslinked to greater than 50% insolubility in boiling toluene by a radiation dose of 10 megareps. A copolymer containing 21% by weight of 2-ethylhexyl acrylate of melt index 8 decigrams per minute required a dose of 25 megareps to reach a 50% level of insolubility.

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. 

Kostov, G.K. and Atanassov, A.N., 1993. Radiation initiated grafting of acryhc acid onto tetrafluoroethylene-ethylene copolymers. J Appl Polym Sci. Al 361-366. 

Wang, B., Wang, X., Shi, Y. et al. 2012. Effect of vinyl acetate content and electron beam irradiation on the flame retardancy, mechanical and thermal properties of intumescent flame retardant ethylene-vinyl acetate copolymer. Radiation Physics and Chemistry 81 308-315. 

Polar copolymers of ethylene, such as ethylene-vinyl acetate (EVA) and ethylene-ethyl acrylate (EEA), are readily crosslinked upon exposure to high energy irradiation [88]. In fact, the melt index of EVA can be controlled by the use of low doses (<50 kGy) of irradiation [89]. The presence in polar ethylene copolymers of comonomer units such as vinyl acetate or alkyl acrylates (methyl, ethyl and n-butyl) proportionately reduces the level of crystallinity, and since the majority of radiation responses of interest take place in the amorphous phase, the responses are more uniform throughout the polymer mass. When the irradiation is done at room temperature, the physical properties after irradiation follow the same trend as polyethylene [90]. 

Seguchi, T., Hayakawa, N., Yoshida, K., and Tamura, N., Fast neutron irradiation effect. II. Crosslinking of polyethylene, ethylene-propylene copolymer, and tetra-fluoroethylene-propylene copolymer, Radiat. Phys. Chem., 26, 221-225 (1985). Keller, A., and Ungar, G., Radiation effects and crystallinity in polyethylene, Radiat. Phys. Chem., 22, 155-181 (1983). 

An interesting investigation on radiation processes is the modification of ethylene copolymers with 2,5-dimethyl-2,5-di(tert-butylperoxy)-hexane (DBPH). The outcome of modifier presence consists of the increase in the concentration of ra/25-vinylene double bonds simultaneously happened with the sharp decrease in the amount of terminal vinyl double bonds [lOSl]. 

Table 10.5 Radiolysis products of ethylene-a-olefin copolymers radiation source) ...

Several authors have discussed the ion exchange potentials and membrane properties of grafted cellulose [135,136]. Radiation grafting of anionic and cationic monomers to impart ion exchange properties to polymer films and other structures is rather promising. Thus, grafting of acrylamide and acrylic acid onto polyethylene, polyethylene/ethylene vinyl acetate copolymer as a blend [98], and waste rubber powder [137,138], allows... 

Table III. Effect of Gamma Radiation on Properties of Ethylene—Butene Copolymer...

NR, styrene-butadiene mbber (SBR), polybutadiene rubber, nitrile mbber, acrylic copolymer, ethylene-vinyl acetate (EVA) copolymer, and A-B-A type block copolymer with conjugated dienes have been used to prepare pressure-sensitive adhesives by EB radiation [116-126]. It is not necessary to heat up the sample to join the elastomeric joints. This has only been possible due to cross-linking procedure by EB irradiation [127]. Polyfunctional acrylates, tackifier resin, and other additives have also been used to improve adhesive properties. Sasaki et al. [128] have studied the EB radiation-curable pressure-sensitive adhesives from dimer acid-based polyester urethane diacrylate with various methacrylate monomers. Acrylamide has been polymerized in the intercalation space of montmorillonite using an EB. The polymerization condition has been studied using a statistical method. The product shows a good water adsorption and retention capacity [129]. 

Since the excellent work of Moore and Watson (6, who cross-linked natural rubber with t-butylperoxide, most workers have assumed that physical cross-links contribute to the equilibrium elastic properties of cross-linked elastomers. This idea seems to be fully confirmed in work by Graessley and co-workers who used the Langley method on radiation cross-linked polybutadiene (.7) and ethylene-propylene copolymer (8) to study trapped entanglements. Two-network results on 1,2-polybutadiene (9.10) also indicate that the equilibrium elastic contribution from chain entangling at high degrees of cross-linking is quantitatively equal to the pseudoequilibrium rubber plateau modulus (1 1.) of the uncross-linked polymer. 

Patri, M., Hande, V. R., Phadnis, S. and Deb, P. C. 2004. Radiation-grafted solid polymer electrolyte membrane thermal and mechanical properties of sulfonated fluormated ethylene propylene copolymer (FEP)-graft-acrylic acid membranes. Polymers for Advanced Technologies 15 622-627. 

Absorption due to main intermediates such as polymer cation radicals and excited states, electrons, and alkyl radicals of saturated hydrocarbon polymers had not been observed for a long time by pulse radiolysis [39]. In 1989, absorption due to the main intermediates was observed clearly in pulse radiolysis of saturated hydrocarbon polymer model compounds except for electrons [39,48]. In 1989, the broad absorption bands due to polymer excited states in the visible region and the tail parts of radical cation and electrons were observed in pulse radiolysis of ethylene-propylene copolymers and the decay of the polymer radical cations were clearly observed [49]. Recently, absorption band due to electrons in saturated hydrocarbon polymer model compounds was observed clearly by pulse radiolysis [49] as shown in Fig. 2. In addition, very broad absorption bands in the infrared region were observed clearly in the pulse radiolysis of ethylene-propylene copolymers [50] as shown in Fig. 3. Radiation protection effects [51] and detailed geminate ion recombination processes [52] of model compounds were studied by nano-, pico-, and subpicosecond pulse radiolyses. 

Enhanced radiation cross-linking in polyethylene, polypropylene, and poly-isobutylene and in copolymers of ethylene and propylene was found when nitrous oxide was incorporated into the polymer matrix. Mechanisms of fhis process have been proposed by several workers. ... 

Commercial grades of ethylene-propylene copolymers (EPR) contain 60-75 mol% of ethylene to minimize crystallization. The addition of a third monomer, such as 1,4-hexadiene, dicyclopentadiene, or 5-ethylidene-2-norbornene, produces generally amorphous faster-curing elastomers. A large number of such terpolymers, referred to as EPDM, is available commercially. Their properties, performance, and response to radiation vary considerably depending on macrostructure, ethylene/propylene ratio, as well as on the type, amount, and distribution of the third monomer. 

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