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8th Combined Meeting Of Orthopaedic Research Societies (CORS)


Summary Statement

In the most recent type of highly cross-linked UHMWPE, stabilised by vitamin E, the majority of this anti-oxidant cannot be leached out. Even more, the vitamin E molecules are grafted to the UHMWPE polymer backbone by an ether bond.


Today, highly cross-linked, vitamin E stabilised UHMWPE is clinically accepted as bearing material in joint replacements. Little is known about the chemistry of this antioxidant in the polymer after irradiation. The present investigation presents a model for the chemical nature of the trapping of vitamin E in PE.


UHMWPE type GUR 1020 (Ticona GmbH, Kelsterbach/Germany) was blended with 0.1 % vitamin E (Merck KGaA, Darmstadt/Germany), compression moulded at Mathys Ltd Bettlach in-house and cross-linked with γ-irradiation dose of nominally 100 kGy. To assess the extent of vitamin E leachable out, three 0.3 mm sections were cut from the centre of the samples. By extraction in heptane for 48 h at 98 °C, this amount of vitamin E trapped in the polymer was determined by Fourier transform infrared spectroscopy (FTIR) as relative vitamin E index (RVEI). The nature of the extracted substances was analysed by GC-MS. For solids, many of modern spectroscopic methods are not applicable. Therefore, 0.1 % vitamin E were dissolved in two model hydrocarbons (cyclohexane and n-octane) and irradiated at the same 100 kGy γ-dose. In order to determine the chemical bond vitamin E – hydrocarbon after irradiation, these liquid solution samples were analysed by different spectroscopic methods, such as GC-MS, MALDI-TOF-SIMS, HPLC and NMR.


Extraction experiments showed that only 23 % of the vitamin E could be extracted by heptane after irradiation whereas from a non-irradiated control sample, all vitamin E was extracted. GC-MS confirmed that the extracted vitamin E was chemically unchanged. Analysing the model hydrocarbons after irradiation, the GC-MS-chromatogram of the cyclohexane solution showed a single peak of the formal cyclohexene adduct of vitamin E. Illustrates this adduct, cyclohexyl-6-O-α-tocopherolether. Contrariwise, the same analysis of the n-octane solution revealed three formal octane adducts. By preparing references substances these three peaks could be attributed to ethers of vitamin E bonded at three different, but chemically equivalent CH2 positions on the eight carbon atom chain of n-octane. The single mass peak of the cyclohexane solution arises from the six chemically equivalent carbon atoms in this cyclic hydrocarbon. The 100 kGy γ-dose transformed 76 % of the vitamin E in the n-octane solution to the corresponding ethers and 68 % of the vitamin E in the cyclohexane to cyclohexyl ether. Therefore we postulate that in highly cross-linked, vitamin E stabilised UHMWPE the vitamin E is grafted to the polymer carbon backbone by an ether bond at the phenolic OH group of the vitamin E molecule.


Upon irradiation, vitamin E is grafted to the UHMWPE polymer backbone to a large amount. This portion of antioxidant cannot leach out. Therefore, vitamin E stabilised HXLPE is protected from oxidation and ageing by a chemically grafted, quasi internal antioxidant.