10.1002/spepro.

003620

How to control migration of slip agents in polyethylene lms

Helmut Reinecke and Rodrigo Navarro Study of the behavior of lubricants in packaging materials shows that their diffusion to the surface strongly depends on their chemical structure and molecular weight. Plastic packaging systems are ubiquitous in manufacturing. They are an integral component of applications from food to industrial shipping, but their usefulness and efciency depend critically on fullling a number of technical requirements. For example, the plastic lms on high-speed packaging lines must show adequate machinabilityi.e., avoid sticking to metals and other parts of the handling linesa characteristic that is determined mainly by the level of friction between the lm and equipment.14 An optimal amount of friction is commonly achieved through the use of so-called slip additives, which are added to the polymer matrix in molten stage and later migrate to the lm surface. Some diffusion in this case is a good and necessary thing, as the slip agent must move to the surface where it should act. However, unpredictable migration caused by environmental and formulation factors can lead, for example, to excess oiliness and inuence the downstream processes that packaging materials usually undergo, such as printing, sealing, and handling. The overall result is occasional loss of productivity on the packaging lines. Here we describe work aimed at investigating the migration process of erucamide, a common lubricant, as a slip additive and how this behavior is inuenced by co-additives incorporated into standard lm formulations of polyolen plastics (e.g., polypropylene and polyethylene, PE).5 We studied three-layer lms of PE produced on a lm co-extrusion line. Layer A was made of 7:5 m-thick PE and layer B of 35 m-thick PE. Layer C was 7:5 m thick and consisted of PE that contained erucamide along with varying amounts of different types of surface modiers. Following a two-month period of aging the samples at room temperature, the amount of erucamide that had diffused to the lm surface of each system was determined by Fourier transform IRattenuated total reection (FTIR-ATR) spectroscopy. In an initial phase of this work, the question was whether it was possible to change the migration behavior of erucamide when a hydroxylterminated co-oligomer of PE and polyethylene oxide (PEO) is added

Figure 1. Erucamide content at the lm surface as a function of the amount and composition of a co-additive. EO: Ethylene oxide. wt%: Weight percent. to the lm. Our experiments show that this co-additive increases the hydrophilicity of the PE matrix, improving its ability to retain erucamide and reducing its migration to the surface, where accordingly we detected a lower signal from the slip agent. In a second set of experiments we used block co-oligomers as modiers consisting of long sequences of ethylene and ethylene oxide (EO). We kept the length of the ethylene sequence constant while varying that of the EO sequences of four different co-oligomers to test the hydrophilic-hydrophobic balance of the co-additive and its inuence on erucamide retention. Figure 1 presents the results in graphic form. The efciency of this co-additive depends on the type and quantity of the system used. Figure 1 shows that an ideal co-oligomer composition of 80wt% (weight percent) of EO units correlates with a low amount (1000ppm) of additive. When the co-oligomer is added in a larger quantity (3000ppm), a composition of around 50wt% of EO gives the best results, that is, the lowest erucamide content at the surface.

Continued on next page

10.1002/spepro.003620 Page 2/2

interior of the lms. Longer chains, on the other hand, are less mobile and can interact physically with the slip agent. In summary, we have tested a series of surface modiers for their efciency in preventing the slip agent erucamide from migrating to the surface of PE lms. Our studies have shown that the system is highly sensitive to the chemical structure of the surface modier and particularly to its hydrophilic-hydrophobic balance and molecular weight. The most efcient surface modier tested in this work was a block co-oligomer consisting of ethylene and EO sequences. This co-additive reduces erucamide migration to both the top and bottom of three-layer PE lms. However, its efciency depends on the type and quantity of the oligomer used. The longer the EO sequences in the co-polymer, the smaller the quantity needed to obtain the desired effect. Future studies will focus on further optimizing additive compositions and developing novel, more efcient surface modiers based on silicon compounds. Figure 2. Relative erucamide content at the lm surface as a function of the molecular weight (Mw ) of the co-additive. Layer B is situated between layers A and C and cannot be studied using the technique described in this article, which is only sensitive to 2 m-thick layers. mol: Mole. We conclude that a critical number of polar (hydrophilic) groups of the surface modier is necessary to obtain an optimal result. In these formulations, the length of the apolar (hydrophobic) PE part was maintained constant, while the length of the EO sequences was increased, which in turn increased both the polarity and the molecular weight of the co-additive. Although higher molecular weight promotes better matrix retention of erucamide, higher polarity favors its out-diffusion. Consequently, we obtained the best overall results using modiers with an optimal balance between apolarity and modier size, specically, in the modier with 80% EO sequences, Mw D 920 and 1000ppm of additive, and in the modier with about 50% PEO sequences, Mw D 2300 and 3000ppm of additive. The reason for the shift from 80 to 50% lies in the fact that the critical number of apolar groups in the surface modier necessary for the optimal retention of erucamide is already reached in the system with shorter PE sequence length when a higher amount of the block oligomer surface modier is used. Finally, in a third series of experiments we maintained the polarity of the co-additive (i.e., a constant relation between ethylene and EO sequences), but we varied the molecular weight from 900 to 1400g/mol (mole). We found that the efciency of erucamide retention depends linearly on the molecular weight of the co-additive (see Figure 2). The explanation for this result might be that lowermolecular-weight surface modiers diffuse more easily to the surface and are therefore less efcient at retaining erucamide in the The authors gratefully acknowledge nancial support from and collaboration with Dow Chemical, Tarragona, Spain.

Author Information Helmut Reinecke and Rodrigo Navarro Instituto de Ciencia y Tecnologa de Polmeros, CSIC Madrid, Spain Helmut Reinecke is a research scientist. His work focuses on chemical modication of polymers and polymer surface science. He has published more than 80 articles in this area.
References 1. G. Van Essche, T. Kromminga, and A. Schmidt, New highly efcient silica anti-blocking aids for PE and PP lms, J. Plast. Film Sheet. 16 (2), pp. 155168, 2000. 2. C. W. Peloso, M. J. OConnor, S. W. Bigger, and J. Scheirs, Characterising the degradation of the polymer slip additive erucamide in the presence of inorganic antiblock agents, Polym. Degrad. Stab. 62 (2), pp. 285290, 1998. 3. S. W. Bigger, M. J. OConnor, J. Scheirs, J. L. Janssens, J. P. H. Linssen, and A. LeggerHuysman, Odor characterization of low-density polyethylene used for food-contact applications, in R. L. Clough, N. C. Billingham, and K. T. Gillen (eds.), Polymer Durability, Advances in Chemistry 249, American Chemical Society, Washington, DC, 1996. 4. J. A. Radosta and W. D. Riley, Treated talc as an effective anti-block for LDPE blown lm, J. Plast. Film Sheet. 7 (3), pp. 247258, 1991. 5. C. Llop, A. Manrique, R. Navarro, C. Mijangos, and H. Reinecke, Control of the migration behaviour of slip agents in polyolen-based lms, Polym. Eng. Sci. 51. Published online, 23 March 2011. doi: 10.1002/pen.21963

c 2011 Society of Plastics Engineers (SPE)