Anda di halaman 1dari 7

Synthesizing a Polymer for Use in Sun Care Applications Karl Burkhardt Summer 2012 Internship Specialty Products, Science

and Technology Division of Arizona Chemical

Synthesizing a Polymer for Use in Sun Care Applications Karl Burkhardt Introduction In order to create a polymer that consumers will want to purchase, the polymer must address a need or a desire of the consumer. Because the current market segment of focus is on sunscreens, the desires of sunscreen manufacturers are of particular interest to Arizona Chemicals Specialty Products team. One of the Arizona Chemical polymers, Sylvaclear C75V, has already addressed one of the desires of manufacturers. The advantage of using SylvaclearC75V in an emulsion based sunscreen formulation is that the sunscreen becomes more waterproof, which is important to manufacturers who wish to label their products as sport or water resistant sunscreens. Another Arizona Chemical polymer which has shown promise in sun care formulations is Sylvasol 200 which was designed specifically for use in ethanol based sunscreen spray applications. Sylvasol 200 is appealing to consumers because the sunscreens it is used in do not tighten when the ethanol dries; as the ethanol evaporates, the Sylvasol 200 traps the actives on the skin. These two polymers have put Arizona Chemical in the sunscreen market, but in order to preserve this presence, Arizona Chemical must continue to produce innovative, desirable products. An idea of Anna Pavlovic was to create a polymer which would boost the SPF ratings of sunscreens which it was used in. This would allow producers to lower the amount of actives in their formulation while keeping the SPF rating the same. Because the actives are expensive, this would give manufacturers incentive to buy the SPF enhancing polymer. The polymer would also promote the photostability of the formulations which it was used in, allowing individuals to use the sunscreen for a longer time without experiencing sunburn. Experimental Once the design of the polymer was finalized, the synthesis was carried out. The setup consisted of a heating mantle, a round bottom flask, a mechanical stirrer, an automated temperature control, a connector which served as a condenser, and a sub-surface nitrogen sparge. The setup was assembled inside of a fume hood where the reaction would take place. The reactants consisted of both diamines and dimer acids which would serve as the backbone of the polymer, and acid terminators in order to cap the polymer and stop the reaction. Diamines and dimer acids were charged into the reaction flask and were kept at a temperature of 180 C for a given time before a sample was pulled in order to track how the ingredients were reacting. Some of the sample was tested for its acid value as well as its amine value while the rest of the sample was sent to analytical for observation with gel permeation chromatography (GPC). While the reaction stayed between 180 and 200 C, samples were taken periodically until it was determined that some of the acid terminating reactants should be added. The addition of the acid terminating reactants was made in order to drive

the amine value down; this process of taking samples and adding acid terminators was continued until the amine value was within 0.5 units of the theoretical final amine value. During the final two hours of the reaction, a vacuum was used in order to pull out the water which had formed during the course of the reaction and also to pull out the residual volatile amines that were left unreacted. When the reaction was complete, the final acid and amine values of the polymer were tested and the final sample was sent to analytical for GPC testing using the refractive index. The polymer, for the rest of the paper, will be referred to as polymer 687-11. Once the synthesis had finished, the Hydrophilic Lipophilic Balance (HLB) value of the polymer was determined by mixing 9 g of 687-11 with 9 g of varied HLB organic solvent and slowly adding 76 g water while mixing. After the emulsion had been left undisturbed for 24 hours, it was observed both macroscopically and, if the emulsion passed visual inspection, microscopically. Polymer 687-11 was used in three different formulations in order to test whether or not the synthesis met the goals. Along with these, a control was made for each formulation, substituting an extra amount of water in place of the polymer in order to create the same volume of product. The first formulation was an inorganic sunscreen which substituted 687-11 for Sylvaclear C75V in formula 57.01 (previously made by Jason Rothouse). The second formulation was the same as the first formulation except the highest and lowest HLB emulsifiers were varied in order to match the HLB of the organic phase. The third formulation was an organic sunscreen which substituted 687-11 with Sylvaclear C75V in formula 87 (previously made by Jason Rothouse). The modified 687-11 formula 87 organic sunscreen and its respective control were then tested for their absorbance in the ultra-violet spectrum using a labsphere UV transmittance analyzer. This was done in concurrence with the 2011 FDA method for critical wavelength determination. A skin feel test was performed while preparing the samples for UV absorbance testing. Samples of each of the six formulations were taken and stored in a 40 C oven to test their stability. They will be kept there for a full three months before any final conclusions are made. Results After the synthesis, the acid and amine values of 687-11 were determined to be 4.00 and 7.60, respectively. The acid number is acceptable and is well below the tolerance required of polymers used in cosmetic formulations. However the amine number is higher than desired in a cosmetic polymer. A typical amine value for a polymer in the cosmetic industry is below 2.00. Because the amine value was so high above this mark, future syntheses will need to address this issue. After testing the HLB value of the polymer, the HLB number assigned to 687-11 was 10.8. Macroscopic observations of the range of HLB values tested are shown in Fig. 1 below.

Fig. 1 The HLB of the organic phases which were tested. The size of the micelles observed in the HLB 10.8 emulsion are shown in Fig. 2 below.

Fig. 2 The size of the micelles in the HLB 10.8 emulsion are between 2 and 5 m. While following the 2011 FDA method for critical wavelength determination, the post-irradiation SPF rating of the control sunscreen was 16.4 while the post-irradiation SPF rating of the sunscreen made with 687-11 was 27.4. The data gathered is shown in Table 1 below.

Table 1 Data table for sunscreen testing. Sample Plate # Plate weight (g) Sample volume (mg) Plate + dried film (g) Film Weight (mg) Avg. Film Weight (mg) Initial SPF Average SPF SPF StDev Crit. Wave Length 4MED SPF Average SPF SPF StDev Crit. Wave Length Average SPF Loss Average % SPF Loss Control 2% 687-11 1 2 3 4 5 6 7 8 9 10 7.3470 7.3840 7.3641 7.411 7.4052 7.3657 7.385 7.3800 7.3806 7.384 25.0 24.8 25.0 24.8 24.8 25.0 25.2 25.0 25.2 24.8 7.3531 7.3898 7.3701 7.4165 7.4118 7.3722 7.3923 7.3862 7.3885 7.3914 6.1 5.8 6.0 5.5 6.6 6.5 7.3 6.2 7.9 7.4 6.0 7.1 18 13 16 18 18 26 27 26 33 32 16.6 28.8 2.2 3.4 376 376 376 376 376 376 376 376 376 376 18 13 16 17 18 26 26 24 31 30 16.4 27.4 2.1 3 376 376 376 376 375 376 376 376 376 376 0.2 1.4 1.2 4.9

Based on these results, a 167% increase was observed when polymer 687-11 was present in the sunscreen. This calculation is shown below in Table 2. Table 2 Percent boosting calculation. Formulation Average SPF Percent Increase Control 16.4 2% 687-11 27.4

The SPF test is based on the absorbance of the sunscreen in the 290 to 400 nm range. The spectra which were taken by the labsphere UV transmittance analyzer are shown below in Fig. 3.

Absorbance of Sunscreen vs. Wavelength


1.6 1.4 1.2

Control Polymer

Absorbance

1 0.8 0.6 0.4 0.2 0 290 310 330

Wavelength (nm)

350

370

390

Fig. 3 The sunscreen with polymer 687-11 absorbs more UV light than the control sunscreen and is especially effective in the UVB range (290-320nm). For this reason, the control sunscreen was determined to have a lower SPF value than the sunscreen that was made with polymer. While preparing the formulations for UV absorbance testing, skin feel tests revealed that the formulations made with 687-11 spread better on the skin than the control formulations. At the time of this paper the samples have only been in the 40 C stability oven for two weeks, but all six sunscreens appear to be stable. Conclusion The synthesis was considered a success because of the significant SPF boost which was observed during SPF testing. The most likely reason for this boost is that more actives were left on the plate after the drying period. This can be seen by comparing the average film weight of the control plate to the average film weight of the 2% polymer plate in Table 1. Future syntheses will need to lower the amine value of the polymer while retaining the SPF boosting which was observed in the formulations made with 687-11. This will most likely be done by adding more acid terminating reactants in order to reduce the amine value even further. The downside of this technique is that it would increase the acid value, potentially causing it to be too high.

One of the sacrifices made in using polymer 687-11 in sunscreen formulations was the sunscreens lacked water resistance. This is in contrast to the properties of sunscreens made with Sylvaclear C75V which cause water to bead on the skin after application. By coincidence the HLB values of 687-11 and Sylvaclear C75V are within 0.3 HLB units of each other (HLB value of Sylvaclear C75V is 11.1); a polymer is generally stable in emulsions with HLB values within 0.5 HLB units of the HLB value of the polymer. Because the HLB values are so close, future testing will hope to combine these two polymers in a sunscreen formulation which will provide both SPF boosting and a water-resistant layer on top of the skin.

Anda mungkin juga menyukai