This action might not be possible to undo. Are you sure you want to continue?
Dissolution of polystyrene into p-cymene and related substances in tree leaf oils Hattori, Kazuyuki, Shikata, Sota, Maekawa, Ryo, Aoyama, Masakazu Journal of wood science, 56(2): 169-171 2010-10 http://hdl.handle.net/10213/1769
Author(s) Citation Issue Date URL Rights Type Text Version Additional information
Journal Article author
Kitami 090-8507.ac. Shikata R.NOTE Dissolution of polystyrene into p-cymene and related substances in tree leaf oils Kazuyuki Hattori Sota Shikata Ryo Maekawa Masakazu Aoyama K. Hattori S. Kitami Institute of Technology.jp Keywords Recycling of polystyrene Tree leaf oil p-Cymene Solubility parameter 1 . Maekawa M. 165 Koen-cho.kitami-it. Aoyama () Department of Biological and Environmental Chemistry. JAPAN e-mail: aoyama@chem.
7-197. (R)-limonene and its structural isomers (181.7 g 100 g solvent -1).0 g 100 g solvent -1) to polystyrene at 50C compared favorably with those of 2-p-cymenol (156.Abstract We examined the dissolution of polystyrene into p-cymene and related substances.1 g 100 g solvent -1) and Abies leaf oil (84.7 g 100 g solvent -1). The dissolving power of p-cymene (212. 2 . p-Cymene and polystyrene can be recovered almost quantitatively from the polystyrene solution by simple steam distillation. The favorable solubility of polystyrene into p-cymene can be explained by the solubility parameter. in order to develop an alternative method for the recycling of expanded polystyrene.
Introduction Expanded polystyrene is widely used as food trays.000 oranges is necessary for extracting 1 liter of the oil.1 Recently great interest has been focused on an alternative method for shrinking expanded polystyrene using Citrus peel oil. Although Citrus peel is a renewable resource. undesirable oxidative degradations of polystyrene occur during the thermal shrinking process.1 of which the main component is a naturally occurring monoterpene. a pile of the peel corresponding to about 10. (R)-limonene. p-Cymene is an aromatic hydrocarbon. Although the recycling rate of plastics has been currently improved. low thermal conductivity and lightweight. In Japan. the output of expanded polystyrene in 2007 amounted to 182. The most commonly employed process for the material recycling of expanded polystyrene includes shrinking by heated air or frictional heat. a good solvent for a certain polymer has a 3 .000 tons. Generally. Increase in the recycling rate of plastics is an important strategy for reducing our dependence on petroleum-derived chemicals. and occurs widely in tree leaf oils. the material recycling of expanded polystyrene is still at the 50% level in Japan. However. packaging materials or adiabators because of its excellent shock absorbing property.2-5 Its chemical structure is similar to that of styrene.
Japan) in August. (St. Polystyrene used for the dissolution experiments was obtained from Sigma-Aldrich Co. MO. Ind. First.e.6 Recently we have found that polystyrene was dissolved into p-cymene and Abies leaf oil at ambient temperature. Louise. -terpinene and terpinolene were purchased from Tokyo Chem. in order to explain the relationship between the chemical structure of the solvent and the dissolution behavior of polystyrene. Abies leaf oil was prepared by steam distillation of the fresh leaves of Abies sachalinensis Masters. (R)-limonene. we examined the solubilities of polystyrene into p-cymene and its related substances in tree leaf oil. and calculated their solubility parameter and apparent activation energy (Ea) for the dissolution. Co. which were collected in the Ainonai forest of Sato Forestry Co. 2-p-cymenol (carvacrol). Certain foliage is. (Kitami.solubility parameter value close to that of the polymer. i. Experimental Materials p-Cymene. therefore. USA). Average molecular weights of the polystyrene were measured by gel permeation chromatography (GPC) in chloroform referenced to standard polystyrene samples (Product # 4 . the structural similarity between a solute and a solvent favors solubility. (Tokyo.. 2006. a potential resource for the recycling solvent of expanded polystyrene. Japan).
SM-105. The 5 . Polystyrene disks with a diameter of 5 mm (average weight: 2. Tokyo. Commercial polystyrene pellets were pressed under 20 MPa at 260C for 5 min. The test tube was sealed by a silicon rubber stopper. K. For the solubility experiments. The shaking speed used throughout the study was 120 strokes min-1. and then placed in a shaking thermostatic water bath. another disk was added to the solution. polystyrene films were prepared.03 mg) were punched out from the film. Viscosities of the polystyrene solutions The steady shear viscosity of 5% of the polystyrene solutions was measured at 40 °C on a Brookfield digital cone and plate rheometer model-III+ equipped with a thermocontroller. when the disk in the test tube disappeared within 24 h..2 ml of the solvent. For the dissolution experiments. Showa Denko K. Japan). Dissolution experiments A polystyrene disk was put in a test tube with 0.30 0. then cooled to ambient temperature. The dissolution of polystyrene was judged by visual and/or crossed polars microscopic observations.
a small block of a commercial food tray made of EPS (20 20 4 mm) was immediately dissolved in a few drops of p-cymene or (R)-limonene at ambient temperature. which is an aromatic and component of Abies leaf oil. 6 .0 g of polystyrene at 50C.05°. The experimental results are listed in Table 1. Water (50 ml) was added to the solution. This dissolving power was higher than those of (R)-limonene. The average of three times measurements was adopted for each sample. All measurements were replicated five times and the means and SDs of analytical data were obtained. respectively. We first examined the solubility of polystyrene into p-cymene and its related substances shown in Fig. A hundred grams of p-cymene dissolved 212. In the preliminary experiments. The recovery yield of the solvent was evaluated by the volume. and then the mixture was subjected to steam distillation for 3 h. 1.5 is similar to that of polystyrene. polystyrene pellets (0.2 g) were dissolved in 2 ml of the solvent. Results and discussion We remarked that the structure of p-cymene. Recovery of the solvent and polystyrene In order to examine the recovery of the solvent and polystyrene. hence both would be mixed well.radius and angle of the cone were 12 mm and 0. The steady shear rate was 100 s-1.
which are the structural isomers of (R)-limonene. -terpinene and terpinolene. It has been found that a good solvent for a solute has a value close to that of the solute. suggesting that 2-p-cymenol has higher temperature dependence on the dissolution of polystyrene than p-cymene. -terpinene and terpinolene were calculated 7 .7 The Ea of p-cymene was similar to that of (R)-limonene.03 mg) was measured at temperatures in the range 30-70C (Table 2).6 The values of p-cymene.30 0. For further investigation on the relationship between chemical structure of the solvents and the dissolution behavior of polystyrene. It is known that the rate constant decreases with increasing the Ea and increases with increasing temperature. On the other hand. (R)-limonene. and Abies leaf oil. so that the position of a double bond would not affect the dissolving power greatly. The Ea was obtained from the slope of the Arrhenius plot of ln t versus the inverse of thermodynamic temperature. Ea for the dissolution and solubility parameter () of the solvents were evaluated. the Ea of 2-p-cymenol was remarkably larger than the other solvents. 2-p-cymenol. Any remarkable difference was not observed among (R)-limonene.-terpinene and terpinolene. The introduction of a hydroxyl group into p-cymene resulted in a significant decrease in the solubility. The time (t) required for the dissolution of a polystyrene disk (2.
according to the method of Hoftyzer and Van Krevelen.4 MPa1/2) explain their dissolution power for polystyrene.6 MPa1/2) and 2-p-cymenol (19.1 reported that.5 because they are poor solvents for polystyrene. The 2-p-cymenol solution exhibited relatively high viscosity compared with the other solutions. Viscosity of the solutions is an important factor for the dissolution of polystyrene. because high viscosity of the solution decreases the mobilities of solute and solvent in the system. the dissolving power of 2-p-cymenol would be poor compared with the other solvents. and that the rate of dissolution was greatly improved. when a small amount of ethanol was added to the (R)-limonene solution containing 20% polystyrene by weight. Noguchi et al. the viscosity of the solution lowered. the occurrence of hydroxyl group in a solvent molecule causes to reduce the accessibility to hydrophobic polymer matrix. As the result. The reduced dissolution power of Abies leaf oil was explained by the existence of acyclic monoterpene alcohols such as geraniol and linalool. 8 . the values of p-cymene (14.8 As shown in Table 2. Generally. Such high viscosity would delay the dissolution time of polystyrene. and prevents the solute from diffusing in the solvent. Table 3 shows the steady shear viscosities of the solutions containing 5% polystyrene by weight.
The favorable solubility of polystyrene into p-cymene can be explained by the solubility parameter. Its dissolving power for polystyrene compared favorably with those of (R)-limonene and its structural isomers. the number-average molecular weight of the polystyrene decreased from 1. On the other hand. The introduction of hydroxyl group into p-cymene resulted in a significant decrease in the solubility. In conclusion. suggesting that certain degradation occurred slightly.To evaluate the recycling system for expanded polystyrene. can be used as an alternative shrinking agent for expanded polystyrene. p-cymene.10 105 (polystyrene recovered from the 2-p-cymenol solution). which is widely distributed in tree leaf oils. the molecular weights of the polystyrene recovered and the recovery yield of the solvents from the solutions were studied (Table 4).9 The use of radical scavengers prevents undesirable degradation of polystyrene.31 105 (virgin polystyrene) to 1. p-Cymene and polystyrene are recovered almost quantitatively by simple steam distillation of the solution. 9 . The degradation may be caused by oxygen radicals from air during the steam distillation. The solvents were mostly recovered by steam distillation of 10% (w/v) of the solutions.
Mokuzai Gakkaishi 29:396-399 4. Yatagai M. Wiley-Interscience. Khait K (2003) Recycling. 3rd edn. Inagaki Y. Hoboken. Barton AF (1975) Solubility parameters. pp 657-678 10 . Chem Rev 75:731-753 7. Biochem Syst Ecol 14:469-478 6. A new recycling technique. Plastics. Yatagai M. Massachusetts. II. Yatagai M. 5th edn. Sato T. Miyashita M. Chang R (1994) Chemistry. Takahashi T (1983) An approach to biomass utilization. Van Krevelen DW (1990) Cohesive properties and solubility.References 1. In: Kroschwitz JI (ed) Encylopedia of polymer science and technology. Sato T (1985) Terpenes of leaf oils from conifers. Watanabe H (1998) A new recycling system for expanded polystyrene using a natural solvent. Part 1. von Rudloff E (1975) Volatile leaf oil analysis in chemosystematic studies of North American conifers. Biochem Syst Ecol 13:377-385 5. pp 189-225 9. Takahashi T (1984) Terpenes of leaf oils from Cupressaceae. pp 538 8.7. vol. New York. Components of Eucalyptus leaf oils. Noguchi T. New Jersey. Biochem Syst Ecol 2:131-167 3. 3rd edn. Elsevier. Packag Technol Sci 11:19-27 2. In: Van Krevelen DW (ed) Properties of polymers. McGraw-Hill.
1 Chemical structures of solvents and solute used in this experiments OH p-Cymene 2-p-Cymenol (R)-Limonene n -Terpinene Terpinolene Polystyrene Fig. 1 11 .Figure caption Fig.
12 . n = 5.7 0.2 181.2 -Terpinene Terpinolene Abies leaf oil a Mean SD.1 0. Solubility of polystyrene into p-cymene and its related substances at 50C Solvent p-Cymene 2-p-Cymenol (R)-Limonene Solubilitya (g 100 g solvent -1) 212.2 84.7 0.Table 1.2 191.7 0.0 0.4 0.2 156.1 197.
991 4 145 1 147 1 134 1 665 1 60C 85 1 829 4 102 2 114 3 103 2 329 1 70C 66 2 403 2 85 1 90 3 74 2 184 2 215 2 11.2 24. n = 5.Table 2.5 Mean SD.1 23.2 14.1 71. 13 .9 54. The value is not given because Abies leaf oil is a mixture of many essential oil components.6 -1 (MPa1/2) 14.458 51 255 2 263 2 228 2 2.7 -b 14.507 8 - Ea (kJ mol ) 25.9 15. apparent activation energy (Ea) for polystyrene dissolution and solubility parameter () Solvent 30C p-Cymene 2-p-Cymenol (R)-Limonene -Terpinene Terpinolene Abies leaf oil Polystyrene a b Time required for dissolution (sec)a 40C 149 1 3.1 23.4 15.6 19. Time required for dissolution (sec).830 16 184 1 191 1 173 2 964 2 50C 109 1 1.
The steady shear rate was 100 s-1.3 31.5 2. 14 .Table 3. Steady shear viscosities of 5% polystyrene solutionsa Solvent p-Cymene 2-p-Cymenol (R)-Limonene Abies leaf oil a Viscosity (cP) 2.8 2.9 The measurements were carried out at 40C.
6 a Molecular weight of polystyrene recovered Mnb 1. Number-average molecular weigh.75 1. Weight-average molecular weight.30 × 105 2.15 × 10 2.5 0. n = 5.3 0 .95 1.86 1.93 (R)-Limonene -Terpinene Terpinolene Abies leaf oil 1.4 92.29 × 105 1.20 × 10 1.9 89.27 × 10 1.53 × 10 5 Mean SD.1 95.26 × 10 5 5 5 5 Dispersion 1.85 1.2 92.81 1. 15 .0 0 .9 94.10 × 10 1.3 0.Table 4.17 × 10 2.25 × 105 2.31 × 10 5 2.9 1.33 × 105 Non-treated a b c - 1.22 × 10 2. Recovery yield of solvents and average molecular weights of polystyrene recovered by steam distillation Solvent p-Cymene 2-p-Cymenol Recovery yield of solvent (%) 96.78 1.22 × 10 5 5 5 5 M wc 2.5 1.