Abstract
This article contains original experimental data, figures and methods to the study of Microwave-assisted emulsion polymerization of styrene under the frame of “Enhanced Microwave Synthesis” (EMS), has been examined to investigate the advantages of Microwave (MW) power use in emulsion polymerization (Ergan et al., Eur. Polym. J. 69, 2015, 374–384). For comparative purpose, MW and conventional heating (CH) method experiments were conducted under similar conditions. By externally cooling the reaction vessel with 1,4-dioxane, constant and continuous MW power was successfully applied at isothermal condition during the polymerization. Here we give the MW power calibration data of MW-experimental system, the complete set of the experimental polymerization data and the analysis data obtained from different polymer characterization test devices (GPC, DSC and Viscometer).
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Specifications Table | |
| Subject area | Chemical Engineering |
| More specific subject area | Microwave reaction systems and Polymer chemistry |
| Type of data | Table, graph |
| How data was acquired | Microwave device (Milestone-start-S model), Macrosizer ( Malvern Mastersizer 2000), Gel permeation chromatography (GPC, Agilent 1100 Series), Differential scanning calorimetry (DSC, Perkin Elmer Jade model), Ubbelohde viscometer (capillary diameter, 0.63 mm) |
| Data format | Calibration data of MW system (raw), polymerization data (raw), Polymer characterization data (analyzed) |
| Experimental factors |
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| Experimental features |
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| Data source location | Gebze Technical University,Kocaeli,Turkey |
| Data accessibility | Data are available with this article |
Value of the data
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The data shows the successful application of continuous and constant MW power during the polymerization while maintaining isothermal condition as well.
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The data provide suitable process conditions for achieving high yields of polystyrene by MW-assisted emulsion polymerization.
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The data provide the proofs for the existence of the “specific MW effect”.
1. Data, experimental design, materials and methods
Styrene (M) received from Merck was purified with a freshly prepared solution of NaOH (0.0025 M) before using in order to eliminate the inhibitor in styrene. Then, styrene was washed with ultrapure water until the pH was 7. Other chemicals; 1,4-dioxane, Potassium persulfate (KPS), Hydroquinone, Sodium dodecyl sulfate (SDS) were used as received from Merck. Bi-distilled water was used in all the experiments.
According to one variable at a time planning technique; temperature (T), MW power density (P), molar ratios; H2O/M, SDS/M, KPS/M and the reaction time (t) were investigated as six experimental variables in the ranges 65–85 °C, 0–0.8 kW dm−3, 3–9, 0.06–0.1, 0.002–0.005, 7.5–90 min. respectively [1].
In a typical run, 60 cm3 water, SDS, KPS, and M mixture were load into the jacketed glass reactor and stirred at room temperature for a complete dissolution. Then, ultrasonic pre-treatment was applied to prepare an effective emulsion mixture. Emulsion droplet sizes were measured three times through a Macrosizer device (Malvern Mastersizer 2000, UK) approximately 30 min after the sample preparation. Finally, emulsion droplet size distributions were obtained typically between 0.8 µm and 10 µm as shown in Fig. 1.
Fig. 1.
Emulsion particle size distribution.
In this study, a multimode MW reactor (Start-S model, Milestone S.r.l. Sorisole, Italy) was used. During the runs, the Fluoroptic (FO) sensor (accuracy±0.2 °C, ATC-FO-300008 type, Zu electronic, Italy) was dipped in the reactor in a glass capillary sheath. By external circulation of 1,4-dioxane as coolant between jacketed glass reactor and cooling bath, continuous and constant MW energy was applied under isothermal conditions as in our previous studies [2–4]. So, our MW experimental system differs from the literatures which use the cooling system by “air cooling“ [5–8] while applying discontinuous MW power [9–11]. A typical experimental plot with the temperature/MW power data received per 1 s time interval is shown in Fig. 2.
Fig. 2.
A typical experimental plot (Exp. code: S1-Exp-6).
1.1. Calibration procedure and data of the microwave power output
According to the IEC 60705 standard method [12–14], empty jacketed glass vessel was weighed, filled with different amount of distilled water and placed into the MW reactor cavity. MW energy (Pnom) was supplied according to amount of water. The water was stirred along the heating period by a magnetic stirrer at 160 rpm. After 60 s, the final temperature of water was measured by Fluoroptic (FO) sensor. Absorbed MW power (P) by the vessel, water, magnet and 1,4-dioxane are calculated by means of Q=mcΔT. The results were given in Table 1. To account for the differences between the absorbed and nominal power values, a correction factor (p) is defined as “P/Pnom” which is used to calculate the required Pnom to achieve a given P value during the polymerization. Mean value of p was calculated as 0.608 under chosen experimental conditions and experimental system (reaction volume: 60 cm3) used in this study.
Table 1.
Calibration data of the microwave power output in the MW system.
| Exp. no | T1 (°C) | T2 (°C) | ΔT | Amount of water (g) | Pnom (W) | P (W) | Correction factor (p) |
|---|---|---|---|---|---|---|---|
| 1 | 9.5 | 16.2 | 6.7 | 40 | 40 | 25 | 0.631 |
| 2 | 9.0 | 15.5 | 6.5 | 50 | 50 | 32 | 0.640 |
| 3 | 9.6 | 13.5 | 3.9 | 30 | 30 | 12 | 0.416 |
| 4 | 9.8 | 20.9 | 11.1 | 30 | 75 | 33 | 0.444 |
| 5 | 10.1 | 20.3 | 10.2 | 50 | 90 | 45 | 0.499 |
| 6 | 9.3 | 19.7 | 10.4 | 40 | 70 | 39 | 0.551 |
| 7 | 9.4 | 21.5 | 12.1 | 80 | 120 | 84 | 0.699 |
| 8 | 9.3 | 25.0 | 15.7 | 50 | 100 | 76 | 0.756 |
| 9 | 9.7 | 16.9 | 7.2 | 60 | 60 | 40 | 0.672 |
| 10 | 9.4 | 17.7 | 8.3 | 80 | 80 | 58 | 0.724 |
| 11 | 9.3 | 18.3 | 9.0 | 90 | 100 | 69 | 0.690 |
| 12 | 9.9 | 18.7 | 8.8 | 100 | 100 | 74 | 0.736 |
| 13 | 9.0 | 17.8 | 8.8 | 100 | 100 | 74 | 0.736 |
| 14 | 9.4 | 22.7 | 13.3 | 100 | 150 | 111 | 0.738 |
| 15 | 9.4 | 20.0 | 10.6 | 60 | 110 | 54 | 0.492 |
| 16 | 9.8 | 24.8 | 15.0 | 60 | 120 | 76 | 0.633 |
| 17 | 9.5 | 27.1 | 17.6 | 70 | 140 | 101 | 0.723 |
| 18 | 9.5 | 24.3 | 14.8 | 70 | 130 | 85 | 0.657 |
| 19 | 9.5 | 23.6 | 14.1 | 110 | 160 | 127 | 0.794 |
| 20 | 9.5 | 24.5 | 15.0 | 150 | 200 | 177 | 0.885 |
| 21 | 9.5 | 23.7 | 14.2 | 200 | 230 | 217 | 0.944 |
| 22 | 9.7 | 22.6 | 12.9 | 250 | 250 | 242 | 0.970 |
| 23 | 9.7 | 17.8 | 8.1 | 60 | 60 | 42 | 0.693 |
| 24 | 9.8 | 24.9 | 15.1 | 60 | 120 | 77 | 0.638 |
| 25 | 9.7 | 24.8 | 15.1 | 60 | 120 | 77 | 0.638 |
| 26 | 9.7 | 17.9 | 8.2 | 60 | 60 | 46 | 0.763 |
| 27 | 9.7 | 18.0 | 8.3 | 60 | 60 | 46 | 0.772 |
| 28 | 9.3 | 24.7 | 15.4 | 150 | 200 | 182 | 0.908 |
| 29 | 9.8 | 14.2 | 4.4 | 60 | 50 | 29 | 0.573 |
| 30 | 9.4 | 15.5 | 6.1 | 60 | 70 | 40 | 0.567 |
| 31 | 9.5 | 17.6 | 8.1 | 60 | 90 | 53 | 0.586 |
| 32 | 9.7 | 19.5 | 9.8 | 60 | 110 | 64 | 0.580 |
| 33 | 9.3 | 20.5 | 11.2 | 60 | 130 | 73 | 0.561 |
| 34 | 9.1 | 22.6 | 13.5 | 60 | 150 | 88 | 0.586 |
| 35 | 9.0 | 24.6 | 15.6 | 60 | 170 | 101 | 0.597 |
| 36 | 9.0 | 27.8 | 18.8 | 60 | 200 | 122 | 0.612 |
| 37 | 9.0 | 29.3 | 20.3 | 60 | 230 | 132 | 0.574 |
| 38 | 9.0 | 32.0 | 23.0 | 60 | 250 | 150 | 0.599 |
Where P: absorbed power (W), m: mass of materials (g) (container, water, magnet, 1,4- dioxane), c: specific heat capacity of the materials, heating time=60 s, T1=initial temperature of water (10±0.5 °C), T2=final temperature of water (approximately ambient temperature).
1.2. Experimental data of MW-assisted emulsion polymerization of styrene
Six experimental variables given in Table 2 were investigated and suitable experimental conditions to achieve polymer yield >95% were determined as T=75 °C, SDS/M=0.06, KPS/M=0.004, H2O/M=6 and P=0.6 kW dm−3.
Table 2.
MW—experimental data.
| Exp. code | t (min) | T (°C) | SDS/M | KPS/M | H2O/M | P (kW dm−3) | Yield % | MW energy (kW h kg−1) | Production rate (kg m−3 h−1) |
|---|---|---|---|---|---|---|---|---|---|
| S1-exp-4 | 60 | 70.0 | 0.06 | 0.002 | 6 | 0.6 | 92.3 | 7.1 | 131.9 |
| S1-exp-5 | 60 | 70.0 | 0.08 | 0.002 | 6 | 0.6 | 91.6 | 6.5 | 130.9 |
| S1-exp-6 | 60 | 70.0 | 0.1 | 0.002 | 6 | 0.6 | 93.2 | 7.1 | 133.1 |
| S1-exp-4 | 60 | 70.0 | 0.06 | 0.002 | 6 | 0.6 | 92.3 | 7.1 | 131.9 |
| S3-exp-1 | 60 | 70.0 | 0.06 | 0.003 | 6 | 0.6 | 93.4 | 6.8 | 133.5 |
| S3-exp-2 | 60 | 70.0 | 0.06 | 0.004 | 6 | 0.6 | 94.3 | 6.5 | 134.7 |
| S3-exp-3 | 60 | 70.0 | 0.06 | 0.005 | 6 | 0.6 | 94.0 | 6.9 | 134.2 |
| S4-exp-3 | 60 | 60.0 | 0.06 | 0.004 | 6 | 0.6 | 84.3 | 7.5 | 120.4 |
| S4-exp-1 | 60 | 65.0 | 0.06 | 0.004 | 6 | 0.6 | 93.0 | 6.9 | 132.8 |
| S3-exp-2 | 60 | 70.0 | 0.06 | 0.004 | 6 | 0.6 | 94.3 | 6.5 | 134.7 |
| S4-exp-2 | 60 | 75.0 | 0.06 | 0.004 | 6 | 0.6 | 95.4 | 6.8 | 136.3 |
| S4-exp-4 | 60 | 80.0 | 0.06 | 0.004 | 6 | 0.6 | 96.5 | 6.7 | 137.8 |
| S4-exp-5 | 60 | 85.0 | 0.06 | 0.004 | 6 | 0.6 | 96.8 | 6.4 | 138.2 |
| S5-exp-13 | 7.5 | 75.0 | 0.06 | 0.004 | 6 | 0.4 | 70.3 | 6.3 | 100.4 |
| S5-exp-9 | 30 | 75.0 | 0.06 | 0.004 | 6 | 0.4 | 93.6 | 4.8 | 133.7 |
| S5-exp-1 | 65 | 75.0 | 0.06 | 0.004 | 6 | 0.4 | 95.3 | 5.0 | 136.2 |
| S5-exp-2 | 75 | 75.0 | 0.06 | 0.004 | 6 | 0.4 | 95.3 | 4.6 | 136.2 |
| S5-exp-3 | 90 | 75.0 | 0.06 | 0.004 | 6 | 0.4 | 96.6 | 5.3 | 137.9 |
| S5-exp-12 | 7.5 | 75.0 | 0.06 | 0.004 | 6 | 0.6 | 71.3 | 8.7 | 101.9 |
| S5-exp-11 | 15 | 75.0 | 0.06 | 0.004 | 6 | 0.6 | 89.8 | 7.5 | 128.3 |
| S5-exp-10 | 30 | 75.0 | 0.06 | 0.004 | 6 | 0.6 | 93.6 | 6.5 | 133.8 |
| S5-exp-4 | 45 | 75.0 | 0.06 | 0.004 | 6 | 0.6 | 94.9 | 7.4 | 135.6 |
| S4-exp-2 | 60 | 75.0 | 0.06 | 0.004 | 6 | 0.6 | 95.4 | 6.8 | 136.3 |
| S5-exp-5 | 75 | 75.0 | 0.06 | 0.004 | 6 | 0.6 | 96.4 | 6.5 | 137.7 |
| S5-exp-14 | 7.5 | 75.0 | 0.06 | 0.004 | 6 | 0.8 | 71.2 | 13.7 | 101.7 |
| S5-exp-6 | 30 | 75.0 | 0.06 | 0.004 | 6 | 0.8 | 93.6 | 9.6 | 133.6 |
| S5-exp-7 | 45 | 75.0 | 0.06 | 0.004 | 6 | 0.8 | 95.6 | 10.3 | 136.5 |
| S5-exp-8 | 60 | 75.0 | 0.06 | 0.004 | 6 | 0.8 | 95.8 | 8.9 | 136.8 |
| add-1 | 7.5 | 75.0 | 0.06 | 0.004 | 6 | 0.3 | 64.4 | 5.1 | 91.9 |
| S6-exp-1 | 90 | 75.0 | 0.06 | 0.004 | 9 | 0.4 | 95.4 | 7.3 | 95.4 |
| S5-exp-3 | 90 | 75.0 | 0.06 | 0.004 | 6 | 0.4 | 96.6 | 5.3 | 137.9 |
| S6-exp-2 | 90 | 75.0 | 0.06 | 0.004 | 3 | 0.4 | 97.2 | 2.9 | 243.0 |
The bold style indicate the “suitable experimental conditions” in each serial.
1.3. Experimental data of CH-emulsion polymerization of styrene
Five CH experiments were conducted also at the experimental conditions (T=75 °C, SDS/M=0.06, KPS/M=0.004, H2O/M=6) at different reaction times. The results are presented in Table 3. The comparison of CH and MW experimental results at the same conditions demonstrate the advantage of MW application in term of polymerization time.
Table 3.
CH/MW experimental data for comparison purpose.
| Method | Exp. code | t (min) | T (°C) | SDS/M | KPS/M | H2O/M | P (kW dm−3) | Yield % | MW energy (kW h kg−1) | Production rate (kg m−3 h−1) |
|---|---|---|---|---|---|---|---|---|---|---|
| CH | CH-1 | 90 | 75 | 0.06 | 0.004 | 6 | 0.0 | 94.6 | 0.0 | 135.3 |
| CH-2 | 45 | 75 | 0.06 | 0.004 | 6 | 0.0 | 91.2 | 0.0 | 130.4 | |
| CH-3 | 30 | 75 | 0.06 | 0.004 | 6 | 0.0 | 89.7 | 0.0 | 128.2 | |
| CH-4 | 15 | 75 | 0.06 | 0.004 | 6 | 0.0 | 86.4 | 0.0 | 123.4 | |
| CH-5 | 7.5 | 75 | 0.06 | 0.004 | 6 | 0.0 | 51.0 | 0.0 | 72.9 | |
| MW | add-1 | 7.5 | 75 | 0.06 | 0.004 | 6 | 0.3 | 64.4 | 5.1 | 91.9 |
| S5-exp-13 | 7.5 | 75 | 0.06 | 0.004 | 6 | 0.4 | 70.3 | 6.3 | 100.4 | |
| S5-exp-12 | 7.5 | 75 | 0.06 | 0.004 | 6 | 0.6 | 71.3 | 8.7 | 101.9 | |
| S5-exp-14 | 7.5 | 75 | 0.06 | 0.004 | 6 | 0.8 | 71.2 | 13.7 | 101.7 | |
| S5-exp-11 | 15 | 75 | 0.06 | 0.004 | 6 | 0.6 | 89.8 | 7.5 | 128.3 | |
| S5-exp-6 | 30 | 75 | 0.06 | 0.004 | 6 | 0.8 | 93.5 | 9.6 | 133.6 | |
| S5-exp-10 | 30 | 75 | 0.06 | 0.004 | 6 | 0.6 | 93.6 | 6.5 | 133.8 | |
| S5-exp-7 | 45 | 75 | 0.06 | 0.004 | 6 | 0.8 | 95.5 | 10.3 | 136.5 | |
| S5-exp-3 | 90 | 75 | 0.06 | 0.004 | 6 | 0.4 | 96.6 | 5.3 | 137.9 |
1.4. Polymer characterization data
MW and CH polymer samples synthesized at the same process conditions were found to have similar structural and thermal characteristics. The analysis data supplied by GPC, DSC and Viscosity instruments is shown in Table 4.
Table 4.
Polymer characterization data of CH and MW experiments at similar process conditions.
| Results | CH | MW |
|---|---|---|
| t (min) | 45 | 90 |
| T (°C) | 75.0 | 75.0 |
| SDS/M | 0.06 | 0.06 |
| KPS/M | 0.004 | 0.004 |
| H2O/M | 6 | 6 |
| P (kW dm−3) | – | 0.6 |
| Mv (g mol−1) | 1715,037 | 1447,770 |
| Mn (g mol−1) | 1179,000 | 969,900 |
| Mw (g mol−1) | 1829,000 | 1665,700 |
| Mz (g mol−1) | 2523,300 | 2447,800 |
| Dp | 11,336 | 9,326 |
| D | 1.5518 | 1.7174 |
| Tg (°C) | 105.6 | 104.1 |
| Tm (°C) | 422 | 425 |
| cp (J g−1 °C−1) | 0.365 | 0.228 |
Acknowledgments
We thank the Gebze Technical University (GTU) research fund for partial support.
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