Synthesis of Ethylene Glycol Dimethacrylate-Methyl Methacrylate Copolymers, Determination of their Reactivity Ratios, and a Study of Dopant and Temperature Effects on their Conductivities
Abstract
:1. Introduction
2. Experimental
2.1. Materials
2.2. Preparation of Polymers
2.3. Preparation of Copolymers
3. Theory
3.1. Mechanisms
EGDMA● + EGDMA ➔ EGDMA● (growing radical)
EGDMA● + MMA ➔ MMA●
MMA● + EGDMA ➔ EGDMA●
MMA● + MMA ➔ MMA● (growing radical)
3.2. Rate of Creation of Radicals
4. Results and Discussion
4.1. IR Analysis of EGDMA/MMA Copolymers
Copolymer | MMA (mL) | EGDMA (mL) | THF (mL) | Volume ratio of EGDMA to MMA in feed |
---|---|---|---|---|
1 | 0.75 | 4.25 | 10 | 5.66 |
2 | 1.00 | 4.00 | 10 | 4.00 |
3 | 1.25 | 3.75 | 10 | 3.00 |
4 | 1.50 | 3.50 | 10 | 2.33 |
5 | 1.75 | 3.25 | 10 | 1.86 |
Copolymer | (A)Copolymer Taken g/mL in chl *103 | Absorbance at 520–540 cm−1 | (B)(MMA)B1 *103 in chl. | (A−B) (EGDMA)A-B2 *103 in chl. | [MMA] mol/L in co-polymer | [EDGMA] mol/L in copolymer | (F2) mol % of MMA in copolymer |
---|---|---|---|---|---|---|---|
1 | 7.0 | 0.27 | 1.35 | 5.66 | 0.01348 | 0.02855 | 32.09 |
2 | 4.2 | 0.32 | 1.80 | 2.40 | 0.01797 | 0.01210 | 59.76 |
3 | 5.4 | 0.37 | 2.20 | 5.03 | 0.02190 | 0.02537 | 46.41 |
4 | 7.7 | 0.48 | 3.10 | 4.61 | 0.03096 | 0.02325 | 57.12 |
5 | 9.9/ | 0.85 | 6.30 | 3.60 | 0.06292 | 0.01816 | 77.60 |
Copolymer | [EGDMA]/[MMA] volume ratio in feed from Table 1 | [MMA] in feed, mol/L, in chloroform | [EGDMA] in feed, mol/L, in chloroform | (f2) mol % MMA in feed |
---|---|---|---|---|
1 | 5.66 | 0.467 | 1.502 | 23.72 |
2 | 4.00 | 0.623 | 1.414 | 30.20 |
3 | 3.00 | 0.779 | 1.325 | 37.02 |
4 | 2.33 | 0.935 | 1.237 | 43.05 |
5 | 1.86 | 1.091 | 1.149 | 48.71 |
Copolymer No. | Mole ratio in feed H = [EGDMA][MMA] from Table 3 | Mole ratio in copolymer H = [EGDMA]/[MMA] | H(1-h)/h | H2/h |
---|---|---|---|---|
1 | 3.216 | 2.118 | −1.697 | 4.883 |
2 | 2.269 | 1.330 | −0.563 | 3.870 |
3 | 1.701 | 1.155 | −0.228 | 2.505 |
4 | 1.323 | 0.751 | 0.439 | 2.331 |
f2 (mol% MMA in feed) | F2 (mol% MMA in Copolymer) |
---|---|
23.72 | 32.09 |
37.02 | 46.41 |
43.05 | 57.12 |
48.71 | 77.60 |
4.2. Conductivity Change of Monomers and Copolymers with Temperature and Dopant
Temperature (°C) | Conductivity (µS) |
---|---|
35.0 | 12.3 |
33.0 | 10.9 |
26.0 | 9.0 |
18.2 | 6.7 |
4.0 | 9.8 |
−4.0 | 12.0 |
4.3. Copolymer Conversion
4.4. Activation Energy Determination for the Reaction of EGDMA/MMA Copolymer with Lithium Perchlorate
Temperature (°C) | Reaction completion time of copolymer with dopant LiClO4 (Min.) |
---|---|
6.5 | 8 |
10.0 | 17 |
15.0 | 19 |
25.0 | 141 |
30.0 | 185 |
33.9 | 231 |
40.0 | 265 |
43.0 | 291 |
5. Conclusions
- Using IR spectroscopy of PEGDMA and PMMA homopolymers and their copolymers, the reactivity ratio of EGDMA (r2) and MMA (r1) were calculated as 0.6993 and 1.8635, respectively.
- The conductivities of PEGDMA (mS region) is much greater than the conductivities of PMMA (µS region).
- The conductivities of PEGDMA and PMMA both increase with added dopant, LiClO4.
- As the MMA concentration in the polymer increases, the conductivity value decreases (mS to µS).
- As the MMA percentage in the monomer feed increases, the percent conversion (polymerization) decreases.
- Conductivity vs. temperature graph for PEGDMA shows a minimum at 18 °C. PMMA and PEGDMA/PMMA copolymers also show the same kind of behavior, with minimum values observed at 22–24 °C. This indicates that these polymers first act as a conductor, then after a minimum temperature become semiconductors and can be potentially used to control the current in electrical devices via temperature change (thermal switch).
- The measurement of conductivity change with time provides an excellent and new way to follow the kinetics of the copolymer-dopant reactions. By measuring the reaction completion times at different temperatures of the PEGDMA/MMA copolymer, activation energy of interaction with perchlorate ion was determined to be 31.52 kJ/mol. For PEGDMA alone this value was found to be 54.7 kJ/mol. As the temperature increases, the reaction completion time also increases.
- When EGDMA is copolymerized with MMA to increase its mechanical properties, copolymers still show the same trend of conductivity change with temperature even though the conductivity of the copolymer decreases slightly with increasing percentage of MMA. Therefore, interest in using these copolymers in industry as thermal switches still exists.
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Ramelow, U.S.; Pingili, S. Synthesis of Ethylene Glycol Dimethacrylate-Methyl Methacrylate Copolymers, Determination of their Reactivity Ratios, and a Study of Dopant and Temperature Effects on their Conductivities. Polymers 2010, 2, 265-285. https://doi.org/10.3390/polym2030265
Ramelow US, Pingili S. Synthesis of Ethylene Glycol Dimethacrylate-Methyl Methacrylate Copolymers, Determination of their Reactivity Ratios, and a Study of Dopant and Temperature Effects on their Conductivities. Polymers. 2010; 2(3):265-285. https://doi.org/10.3390/polym2030265
Chicago/Turabian StyleRamelow, Ulku S., and Sreedhar Pingili. 2010. "Synthesis of Ethylene Glycol Dimethacrylate-Methyl Methacrylate Copolymers, Determination of their Reactivity Ratios, and a Study of Dopant and Temperature Effects on their Conductivities" Polymers 2, no. 3: 265-285. https://doi.org/10.3390/polym2030265