Activator Generated by Electron Transfer Atom Transfer Radical Polymerization.

Craig Machado*, Dahlia Amato, Corey Parada

University of Southern Mississippi, Hattiesburg, MS.

ABSTRACT: Activator generated by electron transfer atom

transfer radical polymerization (AGET ATRP) was used to successfully polymerize methylmethacrylate (MMA). It was found by 1HNMR that molecular weight control depended heavily on monomer to initiator concentration. There was no apparent effect on molecular weight from the amount of reducing agent. Additionally no correlation between molecular weight of the samples and Tg could be drawn. Sample 1 had the highest Tg which could be due to the difference in samples physical properties or possibly poor initiation. TGA data showed that samples 2, 3, and 4 had a residual anisole peak at 100-200 C whereas sample 1 did not. The two-step degradation of PMMA was found to be present in all samples of radically polymerized PMMA.

N,N,N,N ,N -pentamethyldiethylenetriamine (PMDETA) as the ligand and tin (II) 2-ethylhexanoate (Sn(EH)2) as the reducing agent. Four samples are prepared and the relative molar quantities of monomer and reducing agent are varied while keeping the other reagents ratios constant. These parameters are varied in order to study the effect of the amount of monomer and reducing agent on the molecular weight and physical properties of the polymers. The polymers were analyzed by proton nuclear magnetic resonsance spectroscopy (1HNMR), thermal gravimetric analysis (TGA), and differential scanning calorimetry (DSC). DSC is one of the most ubiquitous thermal analysis techniques in chemistry. DSC measures heat flow into or out of a sample over a range of temperatures as compared to a reference cell. (citation). This information can be used for a wide variety of purposes. Purity of a sample can be measured by utilizing the principle of melting point depression (Brown), miscibility properties can be determined, and information about crystallization mechanisms can be inferred all using DSC (Pengbo Liu). In this study, DSC is used to measure the glass transition temperature (Tg) of our polymers. Another important thermal analysis method is TGA. In TGA, the sample is placed on a hook which measures its mass. The sample is then heated and thermally decomposed. As the sample decomposes, its mass changes and this change in mass is measured by the instrument. By monitoring the amount of mass lost in particular temperature ranges, one can infer certain quantities such as the amount of residual solvent left on the sample, composition of a mixture, and more. citation EXPERIMENTAL Materials. Methyl methacrylate (MMA) was used after passing the monomer through basic alumina column to remove the inhibitor. Copper (II) bromide (CuBr2), N,N,N,N ,N pentamethyldiethylenetriamine (PMDETA), anisole, tin(II) 2ethylhexanoate (Sn(EH2)), ethyl -bromoisobutyrate, hexanes, tetrahydrofuran (THF), and methanol were used as received. Preparation of PMMA I. Methyl methacrylate (3 mL, 28.05 mmol), copper (II) bromide (0.0623 g, 0.277 mmol), PMDETA (0.0468 g, 0.270 mmol), anisole (2.25 mL), and a stir bar were loaded into 10 mL test tube and sealed with rubber septa and parafilm. The mixture then stirred for 5 minutes and purged with N2 for 15 minutes. In a second 10 mL test tube, Sn(EH)2 (0.271 g, 0.67 mmol), ethyl -bromoisobutyrate (0.0531 g, 0.272 mmol) anisole (0.75 mL) and stir bar were added and the tube was sealed with a rubber septum and parafilm. The mixture was purged for 15 minutes with N2. The contents of second tube were then transferred to first tube via cannula which turned the solution light blue. The mixture was then placed in 80 C oil bath, in which

INTRODUCION Atom transfer radical polymerization (ATRP) is a controlled radical polymerization technique that utilizes an atom (usually a halogen) that can reversibly bind between propagating polymer chains and a metal/ligand complex. When the halogen is transferred from a propagating chain to the metal/ligand complex, a radical forms on the end of the propagating chain, which allows the chain to add monomer, and the metal is reduced by the incoming halogen. Thus, when the metal is in the reduced state, the halogen is attached to the metal and chains are allowed to propagate, and when the metal is in the oxidized state, the halogen is bound to the polymer chains and the chains remain dormant.(
Wang, J.-S.; Matyjaszewski, K. J. Am. Chem. Soc. 1995, 117, 5614-5615.)

(insert scheme) In activator generated by electron transfer ATRP (AGET ATRP), only the metal in its oxidized state is added to the reaction mixture. In order to reduce the metal and create active chains, a reducing agent is added. One advantage to AGET ATRP over conventional ATRP is that the more oxidatively stable metal can be used. When handling the reduced form of the metal while carrying out ATRP, the metal can be oxidized in the air prior to adding it to the reaction vessel. Since the oxidized form of the metal is used in AGET ATRP, this is not an issue. Additionally, the reducing agent may be able to remove any traces of oxygen that may be left in the system. Jakubowski, W.; Matyjaszewski, K. Macromolecules 2005, 38, 4139-4146.) In this study, AGET ATRP is used to synthesize poly(methyl methacrylate) (PMMA) using ethyl -bromoisobutryate (I) as an intiator. Different reducing agents and ligands can be used for AGET ATRP. Sometimes reagents may function both as the ligand and reducing agent (http://www.tandfonline.com/doi/abs/10.1163/138577210X53058 5#.UkdHHIZvNCo) Copper (II) bromide is used in this study with

solution turned grey. After one hour, the reaction mixture was submerged in liquid N2 and exposed to air to kill the reaction. The mixture was then diluted with THF and then precipitated into hexanes. The suspension was then placed in a Centra GP8 centrifuge for 5 minutes. The mixture was decanted leaving behind a solid pellet. The pellet was then dissolved in THF and precipitated in methanol. The suspension was then centrifuged. This process was repeated (1X). The pellet obtained was then dried at room temperature for 7 days. Other samples of PMMA were prepared following the same process with various ratios of MMA: CuBr2: PMDETA: Sn(EH2): ethyl -bromoisobutyrate (I) shown in Table 1. Table 1. Ratios of reagents for different PMMA samples Sample Number 1 2 3 4
1

Figure Tits. 1HNMR spectrum of sample 1 is shown above. Alkene hydrogen A has an integration value set to 1 and peaks C and D together integrate to 8.83 Once percent conversion is known, it can be multiplied by the monomer to initiator ratio to find the degree of polymerization (DP), assuming complete initiation. Once DP is known, it can be multiplied by the molar mass of the monomer to yield the molecular weight (Mn). Table 2. The effect of monomer to initiator ratio can be seen below Sample Number 1 2 3 4 Monomer/Initiator ratio 103 69.7 203 142 % Conversion 66 87.5 72.6 75.4 DP 68.0 61.0 147.4 107.1 Mn (g/mol) 6,990 6,300 15,000 10,900

MMA 103 69.7 203 142

I 1.00 1.00 1.00 1.00

CuBr2 1.00 0.736 0.938 0.583

PMDETA 1.00 1.09 0.847 0.790

Sn(EH)2 2.48 0.714 1.77 0.859

H NMR was recorded on a Varian Mercury Plus 300 MHz NMR in CDCl3 to determine the percent conversion and degree of polymerization. Thermal Analysis. DSC. Samples 1-4 were weighed (4-10 mg) into hermetic pans and sealed. The samples underwent a three minute isotherm at 25 C, were then heated to 150 C at a rate of 10 C/min, isothermed for 5 minutes at 150 C, and then cooled to 0 C at a cooling rate of 10 C/min. This cycle was repeated one more time. TGA. The samples were equilibrate at --- C for 5 minutes and then heated 20 C/min to 600 C. RESULTS AND DISCUSSION Molecular weights of the polymers were determined via HNMR analysis. By setting the integration of one of the monomer alkene peaks, hydrogen A in Figure BLANK, as 1.00 and comparing that to the integration of the total methoxy hydrogens, peaks C and D, percent conversion can be found using the following equation
1

Comparing the molecular weights of samples one and two to samples three and four, it can clearly be seen that molecular weight is dependent on the monomer to initiator ratio. When the monomer to initiator ratio was approximately doubled, the molecular weight doubled as well. There seems to be no clear correlation between reagent ratios and percent conversion. One factor that did clearly affect percent conversion was the reaction time. Sample two was allowed to react for ten minutes longer than the rest of the samples, and as an effect, its percent conversion is more than ten percent higher than all the other samples. The effect of reducing agent concentration is a bit harder to interpret. The ratio of other reagents was supposed to be held constant in order to see how the amount of reducing agent affected the produced polymer, but since the ratios of the other reagents changed throughout the different tests, no conclusion can be made about the effect of reducing agent. According to Jakubowski and Matyjaszewski, adding less reducing agent than copper allows for better molecular weight control. Since not all of the copper (II) is reduced to copper (I), the number of activated chains is kept lower. Lower radical concentration allows for better molecular weight control.

Figure boob. DSC endotherms of each sample is shown above. Glass transition temperatures have been marked on the traces. Table 3. Tg values for each sample can be seen below Sample Number Tg (oC) Mn (g/mol)

1 2 3 4

121.84 87.35 85.89 95.73

6,990 6,300 15,000 10,900

two peaks are reported in the literature. Thus, the two step degradation shown in TGA 1, 2, 3, and 4 agrees well with the literature,

The Tg values of each of the polymers can be seen in Table 3 above. The Tg values for samples 2-4 are significantly lower than the literature value of 108 oC for atactic (porter blum). This could be due to the fact that our molecular weights are quite low. It is known that Tg is dependent on molecular weight (burfield, Doi). However, there seems to be no correlation between the Tg values and the calculated molecular weights in our study. Although sample 3 has the highest molecular weight, it has the lowest Tg. Sample 1 is on the lower end of molecular weight, but has a Tg more than 25 oC higher than the rest of the samples. One possible explanation for this higher observed Tg of sample 1 is the sample preparation. Sample 1 was a fluffy white powder whereas the other samples were clear solid plastics. The amount of polymer in contact with the bottom of the DSC pan would be very different for a fine powder and a solid plastic. Sample uniformity is very important to the accuracy of results in thermal analysis (Cohen, Carriere). Another possible explanation for the increased Tg of sample 1 is that the molecular weight is actually higher than that calculated. The molecular weight calculations compared the ratio of the methoxy hydrogens in the monomer to those in the polymer. However, this caculation doesnt take into account the number of propagating chains. If poor initiation occurred, the same number of monomers would be added to a lesser number of chains, yielding a larger average molecular weight. One reason this may have occurred is that upon adding the initiator and reducing agent into the reaction tube via cannula, sample 1 was immediately lowered into the heated oil bath. After a few minutes, the reaction became clumpy, appearing almost as if a precipitate had formed. To prevent this problem for the subsequent reactions, the samples were allowed to mix for a few minutes before being lowered into the oil bath. Although it is quite possible that poor initiation may have occurred in sample 1, it is unlikely that any increase in molecular weight due to this caused such a dramatic increase in Tg. Thermogravimetric Analysis Thermogravimetric analysis (TGA) was used to characterize the four experimentally prepared samples of PMMA, and the resulting plots are shown in Figure X. Each TGA experiment was carried out in a ceramic pan, due to possible copper residue within the PMMA which would cause a platinum pan to oxidize. Each TGA experiment was also carried out in an inert nitrogen atmosphere, to prevent thermal oxidative degradation. The effect of thermal oxidative degradation will be discussed in the following paragraphs. The TGA plots of samples 2-4 show three distinct peaks between the 100 oC to 450 oC region. To avoid redundancy, we will designate the TGA plot correlating to sample 1 as TGA 1, TGA 2 for the TGA plot correlating to sample 2, etc. The first peak observed in TGA 2, TGA 3, and TGA 4 was attributed to be residual anisole solvent that was present in the PMMA sample. This peak was not observed in TGA 1 due to the PMMA sample being a very fine powder, while the other three samples were hard, rubber solids. Thus, it can be reasonably assumed that samples 2, 3, and 4 all contained anisole solvent trapped within the lattice structure. For anionically polymerized PMMA, one derivative peak is reported to be present around 360 oC, which correlates to the degradation temperature of regio-selective PMMA. (Kashiwagi et al.) For radically polymerized PMMA however,

Figure

Figure

and confirms that the experimentally obtained PMMA was polymerized via a free radical mechanism. The existence of two TGA peaks for radically polymerized PMMA can be explained via studying the degradation mechanism within the polymer backbone. Previous studies have concluded that irregular structures (such as head-head coupling and unsaturated end groups) present in radically prepared PMMA may cause PMMA to degrade in two steps, which is observed in Plots 1-4. (Kashiwagi et al., Holland et al.) Thermal degradation may involve backbone unzipping to form MMA monomer and a tertiary radical, shown in Scheme X (adapted from Wilkie). It should be emphasized that this mechanism applies for thermal degradation of PMMA in inert atmospheres. For radically polymerized PMMA samples that thermal degradation in oxygen, a four step degradation mechanism has been proposed. Hirata et al. also postulated that PMMA will form a primary radical in the presence of metal halides, such as complexed CuBr, which is shown in Scheme X+1 (adapted from Wilkie). PMMA degradation via this mechanism will either terminate the radical or remove the radical from the polymer backbone, thereby hindering further degradation of the polymer. This will result in prolonged PMMA degradation, which will increase the temperature range required to degrade the PMMA sample and lead to a wider temperature curve.

Conclusion AGET ATRP was successfully performed on all four samples. It was found by 1HNMR that molecular weight control depended heavily on monomer to initiator concentration. There was no apparent effect on molecular weight from the amount of reducing agent. Additionally no correlation between molecular weight of the samples and Tg could be drawn. Sample 1 had the highest Tg which could be due to the difference in samples physical properties or possibly poor initiation. TGA data showed that samples 2, 3, and 4 had a residual anisole peak at 100-200 C whereas sample 1 did not. The two-step degradation of PMMA was found to be present in all samples of radically polymerized PMMA.

ASSOCIATED CONTENT ACKNOWLEDGMENT

We thank Emily Hoff for her help with polymer synthesis and 1 HNMR, Austin Baranek for his help with thermal analysis, and Dr. Derek Patton for his help throughout.

Scheme

REFERENCES
1. Meng, Qinghua, Heng Liu, Sen Cheng, Chengxi Cao, Jicun Ren, and BV ELSEVIER SCIENCE. "A Novel Molecular Probe Sensing Polynuclear Hydrolyzed Aluminum by Chelation-enhanced Fluorescence."TALANTA, 99 (2012): 464-470. 2. Jimrna S. Zugazagitia, Mauricio Maya, Carlos Damian-Zea, Pedro Navarro, Hiram I. Beltran, Jorge Peon. Excited-Sate Dynamics and two-Photon Absorption Cross Sections of Fluorescent Diphenyl-Tin(IV) Derivatives with Schiff Bases: A comparative Study of the Effect of Chelation from the Ultrafast to the Steady-State Time Scale. Journal of Physical Chemistry. 114 (2010): 704-714. 3. MORISIGE, K, and BV ELSEVIER SCIENCE. "Metalcomplexes of Aromatic Schiff-base Compounds .1. Fluorescence Properties of Aluminum and Gallium Complexes of Aromatic Schiff-bases and Their Use in Fluorimetry." Analytica Chimica Acta, 72.2 (1974): 295-305. Scheme

Appendix A