Supporting Information For s5
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Supporting information for
Environmentally Benign Stereoselective Polymerizations of Polar as well as Nonpolar Olefins by a New Postmetallocene Ti(IV) Salicylate Complex at Ambient Temperature in Aqueous Emulsion
K. Sharma, G. Lunawat and S. K. De
Department of Chemistry, Jaypee University of Engineering and Technology, Guna, 473226, India Figure S1 Variation of Activity with Time in the Homopolymerization of Styrene and MMA
Figure S2 Changes in Number Average Molecular Weight with Yield in the Homopolymerization of Styrene and
MMA Figure S3 Comparison of Number Average Molecular Weight with Polymerization Time in Homopolymerization of
Styrene and MMA
Figure S4 Changes in Yield with Time in the Homopolymerization of Styrene and MMA Figure S5 Representative 13C NMR spectrum of Polystyrene Figu re S6 Representative 1H NMR spectrum of PMMA Figure S7 Representative 1H NMR spectrum of PS-co-PMMA(1:1)
Determination of Reactivity Ratio
For determination of reactivity ratio, a set of five copolymerization reactions were conducted using different feed ratio and the conversion was restricted below 10%.The reactivity ratios of the co-monomers were determined using linear least-square methods such as Finemann–Ross, inverted Finemann–Ross and Kelen–Tudos.
Finemann–Ross (F-R) method The reactivity ratio of the co-monomers determined using the Finemann- Ross relation.
G = r H – r 1 2 (1)
2 Where r1 and r2 are reactivity ratio of styrene and MMA respectively and G = f (F-1)/F and H = f /F (f = f1/f2 and F = F1/F2, f1 and f2 are the monomer molar composition in feed and F1 and F2 are the copolymer molar composition of styrene and methyl methacrylate respectively.i
Table S1: Data required for G vs H plot
2 S.N Feed Ratio MMA f = f1/f2 F = F1/F2 G = f (F-1)/F H = f /F . MMA:St Incorporation mol:mol (%)b 1 1:9 11.76 9 7.50 7.80 10.79 2 1:4 21.05 4 3.75 2.93 4.26 3 1:1 41.74 1 1.39 0.28 0.71 4 4:1 71.29 0.25 0.40 0.37 0.15 5 9:1 83.3 0.11 0.20 0.44 0.06
Figure S8: Finemann –Ross plot The reactivity ratios were found to be r1 (styrene) = 0.76 and r2 (MMA) = 0.40.
Inverted Finemann–Ross (F-R) method
The linear relationship in the Finemann–Ross (F-R) method between r1and r2 could be shown for inverted F-R method as
G/H=rst (1/H) rMMA (2)
Table S2: Data for the determination of reactivity ratio by the inverted F-R method
2 Sl Feed MMA f = f1/f2 F = F1/F2 G = f (F-1)/F H = f /F 1/H G/H . Ratio Incorporation MMA:St (%)b mol:mol 1 1:9 11.76 9 7.50 7.80 10.79 0.09 0.72 2 1:4 21.05 4 3.75 2.93 4.26 0.23 0.68 3 1:1 41.74 1 1.39 0.28 0.71 1.39 0.39 4 4:1 71.29 0.25 0.40 0.37 0.15 6.44 -2.38 5 9:1 83.3 0.11 0.20 0.44 0.06 16.23 -7.19
According to the data available in Table S2, G/H versus 1/H has been plotted. The reactivity ratios could be obtained from the slope (rMMA =0.49) and intercept (rSt = 0.87) of the best-fitted line.(Figure S5)
Figure S9: G/H versus 1/H plot for determination of reactivity ratio by the inverted F-R method
KELEN- TUDOS METHOD K-T method aims at preventing the nonsymmetrical characteristic of the composition equation from affecting the reactivity ratio values determined experimentally. The parameters of K-T equation is presented in Table S3. The KT plot is given as Figure S6. In this method the reactivity ratios are related to each other by following equation.
(3)
½ = (H maxH min)
= H + H
= G/ +H
The values of G and H could be extracted from Table S1 and the values of and are calculated in table S3. The domain for variation of and is between 0 and 1 meanwhile this domain for G and H is 0 and.
Table S3: Data for the determination of reactivity ratio by the Kelen Tudos method
2 S.NO f = f1/f2 F = F1/F2 G = f (F-1)/F H = f /F =H/(+H) =G/(+H)
1 9 7.50 7.80 10.79 0.82 0.93 0.67
2 4 3.75 2.93 4.26 0.82 0.83 0.57 3 1 1.39 0.28 0.71 0.82 0.46 0.18 4 0.25 0.40 0.37 0.15 0.82 0.15 0.38 5 0.11 0.20 0.44 0.06 0.82 0.07 0.50
Figure S10: Plot of vs for the determination of reactivity ratio by KELEN-TUDOS method
Calculation: =1.3790.571
=1.3790.571
(rst rMMA/)=1.379
rMMA/=0.571
rMMA=0.46, rst0.80
According to the kelen –Tudos plot, rSt and rMMA were obtained as 0.80 and 0.46 respectively. The data lie on the straight line with very little scatter. The KT method has the advantages that the data are uniformly distributed and the results do not depend on which monomer is labeled as the monomer (A) and which one is labeled as the monomer (B).ii
End group analysis
The end group analysis were carried out using methods developed by Postma et al.iii who have reported that reaction of trichloroacetyl isocyanate with polymers having protic end group in a NMR tube generate the derivative, -O-CO-
1 NH-COCCl3 (Scheme S1) and the imidic proton can easily be detected by H NMR spectroscopy, which typically
31 appear in the region 7.5-11 ppm. A solution of low molecular weight PMMA (Mn ~25500, obtained in very little amount by quenching the polymerization reaction within two minutes of addition of catalyst solution and NaBPh 4)
1 1 in CDCl3 was reacted with one drop of trichloroacetyl isocyanate and the H NMR was recorded. The H NMR spectrum of the derivative shows three additional signals at 10.5 ppm and at 6.6 and 6.2 ppm (Figure 10). The signal at 10.5 ppm is due to the imidic proton of the product of the reaction of trichloroacetyl isocyanate with the polymer (Scheme S1). The other two peaks appear due to the main by-product, trichloro acetamide produced by hydrolysis of trichloroacetyl isocyanate. Similarly, newly synthesized PS and co-polymer samples were analyzed in this fashion and we could detect in all the cases –OH end group.
Scheme S1: Reaction of polymers with hydroxyl end group and trichloroacetyl isocyanate i Ali Reza Mahdavian, Mahdi Abdollahi, Leila Mokhtabad, Hamid Reza Bijanzadeh, Farshid Ziaee, Journal of Applied Polymer Science. 2006, Vol. 101, 2062–2069 ii Gamze Barima, Mustafa Gokhun Yaylab , Mustafa Degirmenci, Designed Monomers and Polymers. 2014, Vol. 17, 610–616. iii. Postma, A.; Davis, T. P.; Donovan, A. R.; Li, G.; Moad, G.; Mulder, R.; O’Shes, M. S. A simple method for determining protic end-groups of synthetic polymers by 1H NMR spectroscopy Polymer, 2006, 47, 1899-1911.