Accepted Manuscript

Polylactic acid, maleic anhydride and dicumyl peroxide: NMR study of the free-radical
melt reaction product

Idejan P. Gross, Felipe S. Schneider, Miguel S.B. Caro, Thiago F. da Conceição,

Giovanni F. Caramori, Alfredo T.N. Pires

PII: S0141-3910(18)30208-8
DOI: 10.1016/j.polymdegradstab.2018.06.016
Reference: PDST 8581

To appear in: Polymer Degradation and Stability

Received Date: 17 April 2018

Revised Date: 21 June 2018
Accepted Date: 27 June 2018

Please cite this article as: Gross IP, Schneider FS, Caro MSB, da Conceição TF, Caramori
GF, Pires ATN, Polylactic acid, maleic anhydride and dicumyl peroxide: NMR study of the
free-radical melt reaction product, Polymer Degradation and Stability (2018), doi: 10.1016/
j.polymdegradstab.2018.06.016.

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 ACCEPTED MANUSCRIPT
1 Polylactic acid, maleic anhydride and dicumyl peroxide:
2 NMR study of the free-radical melt reaction product

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4 Idejan P. Gross*, Felipe S. Schneider, Miguel S. B. Caro, Thiago F. da Conceição,
5 Giovanni F. Caramori, Alfredo T. N. Pires

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7 Chemistry Department, Federal University of Santa Catarina,
8 Florianópolis-SC, Brazil.

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9 *gross.i.p@posgrad.ufsc.br

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11 Abstract
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In this study, a detailed characterization was carried out of a product formed in the
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13 melt reaction of poly(lactic acid) PLA with maleic anhydride, initiated by dicumyl
14 peroxide under the reaction conditions reported herein. The chemical structure of the
reaction product was determined by 1H-NMR and 13
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15 C-NMR spectroscopy and by

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16 DEPT-135 and C-1H HSQC techniques. It was found that, under the conditions
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17 applied in this study, instead of the well-reported grafting of maleic anhydride onto the
18 PLA, a product was formed from the reaction of two PLA macro-radicals, which
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19 probably occurs after the β-scission mechanism. The C-NMR spectrum of the
20 proposed reaction product was also calculated using the GIAO-DFT method and the
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21 result is in agreement with the experimental spectrum.

22 Keywords: Polymer grafting, grafted PLA, chemical modification

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23 Introduction

24 The chemical modification of polymers by means of grafting is an interesting

25 way to adjust the physical-chemical properties of polymeric materials for specific
26 applications. Polymer grafting has been employed for different purposes, for example,
27 to improve the compatibility between components in blends and composites [1-3]. In
28 this regard, maleic anhydride (MA) is one of the most commonly used compounds,
29 since it can be easily grafted onto polyolefins and polyesters in the presence of a

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30 radical initiator, such as dicumyl peroxide (DCP), forming a derivative with a succinic
31 anhydride moiety (which differs from MA in that it lacks unsaturation) as a side
32 group. Some recent studies involving grafting have been focused on biodegradable
33 polyesters, such as poly(hydroxyl alkanoates) [PHA] and poly(lactic acid) [PLA]
34 [1,4,5]. According to the literature, the mechanism of grafting MA onto PLA involves
35 the abstraction of an -hydrogen (in relation to the carbonyl) by a radical, with the

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36 consequent formation of a macro-radical, and the attack of the macro-radical on the
37 MA unsaturation (Figure 1). Similar mechanisms are applied for the branching and

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38 crosslinking of polyesters [1,4,6].
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41 Figure 1. Scheme of the reaction between PLA and MA initiated by DCP, according to the literature.
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43 These reactions can be carried out in solution or in the melt state, but free-radical
44 melt grafting is considered to be the most practical, cost-effective and environment-
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45 friendly method [4,7,8]. However, this type of grafting is associated with many
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46 possible concurrent and undesirable side reactions [4,9], a characteristic that can
47 inhibit the obtainment of the desired product in high yields. In fact, the literature
48 reports that, in the presence of a radical initiator, PLA may undergo -scission, a
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49 process that leads to products other than that shown in Figure 1 [4,10,11,12]. Carlson
50 et al. proposed obtaining a product through a reaction between two macro-radicals that
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51 yields a cross-linked structure, with the use of a radical initiator [10].

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52 Considering that several authors have reported different possible by-products

53 being formed in the grafting reaction, the aim of this study was to demonstrate, by
54 means of a detailed investigation employing 1H-NMR and 13
C-NMR spectroscopy as
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55 well as DEPT-135 and C-1H HSQC analysis, that a new chemical structure can be
56 formed in the reaction of PLA with MA, in the melt state, initiated by DCP. It was
57 found that, under the conditions reported herein, instead of the product shown in
58 Figure 1, the results indicated a PLA derivative product, which is probably formed by
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59 the reaction of two macro-radicals after β-scission of the PLA chain. The C-NMR

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60 spectrum of the derivative formed was also calculated using the gauge-independent
61 atomic orbital (GIAO-DFT) for comparison purposes.

62 Experimental

63 Materials

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64 Poly(lactic acid) Ingeo 3251D (Mw=7.9 x 104, PDI=1.70) with less than 2% of
65 D isomer was purchased from NatureWorks LLC, Cargill (USA). Maleic anhydride

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66 (analytical grade) was supplied by Vetec (Duque de Caxias – RJ, Brazil). Chloroform
67 (99.8%) and ethanol (99.8%) were supplied by LAFAN (Várzea Paulista – SP, Brazil)

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68 and deuterated chloroform (99.96 atom % D) and ethanol (99.5 atom % D) by Sigma-
69 Aldrich (Brazil). All of the chemical reagents were used without further purification.

70 Free-radical melt reaction

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71 The PLA (50 g), MA (1.5 g) and DCP (0.25 g) were mixed in a torque rheometer
72 (Thermo Scientific®, model HAAKE PolyLab QC), at 170 ºC and 30 rpm, after a 5
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73 min period to allow torque stabilization. Also, mixtures of PLA (50 g) with MA (1.5
74 g) and of PLA (50 g) with DCP (0.25 g) were submitted to the same process
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75 conditions to obtain binary mixtures. After the processing in the torque rheometer, the
76 material was ground using a knife mill (Marconi, model MA048) and washed with
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77 ethanol. Finally, the washed material was dissolved in chloroform and precipitated
78 with ethanol, a non-solvent of the polymer, to remove possible unreacted components.
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79 After the solvent evaporation, the samples were kept in a desiccator with silica and the
80 NMR analysis was carried out within five days.
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81 Nuclear Magnetic Resonance (13C, 1H, DEPT-135 and 13C-1H – HSQC)

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82 The nuclear magnetic resonance spectra were recorded on a 400 MHz NMR
83 spectrometer (Varian, model NMR AS400). The samples were dissolved in CDCl3 or
84 in ethanol-d6 depending on the sample solubility.
85 The spectra for the undiluted PLA, PLA/MA and PLA/DCP were obtained
86 with 7000 scans by 13C-NMR, in a spectral width of 239 ppm and the number of raw
87 data points was 32000. Therefore, to obtain a better resolution for the sample
88 PLA/MA/DCP and for the compound extracted in the washing step, data were
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89 collected with 140000 scans by C-NMR at the same spectral width and with the
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90 same number of raw data points cited above. This better resolution was sought after
91 observing new signals related to the functional groups of the new chemical bond,
92 which is discussed below. All 1H NMR spectra were obtained with 16 scans in a
93 spectral width of 20.0 ppm and the number of raw data points was 64000.

94 Computational Methods

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95 Geometry optimizations were carried out for the PLA dimmer, used as a model for
96 PLA, and the respective possible products using ORCA 3.0.3 [13] with a level of

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97 theory recommended elsewhere for NMR calculations [14] (B3LYP-D3(BJ)/6-
98 31+G(d,p) [15-17]). Geometry minima were confirmed by the absence of imaginary

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99 eigenvalues in the Hessian matrix. NMR chemical shifts were calculated using the
100 gauge-independent atomic orbitals (GIAO) approach [18-20], as implemented in

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101 NWChem 6.6 software [21], and employing (PBE0-D3/6-311+G(2d,p)/SMD(CHCl3)
102 [22-25]) as the level of theory, which has been previously validated [14]. Chemical
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103 shifts (δrel, relative to TMS) were calculated from the absolute GIAO values (δabs)
104 through the following linear regression, developed by Lodewyk et al. [26]:
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106 δrel (ppm) = (δabs - a)/b
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108 Here, b = -1.0533 and a = 187.3123 for the 13C NMR [26]. This is a well-established
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109 scaling method which has been shown to provide good results for a wide variety of
110 organic compounds (RMSD = 2.4913 ppm) [26]. Notwithstanding, a custom fitting
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111 between the experimental 13C peaks of PLA and the calculation of a dimer model (r² =
112 0.999763, a = 189.4661, b = -1.1126) was carried out for comparison, with the
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113 structure shown in Figure SB (supporting information).

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114 It can be observed that the sum of the absolute residues of the dimer model is
115 over 2.7 ppm, with particularly large errors for low chemical shift signals. While the
116 fitting of Lodewyk et al. gives a larger sum of absolute residues (over 8.5 ppm) for
117 high chemical shift signals, the largest errors were found for the carbonyl peaks
118 (Figure SA, supporting information). This is expected due to the increased electron
119 correlation error in more electron-rich regions of a molecule. Thus, we decided to use
120 the model of Lodewyk et al. since it provided a better result than our custom fitting for
121 peaks below 80 ppm (Figure SA, supporting information), where the most important
122 signals discussed herein are located.
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123 Results and Discussion

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124 The C-NMR and 1H-NMR spectra of undiluted PLA in CDCl3 can be observed in
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125 Figure 2. In the C-NMR spectrum, the peaks at 16.58, 68.97 and 169.52 ppm are
126 associated with the carbons of CH3, CH and C=O groups, respectively, and are in
127 agreement with reports in the literature [27-29]. Also, in the 1H-NMR spectrum, the

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128 peaks at 1.59 ppm and 5.17 ppm are associated with the hydrogens of CH3 and CH,
129 respectively. Undiluted PLA and the binary mixtures PLA/MA and PLA/DCP were

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130 processed in the torque rheometer to investigate whether the processing could affect
131 the chemical structure of the polymer. After the processing, all of the samples were

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132 submitted to the same purification process described in the methodology section to
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133 remove the remaining unreacted compounds. The C-NMR and 1H-NMR spectra of
134 these processed materials (processed undiluted PLA and binary mixtures) show the
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same chemical shifts as the undiluted unprocessed PLA. Thus, the process does not
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136 affect the chemical structure of the polymer chain. Also, no new peaks were observed
137 for the binary mixtures, suggesting that no chemical reactions occur in the binary
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138 mixtures, only a physical mixture and the components were separated in the
139 purification step. These observations suggest that any change observed in the spectrum
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140 for the product obtained from the processed ternary mixture PLA/MA/DCP is related
141 to a reaction through a specific mechanism involving these three components.
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143
144 Figure 2: 13C-NMR (top) and 1H-NMR (bottom) spectra obtained at 400 MHz for undiluted PLA in CDCl3.
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146 According to reports in the literature, the succinic anhydride moiety presents
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147 H-NMR peaks in the range of 2.0 to 4.0 ppm [30,31]. However, as can be seen in
148 Figure 3, the reaction product shows signals at 1.48 and 4.37 ppm. The signal at 1.48
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149 ppm resembles a triplet, but the relative intensity between the peaks is not consistent
150 with a triplet. Furthermore, two coupling constants are observed (6.8 and 7.1 Hz). The
151 signal at 4.37 ppm appears as a multiplet with the same two coupling constants,
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152 suggesting that these hydrogens are coupled and probably in the vicinal position. This
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153 observation suggests that both signals are, in fact, a convoluted pair of signals (two
154 duplets at 1.48 and two pentets at 4.37). The area of the signals shows a 3:1 proportion
155 of hydrogens at 1.48 ppm to hydrogens at 4.37 ppm, which can be attributed to CH3
156 and CH groups, respectively.
157 In the 13C-NMR spectrum for the reaction product two pairs of peaks can be
158 observed (one at 20.05 and 20.31 ppm and the other at 66.49 and 66.77 ppm) as well
159 as three peaks in the range of 170 to 180 ppm. The literature reports different signals
160 for the succinic anhydride moiety grafted on PLA. For instance, Wu et al. [27]

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161 assigned a peak at 36.2 ppm to the methine carbon (CH), a peak at 42.1 ppm to the
162 methylene carbon (CH2) and a peak at 171.6 ppm to the carbonyl carbon (C=O) of the
163 succinic anhydride moiety. According to Heinen et al. [32] the chemical shifts for the
164 methine and methylene carbons range from 41.2 to 47.9 ppm and from 29.8 to 30.7,
165 respectively. Similar results are described by Chen et al. for PHB grafted with MA
166 (methylene at 29.8 ppm and methine at 43.7 ppm) [33]. Nevertheless, Muenprasat et

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167 al. [34] and Placket et al. [29] report signals similar to those obtained in the study
168 reported herein.

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170
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171 Figure 3: 13C-NMR (top) and 1H-NMR (bottom) spectra for the product of the reaction of PLA, MA and
172 DCP after purification.
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174 In order to identify the nature of these carbon peaks, DEPT-135 (Figure 4) and
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175 C–1H HSQC (Figure 5) experiments were performed. The DEPT-135 spectrum
176 shows no presence of methylene (CH2) in the product, since all of the signals are
177 positive. This is a very significant result as it indicates that the reaction product shown
178 in Figure 1 was not formed. It also suggests that the two pairs of signals observed in
179 the 13C-NMR spectrum are associated with CH3 and CH carbons.
180

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181
182 Figure 4: DEPT-135 spectra for the product of the reaction between PLA, MA and DCP.

183

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184 Based on the HSQC data it was possible to confirm that the hydrogens at 1.48
185 ppm are bonded to the carbons at 20.05 and 20.31 ppm and the hydrogens at 5.18 are

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186 bonded to the carbons at 66.49 and 66.77 ppm. Thus, the data extracted from 1H-
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187 NMR, 13C-NMR, DEPT-135 and HSQC spectra suggest the formation of a –CHCH3–
188 CHCH3 – bond, through the reaction of two macro-radicals, as shown in Figure 6. The
189 duplicity of the signals can be explained based on the formation of two
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190 diastereoisomers R-S and R-R.

191 In order to evaluate the correlation of the experimental 13C chemical shifts with
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192 the structures proposed herein and in some references, electronic structure calculations
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193 at the DFT level were performed according the methodology previously described.
194 The obtainment of data through GIAO calculations offers an effective and robust
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195 approach to validating the peak assignment of the proposed structures.

196 A plot of the experimental data against calculated chemical shifts was obtained
197 in order to evaluate the predictive power of the method. A very good correlation was
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198 found for the calculated chemical shifts of an L-lactic acid dimer (r² = 0.99976, Figure
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199 SC in supporting information), indicating that the dimer model is sufficiently

200 representative for this polymer system.
201 When the experimental ¹³C NMR chemical shifts obtained in this study for the
202 reaction product were plotted against those calculated for Structure A – grafted PLA
203 (assignment as described by Muenprasat et al.), the correlation found was not as good
204 (r² = 0.829). However, when the experimental data reported by Wu et al. [27] were
205 plotted against our GIAO calculations, a good correlation was observed (r² = 0.953).
206 These results suggest that the product obtained in this study was not the grafted

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207 polymer. Furthermore, our computational results contribute to validating the peak
208 assignment performed by Wu et al. and the calculations are also in line with the results
209 obtained by Heinen et al. [32] for methine and methylene carbons at succinic rings
210 bonded to aliphatic chains.
211 Since the product obtained was not the grafted PLA and, based on the NMR
212 results discussed herein, Structure C (Figure 6) was proposed. When the experimental

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213 data were plotted against the chemical shifts calculated for the proposed structure, a
214 reasonable correlation was obtained (r² = 0.994), consistent with the proposal based on

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215 the experimental evidence.

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217 Figure 5: Heteronuclear single quantum coherence (HSQC) 13C - 1H spectra for the product of the reaction
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218 between PLA, MA, and DCP.

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220 However, the mechanism shown in Figure 6 shows the formation of a PLA derivative
221 with a C=C bond (Structure B). The β-scission mechanism is reported in the literature
222 and the formation of Structure B involves a rearrangement step followed by β-scission.
223 The rearrangement was proposed based on the NMR data for the products obtained
224 under the conditions applied in this study, which can be explained by the formation of
225 a more stable radical intermediate.

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226
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228 Figure 6: Suggested mechanism for the reaction of PLA with MA in the presence of DCP under the
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229 conditions applied in this study.

230
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231 Thus, in order to investigate whether Structure B could be formed and removed
232 from the product during the washing process, the ethanol used in the washing was
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233 evaporated and the residue investigated. The ethanol evaporation resulted in a viscous
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234 liquid that was analyzed by C-NMR (Figure 7a) and 1H-NMR (Figure 7b). A
235 possible chemical pathway for the cleaving of the ester bonds at the polymer chain
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236 extremities in Structure B during the washing step is shown in Figure 6.

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237 The number of C=O, CH and CH3 peaks observed in the C NMR spectra
238 suggests that the compound extracted in the washing step contains lactic acid
239 oligomers. Also, as seen in the enlarged area in Figure 7a, a peak at 131 ppm
240 characteristic of C=C bond appears, which can be attributed to the hydrogenated
241 carbon of this double bond observed for the structure formed after β-scission. The
242 other carbon of the C=C bond is not observed on the 13C spectrum, probably due to the
243 relaxation time associated with this type of non-hydrogenated carbon.

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244
245
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246 Figure 7: (a) 13C-NMR and (b) 1H-NMR spectra for extract obtained after washing with ethanol.
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248 Peaks of 1H-NMR at 1.27(t), 4.32(q) and 6.31(s) ppm (Figure 7b) and their
249 relative areas of 3:2:1, respectively, suggest the ethoxylation of the anhydride ring in
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250 the washing step. Also, on the 1H-NMR spectrum only one peak due to C=C-H was
251 identified, which is in agreement with Structure D (Figure 6). Furthermore, the ratio of
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252 the sum of the signal areas assigned as CH3 (52.1 a.u.) to the sum of the signal areas
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253 assigned as CH (16.6 a.u.) of the oligomeric PLA chain was approximately 3, which is
254 stoichiometrically in agreement with the oligomeric fragment bound to the ethoxylated
255 anhydride end-chain group proposed for Structure D in Figure 6.

256 Conclusions

257 Grafting reactions are an interesting strategy widely used for many purposes in
258 the field of polymer modification. Given the complexity of radical reactions, this study

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259 highlights the importance of considering that the diversity of side reactions in a radical
260 mechanism can lead to several, often unwanted, products.
261 Based on the results obtained, it can be concluded that the melt processing of
262 PLA/MA/DCP can lead to a reaction between the PLA macro-radicals formed by β-
263 scission followed by decarboxylation. The product was proposed after the
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264 identification of a CH3CH–CHCH3 bond by C NMR, 1H NMR, DEPT-135 and

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265 HSQC analysis. Also, the 13C-NMR spectrum of the proposed structure was calculated
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266 by GIAO-DFT, and a good correlation with the C-NMR experimental data was
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267 observed. In contrast, a poor correlation was observed between the C-NMR
268 experimental data and calculations for the grafted polymer structure.

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269

270 Acknowledgments The authors are grateful for the financial support provided by CAPES and CNPq.

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272 References

273 [1] C.-S. Wu, H.-T. Liao, Y.-X. Cai, Characterisation, biodegradability and
274 application of palm fibre-reinforced polyhydroxyalkanoate composites, Polym.
275 Degrad. Stab. 140 (2017) 55–63. doi:10.1016/j.polymdegradstab.2017.04.016.
276

PT
277 [2] J.-F. Zhang, X. Sun, Mechanical Properties of Poly(lactic acid)/Starch Composites
278 Compatibilized by Maleic Anhydride, Biomacromolecules. 5 (2004) 1446–1451.

RI
279 doi:10.1021/bm0400022.
280

SC
281 [3] V.H. Sangeetha, H. Deka, T.O. Varghese, S.K. Nayak, State of the art and future
282 prospectives of poly(lactic acid) based blends and composites, Polymer Composites.
283 39 (2016) 81–101. doi:10.1002/pc.23906.
284
U
AN
285 [4] S. Detyothin, S.E.M. Selke, R. Narayan, M. Rubino, R. Auras, Reactive
286 functionalization of poly(lactic acid), PLA: Effects of the reactive modifier, initiator
M

287 and processing conditions on the final grafted maleic anhydride content and molecular
288 weight of PLA, Polym. Degrad. Stab. 98 (2013) 2697–2708.
D

289 doi:10.1016/j.polymdegradstab.2013.10.001.
290
TE

291 [5] P. Ma, X. Cai, X. Lou, W. Dong, M. Chen, P.J. Lemstra, Styrene-assisted melt
292 free-radical grafting of maleic anhydride onto poly(β-hydroxybutyrate), Polymer
EP

293 Degradation and Stability. 100 (2014) 93–100.

294 doi:10.1016/j.polymdegradstab.2013.12.005.
295
C

296 [6] A.R. Kolahchi, M. Kontopoulou, Chain extended poly(3-hydroxybutyrate) with

AC

297 improved rheological properties and thermal stability, through reactive modification in
298 the melt state, Polymer Degradation and Stability. 121 (2015) 222–229.
299 doi:10.1016/j.polymdegradstab.2015.09.008.
300
301 [7] J.-M. Raquez, R. Narayan, P. Dubois, Recent Advances in Reactive Extrusion
302 Processing of Biodegradable Polymer-Based Compositions, Macromolecular
303 Materials and Engineering. 293 (2008) 447–470. doi:10.1002/mame.200700395.
304

13
 ACCEPTED MANUSCRIPT
305 [8] Baker, W.; Scott, C.; Hu, G.-H. Reactive Polymer Blending; Hanser: Munich,
306 Germany, 2001.
307
308 [9] G. Moad, The synthesis of polyolefin graft copolymers by reactive extrusion,
309 Progress in Polymer Science. 24 (1999) 81–142. doi:10.1016/s0079-6700(98)00017-3.
310

PT
311 [10] D. Carlson, P. Dubois, L. Nie, R. Narayan, Free radical branching of polylactide
312 by reactive extrusion, Polymer Engineering & Science. 38 (1998) 311–321.

RI
313 doi:10.1002/pen.10192
314

SC
315 [11] D. Carlson, L. Nie, R. Narayan, P. Dubois, Maleation of polylactide (PLA) by
316 reactive extrusion. J Appl Polym Sci. 72 (1999) 477-485. doi:10.1002/(sici)1097-
317 4628(19990425)72:4<477::aid-app3>3.0.co;2-q

U
318
AN
319
320 [12] M. Avella, G. Bogoeva-Gaceva, A. Bužarovska, M.E. Errico, G. Gentile, A.
M

321 Grozdanov, Poly(lactic acid)-based biocomposites reinforced with kenaf fibers,

322 Journal of Applied Polymer Science. 108 (2008) 3542–3551. doi:10.1002/app.28004.
D

323
324 [13] F. Neese, The ORCA program system, Wiley Interdisciplinary Reviews:
TE

325 Computational Molecular Science. 2 (2011) 73–78. doi:10.1002/wcms.81.

326
EP

327 [14] M.W. Lodewyk, M.R. Siebert, D.J. Tantillo, Computational Prediction of 1H and
328 13C Chemical Shifts: A Useful Tool for Natural Product, Mechanistic, and Synthetic
329 Organic Chemistry, Chemical Reviews. 112 (2011) 1839–1862.
C

330 doi:10.1021/cr200106v.
AC

331
332 [15] W.J. Hehre, R. Ditchfield, J.A. Pople, Self—Consistent Molecular Orbital
333 Methods. XII. Further Extensions of Gaussian—Type Basis Sets for Use in Molecular
334 Orbital Studies of Organic Molecules, The Journal of Chemical Physics. 56 (1972)
335 2257–2261. doi:10.1063/1.1677527.
336

14
 ACCEPTED MANUSCRIPT
337 [16] R. Krishnan, J.S. Binkley, R. Seeger, J.A. Pople, Self‐consistent molecular orbital
338 methods. XX. A basis set for correlated wave functions, The Journal of Chemical
339 Physics. 72 (1980) 650–654. doi:10.1063/1.438955.
340
341 [17] T. Clark, J. Chandrasekhar, G.W. Spitznagel, P.V.R. Schleyer, Efficient diffuse
342 function-augmented basis sets for anion calculations. III. The 3-21+G basis set for

PT
343 first-row elements, Li-F, Journal of Computational Chemistry. 4 (1983) 294–301.
344 doi:10.1002/jcc.540040303.

RI
345
346 [18] F. London, Théorie quantique des courants interatomiques dans les combinaisons

SC
347 aromatiques, Journal de Physique et Le Radium. 8 (1937) 397–409.
348 doi:10.1051/jphysrad:01937008010039700.
349
350
U
[19] R. McWeeny, Perturbation Theory for the Fock-Dirac Density Matrix, Physical
AN
351 Review. 126 (1962) 1028–1034. doi:10.1103/physrev.126.1028.
352
M

353 [20] R. Ditchfield, Self-consistent perturbation theory of diamagnetism, Molecular

354 Physics. 27 (1974) 789–807. doi:10.1080/00268977400100711.
D

355
356 [21] M. Valiev, E.J. Bylaska, N. Govind, K. Kowalski, T.P. Straatsma, H.J.J. Van
TE

357 Dam, D. Wang, J. Nieplocha, E. Apra, T.L. Windus, W.A. de Jong, NWChem: A
358 comprehensive and scalable open-source solution for large scale molecular
EP

359 simulations, Computer Physics Communications. 181 (2010) 1477–1489.

360 doi:10.1016/j.cpc.2010.04.018.
361
C

362 [22] C. Adamo, V. Barone, Toward reliable density functional methods without
AC

363 adjustable parameters: The PBE0 model, The Journal of Chemical Physics. 110 (1999)
364 6158–6170. doi:10.1063/1.478522.
365
366 [23] M. Ernzerhof, G.E. Scuseria, Assessment of the Perdew–Burke–Ernzerhof
367 exchange-correlation functional, The Journal of Chemical Physics. 110 (1999) 5029–
368 5036. doi:10.1063/1.478401.
369

15
 ACCEPTED MANUSCRIPT
370 [24] S. Grimme, S. Ehrlich, L. Goerigk, Effect of the damping function in dispersion
371 corrected density functional theory, Journal of Computational Chemistry. 32 (2011)
372 1456–1465. doi:10.1002/jcc.21759.
373
374 [25] S. Grimme, J. Antony, S. Ehrlich, H. Krieg, A consistent and accurate ab initio
375 parametrization of density functional dispersion correction (DFT-D) for the 94

PT
376 elements H-Pu, The Journal of Chemical Physics. 132 (2010) 154104.
377 doi:10.1063/1.3382344.

RI
378
379 [26] M.W. Lodewyk, M.R. Siebert, D.J. Tantillo, Computational Prediction of 1H and

SC
380 13C Chemical Shifts: A Useful Tool for Natural Product, Mechanistic, and Synthetic
381 Organic Chemistry, Chemical Reviews. 112 (2011) 1839–1862.
382 doi:10.1021/cr200106v.

U
383
AN
384 [27] C.-S. Wu, Renewable resource-based green composites of surface-treated spent
385 coffee grounds and polylactide: Characterisation and biodegradability, Polymer
M

386 Degradation and Stability. 121 (2015) 51–59.

387 doi:10.1016/j.polymdegradstab.2015.08.011.
D

388
389 [28] C.-S. Wu, Renewable resource-based composites of recycled natural fibers and
TE

390 maleated polylactide bioplastic: Characterization and biodegradability, Polymer

391 Degradation and Stability. 94 (2009) 1076–1084.
EP

392 doi:10.1016/j.polymdegradstab.2009.04.002.
393
394 [29] D. Plackett, Maleated Polylactide as an Interfacial Compatibilizer in
C

395 Biocomposites, Journal of Polymers and the Environment. 12 (2004) 131–138.

AC

396 doi:10.1023/b:jooe.0000038544.75554.0e.
397
398 [30] C. Nyambo, A.K. Mohanty, M. Misra, Effect of Maleated Compatibilizer on
399 Performance of PLA/Wheat Straw-Based Green Composites, Macromolecular
400 Materials and Engineering. 296 (2011) 710–718. doi:10.1002/mame.201000403.
401

16
 ACCEPTED MANUSCRIPT
402 [31] L. Gardella, M. Calabrese, O. Monticelli, PLA maleation: an easy and effective
403 method to modify the properties of PLA/PCL immiscible blends, Colloid and Polymer
404 Science. 292 (2014) 2391–2398. doi:10.1007/s00396-014-3328-3.
405
406 [32] W. Heinen, S. W. Erkens, M. Van Duin, J. Lugtenburg. Model Compounds and
13
407 C NMR Increments for the Characterization of Maleic Anhydride-Grafted

PT
408 Polyolefins. Journal of Polymer Science: Part A: Polymer Chemistry. 37 (1999)
409 4368–4385.

RI
410
411 [33] C. Chen, S. Peng, B. Fei, Y. Zhuang, L. Dong, Z. Feng, S. Chen, H. Xia,

SC
412 Synthesis and characterization of maleated poly(3-hydroxybutyrate), Journal of
413 Applied Polymer Science. 88 (2003) 659–668. doi:10.1002/app.11771.
414

U
415 [34] D. Muenprasat, S. Suttireungwong, C. Tongpin. Functionalization of Poly(lactic
AN
416 acid) with Maleic Anhydride for Biomedical Application. J. Met. Mater. Min. 20
417 (2010) 189–192.
M
D
TE
C EP
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• Description of a new product for the melt-reaction of polylactic acid and maleic
anhydride.
• 1
H-NMR, 13C-NMR, DEPT-135 and 13C-1H HSQC characterization of the reaction
product.
• Good correlation between experimental and theoretical 13C-NMR chemical
shifts, calculated using GIAO-DFT method.

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