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Methacrylate copolymers and their composites with nano-CdS: synthesis, characterization, thermal behavior, and antimicrobial properties

Methacrylate copolymers and their composites with nano-CdS: synthesis, characterization, thermal... Homo- and copolymers of 2-(N-phthalimido)ethyl methacrylate (NPEMA) and p-chlorophenyl methacrylate (PCPMA) were prepared in N,N-dimethyl formamide (DMF) solution at 70 °C using 2,2-azo-bisisobutyronitrile (AIBN) as initiator. The nano-CdS-doped polymer composite of NPEMA and PCPMA was prepared via in situ technique. The homo- and copolymers of NPEMA and PCPMA were characterized using FT-IR spectroscopy and gel permeation chromatography (GPC). The poly- mer nano composites were characterized using FT-IR spectroscopy, X-ray diffraction, and transmission electron microscopy. The reactivity ratios (r and r ) were obtained from the various linear graphical methods. The values of r (NPEMA) = 0.55 1 2 1 and r (PCPMA) = 1.30 were found from the same graphical methods. The copolymer microstructures were found from the mean sequence length, run number, and dyad fraction. Thermal behavior of polymers and polymer nano composites under nitrogen atmosphere was studied. The activation energies of neat polymers were varied in the range of 56–85 kJ/mol, while 28–56 kJ/mol energies were found for nano-CdS-doped polymer composites. The thermodynamic parameters of thermal degradation were also obtained. Kinetic and thermodynamic parameters were confirming the stability of the neat polymers than polymer nano composites. The polymers were assessed on different microorganisms for obtaining the antimicrobial properties. Overall, the polymers permit 10–52, 20–58, and 18–56% growth of bacteria, fungi, and yeast, respectively. Keywords Copolymerization · Polymer nano composites · Reactivity ratio · Thermal properties · Antimicrobial properties Introduction [3], atom transfer free radical polymerization (ATRP) [4], reversible addition–fragmentation chain transfer free radi- Copolymerization technique is an adaptable technique to cal polymerization (RAFT) [5], redox polymerization [6], prepare copolymers from two or more different types of photo polymerization [7] living polymerization [8], etc. It monomers. These copolymers have different properties is required to choose the polymerization process to obtain than their individual homopolymers. The acrylates or meth- copolymers having desirable chemical, optical, mechanical, acrylates are normally polymerized through various tech- and electrical properties. Free radical solution polymeriza- niques. These techniques are free radical solution polymeri- tion is a simple, versatile, and effective technique to pre - zation [1], bulk polymerization [2], emulsion polymerization pare the acrylate or methacrylate homo- and copolymers. The functionalized copolymers of acrylates were applied in various fields such as biomedical [ 9], textile [10], coating [11], adhesions [12], food packaging [13], and many more * Mehdihasan I. Shekh mehdi.shekh3@yahoo.com [14, 15]. Knowing the copolymer microstructure is useful to predict the properties of the copolymers. The microstructure Rajnikant M. Patel rmpatel_28@yahoo.co.in of copolymers is easily predicted from the values of reactiv- ity ratios of two monomers and the ratios of these values Department of Advanced Organic Chemistry, P. D. Patel are possible to find from the various linear and non-linear Institute of Applied Sciences, Charotar University of Science methods [16–18]. and Technology, Changa 388421, Gujarat, India 2 Polymers are the most preferable host materials to pre- Department of Chemistry, Sardar Patel University, pare the inorganic nano particles (Nps)-doped composites. Vallabh Vidhyanagar 388120, Gujarat, India Vol.:(0123456789) 1 3 154 International Journal of Industrial Chemistry (2018) 9:153–166 These classes of materials have very good applicable prop- Experimental erties (i.e., electrical, mechanical, and optical). Materi- als having both inorganic and organic characteristics Materials were well researched [19–23]. Recently, many techniques [24–28] were developed to prepare the new potential mate- Ethanol amine, phthalic anhydride, triethyl amine (TEA), rials that were used in various fields [29– 33] such as bio- N,N-dimethyl formamide (DMF), methanol, cadmium logical labeling, light-emitting diodes, transistors, solar nitrate, sodium sulfide, and 2,2-azo-bis-isobutyronitrile cells, organic-based electronics, sensors, optical switch- (AIBN) were purchased from the Loba chem Pvt. Ltd. ing, etc. (India). The nutrient broth, potato dextrose broth, and tryp- The numbers of research reports were published on the tone glucose yeast extract were purchased from the Hime- polymer composites with nano-metal oxides [34, 35], metal dia Laboratories Pvt. Ltd. The pre-grown slants of vari- sulfides [36, 37], and many more [38–41]. Among them, ous microorganisms (i.e., bacteria, yeast, and fungi) were semiconducting polymer nano composites of metal sulfides obtained from the Microbial-Type Culture Collection and are very useful for their optoelectronic properties. A semi- Gene Bank (MTCC), CSIR-Institute of Microbial Technol- conducting polymer composite of CdS Nps is this class of ogy, Chandigarh, India. All chemicals are analytical grade material. It has broad range of applications in the various and are used as received. fields. The various polymers are used as host materials to prepare the CdS/polymer nano composites. The different Synthesis CdS-Nps-doped polymer composites are prepared via dif- ferent techniques. CdS/polystyrene nano-composite was pre- Synthesis of starting materials and monomers pared by a chemical route using an ex situ technique [42]. Oxidization polymerization technique was used to prepare The synthesis of methacryloyl chloride (MAC), N-(2-hy- CdS/polyaniline nano-composite [43]. CO -doped CdS/ droxy ethyl) phthalimide (NHEP), and 2-(N-phthalimido) polyvinyl pyrolidone composite was synthesized by chemi- ethyl methacrylate (NPEMA) was prepared, as reported in cal precipitation method [44]. Spin-coating technique was Ref. [50]. The p-chlorophenyl methacrylate (PCPMA) was used to prepare thin films of CdS/poly[2-methoxy-5-(2′ - prepared by earlier reported synthesis [51]. ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) nano- composite [45]. Several other CdS/polymer nano compos- Copolymerization of NPEMA with PCPMA ites such as CdS/polyamidoamine dendrimer [46], CdS/ poly[4-(n-acryloyloxyalkoxy)benzoic acid] [47], and many The free-radical polymerization technique [50] was more [48, 49] were also investigated. Although the proper- ties and synthesis of CdS/polymer nano composites are well employed to synthesize copolymers of NPEMA with PCPMA having different feed compositions. N ,N-Dimethyl investigated, yet the effect of CdS Nps on the degradation of polymer in inert atmosphere (i.e., N gas) is not investigated. formamide (DMF) was used as a solvent and AIBN as a free-radical initiator. The feed composition of monomers The synthesis of macromolecules having antimicrobial properties is useful in various areas like hospitals, dental is given in Table 1. Appropriate quantities of monomers, DMF, and AIBN (0.5% w/w based on total monomers 1 equipment, water purification systems, food storage, and food packaging units. Polymeric materials having antimi- and 2) were added to a flask fitted with reflux condenser. The reaction mixture was heated to 70 °C for 5 h with stir- crobial properties are prepared mainly by: (1) polymeriza- tion of antimicrobial monomers which have characteristic ring. It was kept for cooling at room temperature, and then, the resulting polymer solution was slowly poured in a large functional groups responsible for antimicrobial properties and (2) chemical modification of synthetic polymers by anti- volume of methanol with stirring. The polymer is followed out. It was filtered and then washed with methanol. Solid microbial agents or biocides. In this article, we have synthe- sized chlorine containing copolymers and assessed various polymers were purified by repeated precipitation from DMF solution using methanol. Synthesis of copolymer is shown microorganisms to confirm the copolymer’s antimicrobial potency. in Scheme 1. The present paper covers the synthesis, characterization, thermal behavior, and antimicrobial screening of homo- and Preparation of CdS‑Nps‑doped polymer composites copolymers of NPEMA with PCPMA. Polymer composites with nano-Cds were prepared and characterized by spectro- Polymer (0.5 g) dissolved in 50-ml DMF with stirring in a scopic tools. The main objective of this paper is to study the 250-ml conical flask, and then, the flask was kept for sonica- effect of CdS Nps on thermal degradation of polymer matrix tion. Under sonication, cadmium nitrate solution (0.1 M) in in nano composites. 1 3 International Journal of Industrial Chemistry (2018) 9:153–166 155 Table 1 Monomer feed ratio of Sample code Monomer feed composition Composition of % Yield NPEMA with PCPMA NPEMA in copoly- M (NPEMA) M (PCPMA) 1 2 mer mol g wt% mol g wt% B1 1.0 259 100 – – – 100 80 B2 0.8 207.2 80 0.2 39.3 20 81 75 B3 0.6 155.4 60 0.4 78.6 40 61 80 B4 0.5 129.5 50 0.5 98.3 50 51 78 B5 0.4 103.6 40 0.6 117.9 60 40 65 B6 0.2 51.8 20 0.8 157.2 80 20 63 B7 – – – 1 196.5 100 – 78 Scheme 1 Copolymerization (B2–B6) of NPEMA with PCPMA DMF was added slowly to polymer solution. Then, 0.1-M (Tecnai 20, Philips, Holland, with W-emitter and LaB6 as sodium sulfide (0.11 M) solution prepared in methanol was electron source and accelerating voltage up to 200  kV). added dropwise to the solution containing cadmium nitrate Thermal analysis was performed at 10 °C/min heating rate and polymer solution under sonication. After complete addi- on Mettler-Toledo thermogravimetric analyzer for TGA/ tion, the solution becomes yellowish and cloudy. The flask is DSC-1. putted for 4 h at room temperature to settle the yellow color polymer composites of nano-CdS. The obtained polymer Antimicrobial screening nano composites were separated by ultracentrifugation. The nano composites were washed several times with methanol The quantitative method [50] was used to assess antimi- to remove unreacted or excess reagents. The polymer nano- crobial properties. The homo- and copolymers of NPEMA/ composite is dried into a vacuum desiccator. PCPMA tested against different microorganisms which are commonly employed for biocompatibility test. These micro- Characterization organisms are bacteria (Escherichia coli, Bacillus subtilis, and Staphylococcus citreus), fungi (Sporotrichum pulveru- The H-NMR resonances were recorded with a Bruckner lentum, Aspergillus niger, and Trichoderma lignorum), and 400 MHZ FT NMR spectrophotometer. The IR spectra of yeast (Candida utilis, Pichia stipitis, and Saccharomyces solid samples in KBr pallets were obtained from Nicolet cerevisiae). The antimicrobial activity of poly(NPEMA) 6700 FT-IR spectrophotometer. Copolymer compositions was already discussed [50]. All microorganism cultures and reactivity ratios were determined by spectroscopic were prepared from their respected slants. All microorgan- data from UV–visible–NIR Schimadzu-3600 spectropho- ism cultures were sub-cultured periodically and maintained tometer. The phase and crystallographic structures of CdS in their respected media. The bacteria, yeast, and fungi in polymer nano composites of NPEMA/CMPMA were cultures were kept overnight at 37, 30, and 27 °C, respec- identified by X-ray diffraction (XRD, Bruckner D2 Phaser tively. In the present study, the bacterial culture’s %OD is 3600 X-ray Diffractometer having Cu-kα radiation source, set at 0.1 in 600 nm which corresponds to 10 CFU/ml. The λ = 0.154 nm). The morphology of polymer nano composites yeast culture’s %OD was set at 0.8 in 600 nm which corre- of CdS was derived using transmission electron microscope sponds to 2 × 10 CFU/ml. The fungi culture was prepared 1 3 156 International Journal of Industrial Chemistry (2018) 9:153–166 by inoculation with 0.7-mm plug (spore) containing actively growing fungi’s slants. Each test was carried out three times and the mean results are shown in a bar graph. Results and discussion H‑NMR spectroscopy The monomers NPEMA and PCPMA were characterized from the proton NMR spectroscopy. The proton NMR spectra of NPEMA monomer have been discussed in earlier report [50]. NPEMA 1H-NMR(CDCl3) δ (ppm) = 7.5–7.8 (4H, m, Ar–CH), 5.9 (1H, d, vinylic-H), 5.5 (1H, d, vinylic-H), 4.3 (2H, t, –CH –O), 3.9 (2H, t, –CH –N), and 1.9 (3H, s, CH ). 2 2 3 PCPMA 1H-NMR(CDCl3) δ (ppm) = 6.9–7.3 (3H, m, Ar–CH), 6.4 (1H, d, vinylic-H), 5.7(1H, d, vinylic-H), 2.3 (3H, s, Ar–CH ), and 2.1 (3H, s, O=C–C–CH3). FT‑IR spectroscopy −1 The combined FT-IR spectra (2000–500 cm ) of homo- Fig. 2 FT-IR spectra of poly(NPEMA-co-PCPMA) (B2–B6) and and copolymers of NPEMA with PCPMA and their poly- nano-Cds-doped polymer composite of poly(NPEMA-co-PCPMA) mer composites with nano-CdS are shown in Figs. 1 and 2, (NB2–NB6) respectively. From the spectra of neat polymers, the bands −1 observed at ~ 1750 cm are assigned for the stretching vibra- the homopolymers of NPEMA, whereas the bands at 1258, tion of –C=O in ester group. Another absorbance observed −1 −1 at ~ 1710  cm corresponds to –C=O stretching in phthal- 1200, 1122, 1084, and 1012 cm are seen in the homopoly- −1 mers of PCPMA which are attributed to the C–C(=O)–O imide [50]. The bands between 1600 and 1400 cm are assigned to the aromatic ring breathing vibration. The same and O–C–C-bending vibration in ester. The bands at 1258, −1 1199, 1160, 1122, 1080, and 1012 cm are seen in copoly- band is also observed in all copolymers IR spectra. Medium −1 bands ~ 1465 and ~ 1387 cm correspond to asymmetrical mers of NPEMA and PCPMA which are assigned for the bending vibration of C–C(=O)–O and O–C–C in ester. The and symmetrical bending vibration of methyl group, respec- −1 −1 tively. The bands at 1173, 1146, and 1048 cm are seen in sharp band at 720 cm is observed in homopolymers of NPEMA. The same absorption band is also observed in the spectra of copolymers and this band’s intensity is decreased with decrease in the NPEMA content in the copolymers. The −1 band ~ 680 cm is assigned for the C–Cl-stretching vibra- tion in homopolymers of PCPMA. The same band is also observed in spectra of copolymers. In the case of nano-CdS-doped polymer compos- ites, the intensity of the bands is decreased. The inten- sity of bands corresponding to –C=O (~ 1750 and −1 −1 ~ 1710 cm ), C–C(=O)–O (1210–1164 cm ), and O–C–C −1 (1164–1000  cm ) is effectively decreased and becomes broader. This suggests that the attraction between CdS Nps and polymer matrix occurring on these sites which depict the presence of CdS Nps in polymer matrix affects the vibra- tion of C–O. As NPEMA content decreased in copolymer feed, the interaction between polymer matrix and inorganic Fig. 1 FT-IR spectra of poly(NPEMA) (B1); poly(PCPMA) (B7) matrix also decreased. This was due to the less sites that and nano-Cds-doped polymer composite of poly(NPEMA) (NB1); were available for interactions in the poly(PCPMA) than poly(PCPMA) (NB7) 1 3 International Journal of Industrial Chemistry (2018) 9:153–166 157 −1 poly(NPEMA). The band at 1387 cm which corresponds Table 3 Reactivity ratios obtained for NPEMA and PCPMA mono- mers using different linear methods to the symmetric vibration of methyl group is not affected by the presence of CdS Nps. This reveals that no interaction is Method Reactivity ratio possible between the methyl and CdS Nps. A weak Van der r r r  × r 1/r 1/r 1 2 1 2 1 2 Waals interaction between polymer matrix and nano-CdS F–R 0.53 1.29 0.68 1.89 0.78 may be envisaged. Invrt. F–R 0.62 1.37 0.85 1.61 0.73 K–T 0.53 1.27 0.67 1.89 0.79 Average molecular weights Ext. K–T 0.5 1.28 0.64 2.00 0.78 Average 0.55 1.30 0.71 1.83 0.77 GPC instrument equipped with Waters 1525 binary pomp, manual injector and connected to Styragel HR 4 column and R.I. detector (waters 2414) is employed to record GPC curves. Tetrahydrofuran (THF) at 1.0 ml/min flow rate is peaks are observed in each composite which corresponds to the three reflection planes. These reflection planes [i.e., used as a mobile phase throughout the analysis. All the measurements are carried out at 30 °C temperature. About (111), (220), and (311)] confirm that the CdS Nps are cubic and match with JCPDE number 089-0440. The size of CdS 5–10 mg of each polymer sample is dissolved in 10-ml THF and the resulting solutions are filtered. 20-μl sample solu- nano particles is calculated using Debye–Scherrer formula [52] for (111) reflection plane of the XRD pattern. The size tion is injected for the GPC analysis. The average molecular weights, namely, Mn, Mw, Mz, Mz + 1, and polydispersity, of CdS Nps varied between 4.11 and 5.32 nm. Figure 4 shows the TEM images of the nano-CdS-doped are shown in Table 2. The GPC data for poly(NPEMA-co- PCPMA) provided the values of Mn, Mw, Mz, and Mz + 1 poly(NPEMA-PCPMA) (0.5/0.5) (NB4) composite. The images clearly show the formation of CdS nano compos- which vary from 20,109 to 22,381, 31,518 to 34,804, 47,784 to 51,883, and 65,954 to 71,200, respectively, for copoly- ites with a spherical shape and homogeneous distribution in polymer matrix. mers with different feed ratio of the monomers; polydisper - sity index lies between 1.54 and 1.60 (Table 2). The results Monomer reactivity ratio reveal that molecular weights decrease and polydispersity index changes randomly as the NPEMA content decreases The copolymer composition depends on the monomer feed in the copolymers. The values of Mn, Mw, Mz, and Mz + 1 are, respectively, 26,052, 43,620, 67,474, 91, and 839 for composition and on the relative monomer reactivity. The UV spectroscopy was employed to n fi d the concentration of poly(PCPMA) and the polydispersity index is 1.67. The polydispersity of homopolymers and copolymers was nearly NPEMA monomer in copolymer. The procedure to find con- centration of NPEMA in copolymers using UV spectroscopy 1.5, indicating termination of growing chain by radical com- bination (Table 2). was already discussed [50]. The monomer reactivity ratios X‑ray diffraction study and transmission electron microscopy Powder XRD pattern of nano-CdS-doped poly(NPEMA-co- PCPMA) (0.5/0.5 mol ratio) is shown in Fig. 3. The three Table 2 Average molecular weights of homo- (B1 and B7) and copol- ymers (B2–B6) of NPEMA with PCPMA Sample no. Average molecular weights (in Dalton) Polydis- persity M M M M n w z z+1 (Ð) B1 18310 26613 37812 50279 1.45 B2 20109 31518 47784 65954 1.57 B3 21080 33782 51641 71153 1.60 B4 21225 33511 50566 69333 1.58 B5 22127 34044 50094 67778 1.54 B6 22381 34804 51883 71200 1.56 Fig. 3 XRD pattern of nano-CdS-doped poly(NPEMA-co-PCPMA) B7 26052 43620 67474 91839 1.67 composite (mole ratio: 0.5/0.5) (NB4) 1 3 158 International Journal of Industrial Chemistry (2018) 9:153–166 Fig. 4 TEM images of nano- CdS-doped poly(NPEMA-co- PCPMA) composite (mole ratio: 0.5/0.5) (NB4) were determined using four linear methods Fineman–Rose where [M ] and [M ] are concentrations of NPEMA and 1 2 (F–R) [53], inverted Fineman–Rose (Invrt. F–R), Kelan–Tudos PCPMA, respectively. The ratio of the mean sequence length (K–T) [54], and extended Kelen–Tudos (Ext. K–T) [55]. The distribution μ /μ which theoretically corresponds NPEMA PCPMA, values of r (NPEMA), r (PCPMA), 1/r , and 1/r and product to the ratio [M ]/[M ], is tabulated in Table 4. For example, 1 2 1 2 1 2 of r and r are tabulated in Table 3. at [M ] = 20.0% and [M ] = 80.0%, each copolymer segment 1 2 1 2 It was seen that the value of r is less than r ; this sug- with M units was approximately six times longer than its 1 2 2 gests that the reactivity of NPEMA monomer is less than adjoining segment with M units. The sequence may be that of PCPMA. This also proves that the PCPMA units were expressed as NPPPPPPN, where P stands for PCPMA and N found more in the copolymer content. r < r suggest that is for NPEMA. The number of NPEMA units in copolymer 1 2 the NPEMA favors the cross propagation, whereas PCPMA increases with increasing concentration of NPEMA in the favors the homopropagation. As 1/r > 1/r , it was concluded feed. The results of mean sequence length and values of 1/r 1 2 1 that there were more growing radicals with NPEMA ends and 1/r compare each other very well; 1/r is greater than 2 1 than with PCPMA ends due to r < r , which identified which 1/r , and as expected in copolymers, the homopropagation 1 2 2 monomer amongst the two was more reactive. of PCPMA decreased with decreasing PCPMA in monomer feed, while cross propagation of monomeric units increased Copolymer microstructure with increasing concentration of NPEMA in monomer feed. Mean sequence length Run number and dyad fraction The mean sequence lengths μ and μ are calculated From the reactivity ratios of monomers, the run number, R NPEMA PCPMA N, using the following equation [56]: was determined following Harwood and Reichy [57] as the average number of monomer alternations per 100 monomeric [M ] = 1 + r units in a copolymer chain: (1) NPEMA 1 [M ] R = . [M ] (3) 2 + r × X + = 1 + r , 1 (2) X PCPMA 2 [M ] Table 4 Mean sequence length Sample no. Monomer feed μ μ μ :μ μ /μ Distribution 1 2 1 2 1 2 of copolymers of NPEMA with PCPMA M M 1 2 B2 0.8 0.2 3.2 1.3 3:1 2.41 NNNPNNN B3 0.6 0.4 1.8 1.8 2:2 0.98 NNPPNN B4 0.5 0.5 1.6 2.3 2:2 0.67 NNPPNN B5 0.4 0.6 1.4 2.9 1:3 0.46 NPPPN B6 0.2 0.8 1.1 6.2 1:6 0.18 NPPPPPPN μ = NPEMA (N); μ = PCPMA (P) 1 2 1 3 International Journal of Industrial Chemistry (2018) 9:153–166 159 Table 5 TGA data of homo- a b c Sample no. % Weight loss at various tem- Decomposition tem- T T IPDT max 50 (B1 and B7) and copolymers perature (°C) perature range (°C) (B2–B6) of NPEMA with PCPMA 200 300 400 500 600 Step-I Step-II Step-I Step-II B1 2 22 65 100 100 172–318 318–430 281 405 377 351 B2 4 35 85 98 99 170–314 314–446 257 394 357 340 B3 3 33 79 97 97 173–314 314–449 260 394 364 333 B4 4 38 83 98 98 165–316 316–443 261 395 351 334 B5 3 35 74 98 98 170–330 330–457 269 400 365 341 B6 3 30 74 96 96 203–333 333–451 275 407 372 347 B7 2 16 37 95 95 227–397 397–530 349 472 448 437 Temperature for maximum rate of decomposition Temperature for 50% weight loss Integral procedural decomposition temperature by Doyle’s method The R value provides a view of sequence distributions in 1∕2 copolymer chains, and consequently, it is possible to assess S = 4m m ∕ 1 + 2m − 1 + 4r r m m . 1−2 1 2 1 1 2 1 2 the relationship between physical properties of copolymers (6) and their compositions. The value of R can be calculated The variation of the dyad fractions with the NPEMA from reactivity ratios. The variation of R with X (= [M ]/ N 1 mole fraction in the copolymers is depicted in Fig. 5b. Fig- [M ]) is shown in Fig. 5a. ure 5b shows S is less than S , suggesting that NPEMA The maximum value of R is 54.2 at X = 1.5 for the 1–1 2–2 has negligible attraction with NPEMA monomer, and so, poly(NPEMA-co-PCPMA) system. To gain further infor- NPEMA homopolymerization is not favorable. The value mation about the copolymer structure, the formation prob- of S implied that homopolymerization of PCPMA is abilities of dyad fractions as a function of the molar fraction 1–2 quite dominant. The consequences of these calculations of monomeric units in the copolymer can be calculated from are the same as those obtained from reactivity ratios. the monomer feed compositions and reactivity ratios [58]: 1∕2 S = m − 2m m ∕ 1 + 2m − 1 + 4r r m m 1−1 1 1 2 1 1 2 1 2 (4) 1∕2 S = m − 2m m ∕ 1 + 2m − 1 + 4r r m m 2−2 2 1 2 1 1 2 1 2 (5) Fig. 5 a Run number for NPEMA and PCPMA monomer pair; b dyad monomer sequence fractions vs. the NPEMA mole fractions for the copolymers NPEMA with PCPMA 1 3 160 International Journal of Industrial Chemistry (2018) 9:153–166 that the decomposition of polymers occurs in two steps. The first decomposition step was in the range of 165–397 °C, whereas the range between 314 and 530 °C was observed for second decomposition step. The first step seen at lower temperature range corresponds to the smaller polymeric chain degradation. The second step observed at higher range corresponds to the scission of main polymeric chain. Poly(PCPMA) has higher thermal decomposition steps than other polymers which confirms that the thermal degrada- tion of poly(PCPMA) was slower. It was also notable (from Table 5) that the % weight loss of poly(PCPMA) at 700 °C was slightly lower than the poly(NPEMA), whereas the % weight loss of copolymers (B2–B6) was relatively higher than each other. The IPDT of homopolymers of NPEMA and PCPMA is, respectively, 351 and 467 °C. The IPDT of copolymers of NPEMA with PCPMA varied between 333 and 347 °C. It was concluded that with the increase of Fig. 6 TGA traces of neat homo- (B1 and B7) and copolymers (B2– PCPMA feed in copolymers, the thermal stability of copoly- B6) of NPEMA/PCPMA mers (B2–B6) was also increased. Overall, the neat polymers and polymer nano composites show the two-step thermal degradation. Kinetic and thermodynamic parameters of the thermal degradation The stability of polymers and their composites with nano- CdS was also confirmed from the kinetic (i.e., E ) and ther- modynamic (i.e., ΔH, ΔS, and ΔG) parameters of the ther- mal degradation of respective polymers and polymer nano composites. The kinetic parameters of thermal degradation were obtained using Briodo (BR) [59] and Coats–Redfern (CR) [60] methods. The activation energy (by BR) was evaluated from the slope of the ln [ln (1/y)] vs. 1/T plot, whereas activation energy (by CR) was obtained from the slope of ln [− ln (1 − y)/T ] vs. 1/T plot. In these entire cal- culations. y = (W − W )/(W − W ), where W is the weight t α 0 α t Fig. 7 TGA traces of nano-CdS-doped homo- (NB1 and NB7) and at temperature, W is initial weight, and W is the weight at 0 α copolymers (NB2–NB6) of NPEMA/PCPMA the end of pyrolysis. Activation energies (in kJ/mol) for homopolymers of Thermal analysis NPEMA and PCPMA for both degradation steps obtained from Broido method were, respectively (56 and 83 kJ/mol) Thermal stability of polymer and their composites and (80 and 145 kJ/mol); the same from Coats–Redfern were (56 and 80 kJ/mol) and (85 and 150 kJ/mol). The energy with nano‑CdS of activation in copolymers B2 (80:20; NPEMA:PCPMA) obtained from Broido was (50 and 69  kJ/mol) and Thermogravimetric analysis (TGA) technique was used to investigate the thermal stability of polymers and their com- Coats–Redfern provided the same values. The energies of activation for other copolymers (B3–B7) with different posite with nano-CdS. TGA traces of homo- (B1 and B7) and copolymers of NPEMA with PCPMA (B2–B6) and its monomer feed are shown in Table 6. It was noticeable that the activation energy of the first degradation step was lower nano composites (NB1–NB7) are shown in Figs. 6 and 7, respectively. The % weight loss at various temperatures, than that of the second step. This concludes that less energy is required for degradation of shorter polymeric chains, decomposition range, T , T and integral decomposition max 50, temperature (IPDT) for homo- and copolymers of NPEMA whereas higher activation energy corresponds to the higher energy needed for degradation of higher polymeric chains. with PCPMA are tabulated in Table 5. The TGA traces show 1 3 International Journal of Industrial Chemistry (2018) 9:153–166 161 Table 6 Kinetic and thermal Kinetic/thermal parameters Method Steps Polymer numbers parameters of degradation for homo- (B1 and B7) and B1 B2 B3 B4 B5 B6 B7 copolymers (B2–B6) of E* (kJ/mol) BR I 56 50 62 53 54 56 80 NPEMA with PCPMA II 83 69 69 90 72 80 145 CR I 56 50 62 53 54 56 85 II 80 69 69 90 72 80 150 ∆S* (J/mol K) BR I − 249 − 242 − 263 − 246 − 248 − 251 − 285 II − 272 − 254 − 253 − 284 − 257 − 261 − 342 CR I − 190 − 197 − 187 − 198 − 201 − 199 − 193 II − 203 − 195 − 221 − 205 − 214 − 195 − 197 ∆H* (kJ/mol) BR I 52 46 58 48 50 52 75 II 77 63 63 85 66 74 139 CR I 52 46 58 48 50 52 40 II 75 63 63 85 66 74 144 ∆G* (kJ/mol) BR I 190 174 198 180 184 187 239 II 261 232 232 274 239 255 394 CR I 157 150 158 154 159 159 151 II 213 193 210 221 210 205 290 a, b, c These three parameters are thermodynamic parameters. Those are calculated from the values of acti- vation energies (E*) and pre-exponational factor (A). So, these parameters are not belongs to Broido or Coat-redferns method The activation energy of poly(PCPMA) was higher than that decomposition step. This was further supported from the of poly(NPEMA). The activation energies of copolymers higher value of ∆S for first decomposition step. (B2–B6) randomly increased or decreased with increase in The obtained values of kinetic and thermodynamic PCPMA content in copolymer feed. parameters for polymer composites with nano-CdS are Thermodynamic parameters (i.e., ∆S, ∆H, and ∆G) of tabulated in Table 7. The values of the activation energy thermal degradation were also useful to confirm the ther - obtained from both Broido and Coats–Redfern were found mal stability of polymers. The value of enthalpy change to be same. The values of activation energies for both steps (∆H) was positive, which indicated the endothermic nature of degradation for polymer composites of poly(NPEMA) of thermal degradation of polymers. Lower the value of and poly(PCPMA) doped with nano-CdS were 28 and 30 ∆H, lower the difference between potential energy barrier and 27 and 83 kJ/mol, respectively. The values of activation of reagents and activated complex. This suggests that the energies for both degradation steps of copolymer compos- formation of activated complex was easily favored, and ites of poly(NPEMA-co-PCPMA) with nano-CdS varied hence, degradation process was faster [61, 62]. How close between 20–34 and 30–78 kJ/mol, respectively. The values the system to its equilibrium could define from the value of activation energy were found relatively lower for poly- of entropy change (ΔS). Lower the value of ΔS suggests mer nano composites (NB1–NB7) than the neat polymers that the formation of activated complex was slow and vice (B1–B7). It was also noticed that the values of ∆H and ∆G versa [61, 62]. The negative value of ∆S and positive value for polymer composites were found to be relatively lower of ∆G for a decomposition process indicate that steps are than their corresponding neat polymers. In case of ∆S, the non-spontaneous. As the values of ∆G increase, the process values were found higher than the neat polymers. Overall, of formation of activated complex was slow which means the result reveals that the decomposition of polymer matrix that thermal degradation process was slower and vice versa. in polymer nano composites was easily favorable than in The values of thermodynamic parameters for neat neat polymers. It was also concluded that the neat polymers polymers indicate that poly(NPEMA) (B1) was less sta- were relatively more stable than their respective polymer ble than the poly(PCPMA) (B7) and poly(NPEMA-co- nano composites. In case of polymer nano composites, the PCPMA) (B2–B6). It was notified from Table  6, and the inorganic nano particles can affect the structure of polymers. first decomposition step has the lowest values of E , ∆H, These result in higher or lower thermal stability of polymer and ∆G than the second decomposition step. This reveals nano composites. Few research papers were found in this that the first decomposition step was faster than the second area (Table 8). The neat polyamide 6, polyethylene oxide (PEO)/polyvinyl alcohol (PVA), isotactic polypropylene 1 3 162 International Journal of Industrial Chemistry (2018) 9:153–166 Table 7 Kinetic and Kinetic/thermal parameters Method Steps Polymer numbers thermodynamic parameters of nano-CdS-doped homo- (NB1 NB1 NB2 NB3 NB4 NB5 NB6 NB7 and NB7) and copolymers E* (kJ/mol) BR I 28 27 34 26 20 23 27 (NB2–NB6) of NPEMA and PCPMA II 30 78 66 74 62 78 83 CR I 28 27 34 26 20 23 27 II 30 78 66 74 62 78 83 ∆S* (J/mol K) BR I − 203 − 203 − 213 − 200 − 193 − 196 − 202 II − 202 − 271 − 255 − 265 − 247 − 269 − 277 CR I − 182 − 183 − 184 − 182 − 182 − 183 − 181 II − 183 − 186 − 188 − 186 − 186 − 184 − 184 ∆H* (kJ/mol) BR I 23 23 29 21 16 18 23 II 24 73 61 68 56 73 77 CR I 23 23 29 21 16 18 23 II 24 73 61 68 56 73 77 ∆G* (kJ/mol) BR I 139 135 145 132 123 125 138 II 158 246 222 237 215 247 256 CR I 127 124 130 121 117 120 123 II 146 191 182 188 177 191 195 a, b, c These three parameters are thermodynamic parameters. Those are calculated from the values of acti- vation energies (E*) and pre-exponational factor (A). So, these parameters are not belongs to Broido or Coat-redferns method (iPP), and poly(butylene succinate-co-adipate) (PBSA) have and S. citreus, respectively. The poly(NPEMA) tolerated, 175, 101, 220.57, and 159.9 kJ/mol of activation energies, respectively, 35, 42, and 52% growth for E. coli, B. subtilis, respectively. The activation energies of their nano compos- and S. citreus; poly(PCPMA) allowed, respectively, 10, 18, ites, respectively, with clay, ZnO, palladium (Pd), and organ- and 20% growth for the species indicated above. ically modified synthetic fluorine mica were higher than The effect of homo- and copolymers of NPEMA and neat polymers. These suggest that the stronger interaction PCPMA on the growth of different fungi is demonstrated between polymer matrix and inorganic nano particles than in Fig.  8b. It is seen that the hindrance to growth by the polymer nano composites has higher value of activation poly(NPEMA) was less than their corresponding copoly- energy than the corresponding neat polymers [63, 66–68]. mers with PCPMA. The effect of poly(NPEMA) on the The activation energies of neat poly(3-hydroxy butyrate) fungi has already been indicated in the preceding section. (PHB), polyvinyl ester and nylon 6 were, respectively, 136.8, Growths of A. niger, S. pulverulentum, and T. lignorum, 186.3, and 276 kJ/mol, while the activation energies of their respectively, were 30, 20, and 34% in poly(PCPMA). The nano-composite, respectively, with Ag S, O-montmorillon- copolymers allowed 52–28, 48–28, and 58–40% growth of ite (O-MMT), and Glass fibers were found lower than neat A. niger, S. pulverulentum, and T. lignorum, respectively. polymers. This is due to the weak interaction between poly- The poly(NPEMA-co-PCPMA) and poly(PCPMA) mer matrix and inorganic nano particles [64, 65]. The lower were more effective than the poly(NPEMA) to reduce the value of kinetic and thermodynamic parameters suggests the growth of yeast (Fig. 8c). The poly(NPEMA) permitted catalytic effect arises in polymer nano composites. 40, 50, and 58% growth of S. cerevisiae, C. utilis and P. stipitis, respectively; poly(PCPMA) allowed, respectively, Antimicrobial screening 18, 32, and 28% growth of the same. The copolymers tol- erated 38–22, 50–38, and 56–40% growth of S. cerevisiae, The functional polymers having chlorine and fluorine groups C. utilis, and P. stipitis, respectively. were mostly used for antimicrobial properties. The effective- In general, poly(PCPMA) hindered the growth of all ness of homo- and copolymers of NPEMA and PCPMA to the microorganisms effectively, while the poly(NPEMA) hinder the growth of microorganisms is shown in Fig. 8. It was less effective than poly(PCPMA) and their copoly - appears that compared to poly(NPEMA) and poly(NPEMA- mers. This may be traced to the presence of chlorine in co-PCPMA), the poly(PCPMA) more effectively hinders the poly(PCPMA) and poly(NPEMA-co-PCPMA). It was microorganism’s growth. The copolymers (Fig. 8a) allowed observed that increasing the concentration of PCPMA in growth of 30–20, 32–25, and 50–38% for E. coli, B. subtilis, copolymers resulted in increase of antimicrobial properties 1 3 International Journal of Industrial Chemistry (2018) 9:153–166 163 Table 8 Activation energies for other polymer nano composites No. Polymer/polymer nano-composite Method name Activation energy References E (KJ/mol) 1. Polyamide 6 Kissinger 175 [63] Polyamide 6/clay 199 2. Poly(3-hydroxy butyrate) (PHB) Kissinger 136.8 [64] 0.05% Ag S/PHB 110.2 2 2000 0.12% Ag S/PHB 95.1 2 1000 0.5% Ag S/PHB 91.8 2 250 1.28% Ag S/PHB 94.5 2 100 2.6% Ag S/PHB 99.1 2 50 3. Polyvinyl ester Coats–Redfern 186.3 [65] Polyvinyl ester/1% O-montmorillonite (O-MMT) 173.4 Polyvinyl ester/5% O-MMT 154.9 4. Polyvinyl ester Briodo 190.2 [65] Polyvinyl ester/1% O-montmorillonite (O-MMT) 185.2 Polyvinyl ester/5% O-MMT 166.7 5. Polyethylene oxide (PEO)/polyvinyl alcohol (PVA) Coats–Redfern 101 [66] PEO-PVA/1% ZnO 122 PEO-PVA/5% ZnO 130 5. Polyethylene oxide (PEO)/polyvinyl alcohol (PVA) Briodo 159 [66] PEO-PVA/1% ZnO 164 PEO-PVA/5% ZnO 169 6. Isotactic polypropylene (iPP) Flynn-Wall 220.57 [67] iPP/0.27% Pd 227.85 7. Nylon 6 Coats–Redfern 264 [40] Nylon 6/Glass fiber 181 Nylon 6/3 5% crysnano nano-clay 219 Nylon 6/5% crysnano nano-clay 247 8. Nylon 6 Briodo 276 [40] Nylon 6/glass fiber 193 Nylon 6/3 5% crysnano nano-clay 231 Nylon 6/5% crysnano nano-clay 259 9. Poly(butylene succinate-co-adipate) (PBSA) Kissinger 159.9 [68] PBSA/OSFM (organically modified synthetic fluorine mica) 168.9 and vice versa. It was further seen that the homo- and Conclusion copolymers of PCPMA effectively hindered the growth of bacteria, while the growth of yeast and fungi was moder- The homo- and copolymers (with different monomer feeds) ately hindered. of NPEMA and PCPMA were prepared via free radical solu- Overall, the percentage of NPEMA in the copolymers tion polymerization technique. The relative intensity of dif- increased, the effectiveness of the copolymers to inhibit ferent bands (i.e., C=O group, –CH rocking vibration) in the growth of microorganisms decreased, while increase FT-IR spectra of copolymers was increased or decreased. in the percentage of monomers which have active groups This reveals that the composition of monomers in copoly- (i.e., –Cl) will increase the ability of polymers to inhibit mers was well matched. The polydispersity of homo- and the growth of microorganisms. This investigation indicates copolymers varied between 1.45 and 1.67. Nano-CdS-doped that monomers containing chlorine can be used to pre- polymer composite was prepared via in  situ technique. pare polymers which can be used as general antimicrobial The nano-CdS-doped polymer composite is characterized agents in water purification systems and food packaging by XRD and FT-IR. The XRD pattern confirms the cubic materials. structure of CdS nano particles with three reflection planes (111), (222), and (311). The FT-IR spectra of polymer nano 1 3 164 International Journal of Industrial Chemistry (2018) 9:153–166 composites confirm the weak interaction between inorganic nano particles and polymer matrix. The TGA analysis of polymers confirms that the poly(PCPMA) was more stable than poly(NPEMA-co-PCPMA) and poly(NPEMA). The values of activation energy, ∆S, ∆H, and ∆G, confirm the stability of poly(PCPMA). The values of activation energy for polymer nano composites were found lower than the neat polymers. 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Methacrylate copolymers and their composites with nano-CdS: synthesis, characterization, thermal behavior, and antimicrobial properties

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Springer Journals
Copyright
Copyright © 2018 by The Author(s)
Subject
Chemistry; Industrial Chemistry/Chemical Engineering; Polymer Sciences; Nanochemistry; Environmental Chemistry
ISSN
2228-5970
eISSN
2228-5547
DOI
10.1007/s40090-018-0146-3
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Abstract

Homo- and copolymers of 2-(N-phthalimido)ethyl methacrylate (NPEMA) and p-chlorophenyl methacrylate (PCPMA) were prepared in N,N-dimethyl formamide (DMF) solution at 70 °C using 2,2-azo-bisisobutyronitrile (AIBN) as initiator. The nano-CdS-doped polymer composite of NPEMA and PCPMA was prepared via in situ technique. The homo- and copolymers of NPEMA and PCPMA were characterized using FT-IR spectroscopy and gel permeation chromatography (GPC). The poly- mer nano composites were characterized using FT-IR spectroscopy, X-ray diffraction, and transmission electron microscopy. The reactivity ratios (r and r ) were obtained from the various linear graphical methods. The values of r (NPEMA) = 0.55 1 2 1 and r (PCPMA) = 1.30 were found from the same graphical methods. The copolymer microstructures were found from the mean sequence length, run number, and dyad fraction. Thermal behavior of polymers and polymer nano composites under nitrogen atmosphere was studied. The activation energies of neat polymers were varied in the range of 56–85 kJ/mol, while 28–56 kJ/mol energies were found for nano-CdS-doped polymer composites. The thermodynamic parameters of thermal degradation were also obtained. Kinetic and thermodynamic parameters were confirming the stability of the neat polymers than polymer nano composites. The polymers were assessed on different microorganisms for obtaining the antimicrobial properties. Overall, the polymers permit 10–52, 20–58, and 18–56% growth of bacteria, fungi, and yeast, respectively. Keywords Copolymerization · Polymer nano composites · Reactivity ratio · Thermal properties · Antimicrobial properties Introduction [3], atom transfer free radical polymerization (ATRP) [4], reversible addition–fragmentation chain transfer free radi- Copolymerization technique is an adaptable technique to cal polymerization (RAFT) [5], redox polymerization [6], prepare copolymers from two or more different types of photo polymerization [7] living polymerization [8], etc. It monomers. These copolymers have different properties is required to choose the polymerization process to obtain than their individual homopolymers. The acrylates or meth- copolymers having desirable chemical, optical, mechanical, acrylates are normally polymerized through various tech- and electrical properties. Free radical solution polymeriza- niques. These techniques are free radical solution polymeri- tion is a simple, versatile, and effective technique to pre - zation [1], bulk polymerization [2], emulsion polymerization pare the acrylate or methacrylate homo- and copolymers. The functionalized copolymers of acrylates were applied in various fields such as biomedical [ 9], textile [10], coating [11], adhesions [12], food packaging [13], and many more * Mehdihasan I. Shekh mehdi.shekh3@yahoo.com [14, 15]. Knowing the copolymer microstructure is useful to predict the properties of the copolymers. The microstructure Rajnikant M. Patel rmpatel_28@yahoo.co.in of copolymers is easily predicted from the values of reactiv- ity ratios of two monomers and the ratios of these values Department of Advanced Organic Chemistry, P. D. Patel are possible to find from the various linear and non-linear Institute of Applied Sciences, Charotar University of Science methods [16–18]. and Technology, Changa 388421, Gujarat, India 2 Polymers are the most preferable host materials to pre- Department of Chemistry, Sardar Patel University, pare the inorganic nano particles (Nps)-doped composites. Vallabh Vidhyanagar 388120, Gujarat, India Vol.:(0123456789) 1 3 154 International Journal of Industrial Chemistry (2018) 9:153–166 These classes of materials have very good applicable prop- Experimental erties (i.e., electrical, mechanical, and optical). Materi- als having both inorganic and organic characteristics Materials were well researched [19–23]. Recently, many techniques [24–28] were developed to prepare the new potential mate- Ethanol amine, phthalic anhydride, triethyl amine (TEA), rials that were used in various fields [29– 33] such as bio- N,N-dimethyl formamide (DMF), methanol, cadmium logical labeling, light-emitting diodes, transistors, solar nitrate, sodium sulfide, and 2,2-azo-bis-isobutyronitrile cells, organic-based electronics, sensors, optical switch- (AIBN) were purchased from the Loba chem Pvt. Ltd. ing, etc. (India). The nutrient broth, potato dextrose broth, and tryp- The numbers of research reports were published on the tone glucose yeast extract were purchased from the Hime- polymer composites with nano-metal oxides [34, 35], metal dia Laboratories Pvt. Ltd. The pre-grown slants of vari- sulfides [36, 37], and many more [38–41]. Among them, ous microorganisms (i.e., bacteria, yeast, and fungi) were semiconducting polymer nano composites of metal sulfides obtained from the Microbial-Type Culture Collection and are very useful for their optoelectronic properties. A semi- Gene Bank (MTCC), CSIR-Institute of Microbial Technol- conducting polymer composite of CdS Nps is this class of ogy, Chandigarh, India. All chemicals are analytical grade material. It has broad range of applications in the various and are used as received. fields. The various polymers are used as host materials to prepare the CdS/polymer nano composites. The different Synthesis CdS-Nps-doped polymer composites are prepared via dif- ferent techniques. CdS/polystyrene nano-composite was pre- Synthesis of starting materials and monomers pared by a chemical route using an ex situ technique [42]. Oxidization polymerization technique was used to prepare The synthesis of methacryloyl chloride (MAC), N-(2-hy- CdS/polyaniline nano-composite [43]. CO -doped CdS/ droxy ethyl) phthalimide (NHEP), and 2-(N-phthalimido) polyvinyl pyrolidone composite was synthesized by chemi- ethyl methacrylate (NPEMA) was prepared, as reported in cal precipitation method [44]. Spin-coating technique was Ref. [50]. The p-chlorophenyl methacrylate (PCPMA) was used to prepare thin films of CdS/poly[2-methoxy-5-(2′ - prepared by earlier reported synthesis [51]. ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) nano- composite [45]. Several other CdS/polymer nano compos- Copolymerization of NPEMA with PCPMA ites such as CdS/polyamidoamine dendrimer [46], CdS/ poly[4-(n-acryloyloxyalkoxy)benzoic acid] [47], and many The free-radical polymerization technique [50] was more [48, 49] were also investigated. Although the proper- ties and synthesis of CdS/polymer nano composites are well employed to synthesize copolymers of NPEMA with PCPMA having different feed compositions. N ,N-Dimethyl investigated, yet the effect of CdS Nps on the degradation of polymer in inert atmosphere (i.e., N gas) is not investigated. formamide (DMF) was used as a solvent and AIBN as a free-radical initiator. The feed composition of monomers The synthesis of macromolecules having antimicrobial properties is useful in various areas like hospitals, dental is given in Table 1. Appropriate quantities of monomers, DMF, and AIBN (0.5% w/w based on total monomers 1 equipment, water purification systems, food storage, and food packaging units. Polymeric materials having antimi- and 2) were added to a flask fitted with reflux condenser. The reaction mixture was heated to 70 °C for 5 h with stir- crobial properties are prepared mainly by: (1) polymeriza- tion of antimicrobial monomers which have characteristic ring. It was kept for cooling at room temperature, and then, the resulting polymer solution was slowly poured in a large functional groups responsible for antimicrobial properties and (2) chemical modification of synthetic polymers by anti- volume of methanol with stirring. The polymer is followed out. It was filtered and then washed with methanol. Solid microbial agents or biocides. In this article, we have synthe- sized chlorine containing copolymers and assessed various polymers were purified by repeated precipitation from DMF solution using methanol. Synthesis of copolymer is shown microorganisms to confirm the copolymer’s antimicrobial potency. in Scheme 1. The present paper covers the synthesis, characterization, thermal behavior, and antimicrobial screening of homo- and Preparation of CdS‑Nps‑doped polymer composites copolymers of NPEMA with PCPMA. Polymer composites with nano-Cds were prepared and characterized by spectro- Polymer (0.5 g) dissolved in 50-ml DMF with stirring in a scopic tools. The main objective of this paper is to study the 250-ml conical flask, and then, the flask was kept for sonica- effect of CdS Nps on thermal degradation of polymer matrix tion. Under sonication, cadmium nitrate solution (0.1 M) in in nano composites. 1 3 International Journal of Industrial Chemistry (2018) 9:153–166 155 Table 1 Monomer feed ratio of Sample code Monomer feed composition Composition of % Yield NPEMA with PCPMA NPEMA in copoly- M (NPEMA) M (PCPMA) 1 2 mer mol g wt% mol g wt% B1 1.0 259 100 – – – 100 80 B2 0.8 207.2 80 0.2 39.3 20 81 75 B3 0.6 155.4 60 0.4 78.6 40 61 80 B4 0.5 129.5 50 0.5 98.3 50 51 78 B5 0.4 103.6 40 0.6 117.9 60 40 65 B6 0.2 51.8 20 0.8 157.2 80 20 63 B7 – – – 1 196.5 100 – 78 Scheme 1 Copolymerization (B2–B6) of NPEMA with PCPMA DMF was added slowly to polymer solution. Then, 0.1-M (Tecnai 20, Philips, Holland, with W-emitter and LaB6 as sodium sulfide (0.11 M) solution prepared in methanol was electron source and accelerating voltage up to 200  kV). added dropwise to the solution containing cadmium nitrate Thermal analysis was performed at 10 °C/min heating rate and polymer solution under sonication. After complete addi- on Mettler-Toledo thermogravimetric analyzer for TGA/ tion, the solution becomes yellowish and cloudy. The flask is DSC-1. putted for 4 h at room temperature to settle the yellow color polymer composites of nano-CdS. The obtained polymer Antimicrobial screening nano composites were separated by ultracentrifugation. The nano composites were washed several times with methanol The quantitative method [50] was used to assess antimi- to remove unreacted or excess reagents. The polymer nano- crobial properties. The homo- and copolymers of NPEMA/ composite is dried into a vacuum desiccator. PCPMA tested against different microorganisms which are commonly employed for biocompatibility test. These micro- Characterization organisms are bacteria (Escherichia coli, Bacillus subtilis, and Staphylococcus citreus), fungi (Sporotrichum pulveru- The H-NMR resonances were recorded with a Bruckner lentum, Aspergillus niger, and Trichoderma lignorum), and 400 MHZ FT NMR spectrophotometer. The IR spectra of yeast (Candida utilis, Pichia stipitis, and Saccharomyces solid samples in KBr pallets were obtained from Nicolet cerevisiae). The antimicrobial activity of poly(NPEMA) 6700 FT-IR spectrophotometer. Copolymer compositions was already discussed [50]. All microorganism cultures and reactivity ratios were determined by spectroscopic were prepared from their respected slants. All microorgan- data from UV–visible–NIR Schimadzu-3600 spectropho- ism cultures were sub-cultured periodically and maintained tometer. The phase and crystallographic structures of CdS in their respected media. The bacteria, yeast, and fungi in polymer nano composites of NPEMA/CMPMA were cultures were kept overnight at 37, 30, and 27 °C, respec- identified by X-ray diffraction (XRD, Bruckner D2 Phaser tively. In the present study, the bacterial culture’s %OD is 3600 X-ray Diffractometer having Cu-kα radiation source, set at 0.1 in 600 nm which corresponds to 10 CFU/ml. The λ = 0.154 nm). The morphology of polymer nano composites yeast culture’s %OD was set at 0.8 in 600 nm which corre- of CdS was derived using transmission electron microscope sponds to 2 × 10 CFU/ml. The fungi culture was prepared 1 3 156 International Journal of Industrial Chemistry (2018) 9:153–166 by inoculation with 0.7-mm plug (spore) containing actively growing fungi’s slants. Each test was carried out three times and the mean results are shown in a bar graph. Results and discussion H‑NMR spectroscopy The monomers NPEMA and PCPMA were characterized from the proton NMR spectroscopy. The proton NMR spectra of NPEMA monomer have been discussed in earlier report [50]. NPEMA 1H-NMR(CDCl3) δ (ppm) = 7.5–7.8 (4H, m, Ar–CH), 5.9 (1H, d, vinylic-H), 5.5 (1H, d, vinylic-H), 4.3 (2H, t, –CH –O), 3.9 (2H, t, –CH –N), and 1.9 (3H, s, CH ). 2 2 3 PCPMA 1H-NMR(CDCl3) δ (ppm) = 6.9–7.3 (3H, m, Ar–CH), 6.4 (1H, d, vinylic-H), 5.7(1H, d, vinylic-H), 2.3 (3H, s, Ar–CH ), and 2.1 (3H, s, O=C–C–CH3). FT‑IR spectroscopy −1 The combined FT-IR spectra (2000–500 cm ) of homo- Fig. 2 FT-IR spectra of poly(NPEMA-co-PCPMA) (B2–B6) and and copolymers of NPEMA with PCPMA and their poly- nano-Cds-doped polymer composite of poly(NPEMA-co-PCPMA) mer composites with nano-CdS are shown in Figs. 1 and 2, (NB2–NB6) respectively. From the spectra of neat polymers, the bands −1 observed at ~ 1750 cm are assigned for the stretching vibra- the homopolymers of NPEMA, whereas the bands at 1258, tion of –C=O in ester group. Another absorbance observed −1 −1 at ~ 1710  cm corresponds to –C=O stretching in phthal- 1200, 1122, 1084, and 1012 cm are seen in the homopoly- −1 mers of PCPMA which are attributed to the C–C(=O)–O imide [50]. The bands between 1600 and 1400 cm are assigned to the aromatic ring breathing vibration. The same and O–C–C-bending vibration in ester. The bands at 1258, −1 1199, 1160, 1122, 1080, and 1012 cm are seen in copoly- band is also observed in all copolymers IR spectra. Medium −1 bands ~ 1465 and ~ 1387 cm correspond to asymmetrical mers of NPEMA and PCPMA which are assigned for the bending vibration of C–C(=O)–O and O–C–C in ester. The and symmetrical bending vibration of methyl group, respec- −1 −1 tively. The bands at 1173, 1146, and 1048 cm are seen in sharp band at 720 cm is observed in homopolymers of NPEMA. The same absorption band is also observed in the spectra of copolymers and this band’s intensity is decreased with decrease in the NPEMA content in the copolymers. The −1 band ~ 680 cm is assigned for the C–Cl-stretching vibra- tion in homopolymers of PCPMA. The same band is also observed in spectra of copolymers. In the case of nano-CdS-doped polymer compos- ites, the intensity of the bands is decreased. The inten- sity of bands corresponding to –C=O (~ 1750 and −1 −1 ~ 1710 cm ), C–C(=O)–O (1210–1164 cm ), and O–C–C −1 (1164–1000  cm ) is effectively decreased and becomes broader. This suggests that the attraction between CdS Nps and polymer matrix occurring on these sites which depict the presence of CdS Nps in polymer matrix affects the vibra- tion of C–O. As NPEMA content decreased in copolymer feed, the interaction between polymer matrix and inorganic Fig. 1 FT-IR spectra of poly(NPEMA) (B1); poly(PCPMA) (B7) matrix also decreased. This was due to the less sites that and nano-Cds-doped polymer composite of poly(NPEMA) (NB1); were available for interactions in the poly(PCPMA) than poly(PCPMA) (NB7) 1 3 International Journal of Industrial Chemistry (2018) 9:153–166 157 −1 poly(NPEMA). The band at 1387 cm which corresponds Table 3 Reactivity ratios obtained for NPEMA and PCPMA mono- mers using different linear methods to the symmetric vibration of methyl group is not affected by the presence of CdS Nps. This reveals that no interaction is Method Reactivity ratio possible between the methyl and CdS Nps. A weak Van der r r r  × r 1/r 1/r 1 2 1 2 1 2 Waals interaction between polymer matrix and nano-CdS F–R 0.53 1.29 0.68 1.89 0.78 may be envisaged. Invrt. F–R 0.62 1.37 0.85 1.61 0.73 K–T 0.53 1.27 0.67 1.89 0.79 Average molecular weights Ext. K–T 0.5 1.28 0.64 2.00 0.78 Average 0.55 1.30 0.71 1.83 0.77 GPC instrument equipped with Waters 1525 binary pomp, manual injector and connected to Styragel HR 4 column and R.I. detector (waters 2414) is employed to record GPC curves. Tetrahydrofuran (THF) at 1.0 ml/min flow rate is peaks are observed in each composite which corresponds to the three reflection planes. These reflection planes [i.e., used as a mobile phase throughout the analysis. All the measurements are carried out at 30 °C temperature. About (111), (220), and (311)] confirm that the CdS Nps are cubic and match with JCPDE number 089-0440. The size of CdS 5–10 mg of each polymer sample is dissolved in 10-ml THF and the resulting solutions are filtered. 20-μl sample solu- nano particles is calculated using Debye–Scherrer formula [52] for (111) reflection plane of the XRD pattern. The size tion is injected for the GPC analysis. The average molecular weights, namely, Mn, Mw, Mz, Mz + 1, and polydispersity, of CdS Nps varied between 4.11 and 5.32 nm. Figure 4 shows the TEM images of the nano-CdS-doped are shown in Table 2. The GPC data for poly(NPEMA-co- PCPMA) provided the values of Mn, Mw, Mz, and Mz + 1 poly(NPEMA-PCPMA) (0.5/0.5) (NB4) composite. The images clearly show the formation of CdS nano compos- which vary from 20,109 to 22,381, 31,518 to 34,804, 47,784 to 51,883, and 65,954 to 71,200, respectively, for copoly- ites with a spherical shape and homogeneous distribution in polymer matrix. mers with different feed ratio of the monomers; polydisper - sity index lies between 1.54 and 1.60 (Table 2). The results Monomer reactivity ratio reveal that molecular weights decrease and polydispersity index changes randomly as the NPEMA content decreases The copolymer composition depends on the monomer feed in the copolymers. The values of Mn, Mw, Mz, and Mz + 1 are, respectively, 26,052, 43,620, 67,474, 91, and 839 for composition and on the relative monomer reactivity. The UV spectroscopy was employed to n fi d the concentration of poly(PCPMA) and the polydispersity index is 1.67. The polydispersity of homopolymers and copolymers was nearly NPEMA monomer in copolymer. The procedure to find con- centration of NPEMA in copolymers using UV spectroscopy 1.5, indicating termination of growing chain by radical com- bination (Table 2). was already discussed [50]. The monomer reactivity ratios X‑ray diffraction study and transmission electron microscopy Powder XRD pattern of nano-CdS-doped poly(NPEMA-co- PCPMA) (0.5/0.5 mol ratio) is shown in Fig. 3. The three Table 2 Average molecular weights of homo- (B1 and B7) and copol- ymers (B2–B6) of NPEMA with PCPMA Sample no. Average molecular weights (in Dalton) Polydis- persity M M M M n w z z+1 (Ð) B1 18310 26613 37812 50279 1.45 B2 20109 31518 47784 65954 1.57 B3 21080 33782 51641 71153 1.60 B4 21225 33511 50566 69333 1.58 B5 22127 34044 50094 67778 1.54 B6 22381 34804 51883 71200 1.56 Fig. 3 XRD pattern of nano-CdS-doped poly(NPEMA-co-PCPMA) B7 26052 43620 67474 91839 1.67 composite (mole ratio: 0.5/0.5) (NB4) 1 3 158 International Journal of Industrial Chemistry (2018) 9:153–166 Fig. 4 TEM images of nano- CdS-doped poly(NPEMA-co- PCPMA) composite (mole ratio: 0.5/0.5) (NB4) were determined using four linear methods Fineman–Rose where [M ] and [M ] are concentrations of NPEMA and 1 2 (F–R) [53], inverted Fineman–Rose (Invrt. F–R), Kelan–Tudos PCPMA, respectively. The ratio of the mean sequence length (K–T) [54], and extended Kelen–Tudos (Ext. K–T) [55]. The distribution μ /μ which theoretically corresponds NPEMA PCPMA, values of r (NPEMA), r (PCPMA), 1/r , and 1/r and product to the ratio [M ]/[M ], is tabulated in Table 4. For example, 1 2 1 2 1 2 of r and r are tabulated in Table 3. at [M ] = 20.0% and [M ] = 80.0%, each copolymer segment 1 2 1 2 It was seen that the value of r is less than r ; this sug- with M units was approximately six times longer than its 1 2 2 gests that the reactivity of NPEMA monomer is less than adjoining segment with M units. The sequence may be that of PCPMA. This also proves that the PCPMA units were expressed as NPPPPPPN, where P stands for PCPMA and N found more in the copolymer content. r < r suggest that is for NPEMA. The number of NPEMA units in copolymer 1 2 the NPEMA favors the cross propagation, whereas PCPMA increases with increasing concentration of NPEMA in the favors the homopropagation. As 1/r > 1/r , it was concluded feed. The results of mean sequence length and values of 1/r 1 2 1 that there were more growing radicals with NPEMA ends and 1/r compare each other very well; 1/r is greater than 2 1 than with PCPMA ends due to r < r , which identified which 1/r , and as expected in copolymers, the homopropagation 1 2 2 monomer amongst the two was more reactive. of PCPMA decreased with decreasing PCPMA in monomer feed, while cross propagation of monomeric units increased Copolymer microstructure with increasing concentration of NPEMA in monomer feed. Mean sequence length Run number and dyad fraction The mean sequence lengths μ and μ are calculated From the reactivity ratios of monomers, the run number, R NPEMA PCPMA N, using the following equation [56]: was determined following Harwood and Reichy [57] as the average number of monomer alternations per 100 monomeric [M ] = 1 + r units in a copolymer chain: (1) NPEMA 1 [M ] R = . [M ] (3) 2 + r × X + = 1 + r , 1 (2) X PCPMA 2 [M ] Table 4 Mean sequence length Sample no. Monomer feed μ μ μ :μ μ /μ Distribution 1 2 1 2 1 2 of copolymers of NPEMA with PCPMA M M 1 2 B2 0.8 0.2 3.2 1.3 3:1 2.41 NNNPNNN B3 0.6 0.4 1.8 1.8 2:2 0.98 NNPPNN B4 0.5 0.5 1.6 2.3 2:2 0.67 NNPPNN B5 0.4 0.6 1.4 2.9 1:3 0.46 NPPPN B6 0.2 0.8 1.1 6.2 1:6 0.18 NPPPPPPN μ = NPEMA (N); μ = PCPMA (P) 1 2 1 3 International Journal of Industrial Chemistry (2018) 9:153–166 159 Table 5 TGA data of homo- a b c Sample no. % Weight loss at various tem- Decomposition tem- T T IPDT max 50 (B1 and B7) and copolymers perature (°C) perature range (°C) (B2–B6) of NPEMA with PCPMA 200 300 400 500 600 Step-I Step-II Step-I Step-II B1 2 22 65 100 100 172–318 318–430 281 405 377 351 B2 4 35 85 98 99 170–314 314–446 257 394 357 340 B3 3 33 79 97 97 173–314 314–449 260 394 364 333 B4 4 38 83 98 98 165–316 316–443 261 395 351 334 B5 3 35 74 98 98 170–330 330–457 269 400 365 341 B6 3 30 74 96 96 203–333 333–451 275 407 372 347 B7 2 16 37 95 95 227–397 397–530 349 472 448 437 Temperature for maximum rate of decomposition Temperature for 50% weight loss Integral procedural decomposition temperature by Doyle’s method The R value provides a view of sequence distributions in 1∕2 copolymer chains, and consequently, it is possible to assess S = 4m m ∕ 1 + 2m − 1 + 4r r m m . 1−2 1 2 1 1 2 1 2 the relationship between physical properties of copolymers (6) and their compositions. The value of R can be calculated The variation of the dyad fractions with the NPEMA from reactivity ratios. The variation of R with X (= [M ]/ N 1 mole fraction in the copolymers is depicted in Fig. 5b. Fig- [M ]) is shown in Fig. 5a. ure 5b shows S is less than S , suggesting that NPEMA The maximum value of R is 54.2 at X = 1.5 for the 1–1 2–2 has negligible attraction with NPEMA monomer, and so, poly(NPEMA-co-PCPMA) system. To gain further infor- NPEMA homopolymerization is not favorable. The value mation about the copolymer structure, the formation prob- of S implied that homopolymerization of PCPMA is abilities of dyad fractions as a function of the molar fraction 1–2 quite dominant. The consequences of these calculations of monomeric units in the copolymer can be calculated from are the same as those obtained from reactivity ratios. the monomer feed compositions and reactivity ratios [58]: 1∕2 S = m − 2m m ∕ 1 + 2m − 1 + 4r r m m 1−1 1 1 2 1 1 2 1 2 (4) 1∕2 S = m − 2m m ∕ 1 + 2m − 1 + 4r r m m 2−2 2 1 2 1 1 2 1 2 (5) Fig. 5 a Run number for NPEMA and PCPMA monomer pair; b dyad monomer sequence fractions vs. the NPEMA mole fractions for the copolymers NPEMA with PCPMA 1 3 160 International Journal of Industrial Chemistry (2018) 9:153–166 that the decomposition of polymers occurs in two steps. The first decomposition step was in the range of 165–397 °C, whereas the range between 314 and 530 °C was observed for second decomposition step. The first step seen at lower temperature range corresponds to the smaller polymeric chain degradation. The second step observed at higher range corresponds to the scission of main polymeric chain. Poly(PCPMA) has higher thermal decomposition steps than other polymers which confirms that the thermal degrada- tion of poly(PCPMA) was slower. It was also notable (from Table 5) that the % weight loss of poly(PCPMA) at 700 °C was slightly lower than the poly(NPEMA), whereas the % weight loss of copolymers (B2–B6) was relatively higher than each other. The IPDT of homopolymers of NPEMA and PCPMA is, respectively, 351 and 467 °C. The IPDT of copolymers of NPEMA with PCPMA varied between 333 and 347 °C. It was concluded that with the increase of Fig. 6 TGA traces of neat homo- (B1 and B7) and copolymers (B2– PCPMA feed in copolymers, the thermal stability of copoly- B6) of NPEMA/PCPMA mers (B2–B6) was also increased. Overall, the neat polymers and polymer nano composites show the two-step thermal degradation. Kinetic and thermodynamic parameters of the thermal degradation The stability of polymers and their composites with nano- CdS was also confirmed from the kinetic (i.e., E ) and ther- modynamic (i.e., ΔH, ΔS, and ΔG) parameters of the ther- mal degradation of respective polymers and polymer nano composites. The kinetic parameters of thermal degradation were obtained using Briodo (BR) [59] and Coats–Redfern (CR) [60] methods. The activation energy (by BR) was evaluated from the slope of the ln [ln (1/y)] vs. 1/T plot, whereas activation energy (by CR) was obtained from the slope of ln [− ln (1 − y)/T ] vs. 1/T plot. In these entire cal- culations. y = (W − W )/(W − W ), where W is the weight t α 0 α t Fig. 7 TGA traces of nano-CdS-doped homo- (NB1 and NB7) and at temperature, W is initial weight, and W is the weight at 0 α copolymers (NB2–NB6) of NPEMA/PCPMA the end of pyrolysis. Activation energies (in kJ/mol) for homopolymers of Thermal analysis NPEMA and PCPMA for both degradation steps obtained from Broido method were, respectively (56 and 83 kJ/mol) Thermal stability of polymer and their composites and (80 and 145 kJ/mol); the same from Coats–Redfern were (56 and 80 kJ/mol) and (85 and 150 kJ/mol). The energy with nano‑CdS of activation in copolymers B2 (80:20; NPEMA:PCPMA) obtained from Broido was (50 and 69  kJ/mol) and Thermogravimetric analysis (TGA) technique was used to investigate the thermal stability of polymers and their com- Coats–Redfern provided the same values. The energies of activation for other copolymers (B3–B7) with different posite with nano-CdS. TGA traces of homo- (B1 and B7) and copolymers of NPEMA with PCPMA (B2–B6) and its monomer feed are shown in Table 6. It was noticeable that the activation energy of the first degradation step was lower nano composites (NB1–NB7) are shown in Figs. 6 and 7, respectively. The % weight loss at various temperatures, than that of the second step. This concludes that less energy is required for degradation of shorter polymeric chains, decomposition range, T , T and integral decomposition max 50, temperature (IPDT) for homo- and copolymers of NPEMA whereas higher activation energy corresponds to the higher energy needed for degradation of higher polymeric chains. with PCPMA are tabulated in Table 5. The TGA traces show 1 3 International Journal of Industrial Chemistry (2018) 9:153–166 161 Table 6 Kinetic and thermal Kinetic/thermal parameters Method Steps Polymer numbers parameters of degradation for homo- (B1 and B7) and B1 B2 B3 B4 B5 B6 B7 copolymers (B2–B6) of E* (kJ/mol) BR I 56 50 62 53 54 56 80 NPEMA with PCPMA II 83 69 69 90 72 80 145 CR I 56 50 62 53 54 56 85 II 80 69 69 90 72 80 150 ∆S* (J/mol K) BR I − 249 − 242 − 263 − 246 − 248 − 251 − 285 II − 272 − 254 − 253 − 284 − 257 − 261 − 342 CR I − 190 − 197 − 187 − 198 − 201 − 199 − 193 II − 203 − 195 − 221 − 205 − 214 − 195 − 197 ∆H* (kJ/mol) BR I 52 46 58 48 50 52 75 II 77 63 63 85 66 74 139 CR I 52 46 58 48 50 52 40 II 75 63 63 85 66 74 144 ∆G* (kJ/mol) BR I 190 174 198 180 184 187 239 II 261 232 232 274 239 255 394 CR I 157 150 158 154 159 159 151 II 213 193 210 221 210 205 290 a, b, c These three parameters are thermodynamic parameters. Those are calculated from the values of acti- vation energies (E*) and pre-exponational factor (A). So, these parameters are not belongs to Broido or Coat-redferns method The activation energy of poly(PCPMA) was higher than that decomposition step. This was further supported from the of poly(NPEMA). The activation energies of copolymers higher value of ∆S for first decomposition step. (B2–B6) randomly increased or decreased with increase in The obtained values of kinetic and thermodynamic PCPMA content in copolymer feed. parameters for polymer composites with nano-CdS are Thermodynamic parameters (i.e., ∆S, ∆H, and ∆G) of tabulated in Table 7. The values of the activation energy thermal degradation were also useful to confirm the ther - obtained from both Broido and Coats–Redfern were found mal stability of polymers. The value of enthalpy change to be same. The values of activation energies for both steps (∆H) was positive, which indicated the endothermic nature of degradation for polymer composites of poly(NPEMA) of thermal degradation of polymers. Lower the value of and poly(PCPMA) doped with nano-CdS were 28 and 30 ∆H, lower the difference between potential energy barrier and 27 and 83 kJ/mol, respectively. The values of activation of reagents and activated complex. This suggests that the energies for both degradation steps of copolymer compos- formation of activated complex was easily favored, and ites of poly(NPEMA-co-PCPMA) with nano-CdS varied hence, degradation process was faster [61, 62]. How close between 20–34 and 30–78 kJ/mol, respectively. The values the system to its equilibrium could define from the value of activation energy were found relatively lower for poly- of entropy change (ΔS). Lower the value of ΔS suggests mer nano composites (NB1–NB7) than the neat polymers that the formation of activated complex was slow and vice (B1–B7). It was also noticed that the values of ∆H and ∆G versa [61, 62]. The negative value of ∆S and positive value for polymer composites were found to be relatively lower of ∆G for a decomposition process indicate that steps are than their corresponding neat polymers. In case of ∆S, the non-spontaneous. As the values of ∆G increase, the process values were found higher than the neat polymers. Overall, of formation of activated complex was slow which means the result reveals that the decomposition of polymer matrix that thermal degradation process was slower and vice versa. in polymer nano composites was easily favorable than in The values of thermodynamic parameters for neat neat polymers. It was also concluded that the neat polymers polymers indicate that poly(NPEMA) (B1) was less sta- were relatively more stable than their respective polymer ble than the poly(PCPMA) (B7) and poly(NPEMA-co- nano composites. In case of polymer nano composites, the PCPMA) (B2–B6). It was notified from Table  6, and the inorganic nano particles can affect the structure of polymers. first decomposition step has the lowest values of E , ∆H, These result in higher or lower thermal stability of polymer and ∆G than the second decomposition step. This reveals nano composites. Few research papers were found in this that the first decomposition step was faster than the second area (Table 8). The neat polyamide 6, polyethylene oxide (PEO)/polyvinyl alcohol (PVA), isotactic polypropylene 1 3 162 International Journal of Industrial Chemistry (2018) 9:153–166 Table 7 Kinetic and Kinetic/thermal parameters Method Steps Polymer numbers thermodynamic parameters of nano-CdS-doped homo- (NB1 NB1 NB2 NB3 NB4 NB5 NB6 NB7 and NB7) and copolymers E* (kJ/mol) BR I 28 27 34 26 20 23 27 (NB2–NB6) of NPEMA and PCPMA II 30 78 66 74 62 78 83 CR I 28 27 34 26 20 23 27 II 30 78 66 74 62 78 83 ∆S* (J/mol K) BR I − 203 − 203 − 213 − 200 − 193 − 196 − 202 II − 202 − 271 − 255 − 265 − 247 − 269 − 277 CR I − 182 − 183 − 184 − 182 − 182 − 183 − 181 II − 183 − 186 − 188 − 186 − 186 − 184 − 184 ∆H* (kJ/mol) BR I 23 23 29 21 16 18 23 II 24 73 61 68 56 73 77 CR I 23 23 29 21 16 18 23 II 24 73 61 68 56 73 77 ∆G* (kJ/mol) BR I 139 135 145 132 123 125 138 II 158 246 222 237 215 247 256 CR I 127 124 130 121 117 120 123 II 146 191 182 188 177 191 195 a, b, c These three parameters are thermodynamic parameters. Those are calculated from the values of acti- vation energies (E*) and pre-exponational factor (A). So, these parameters are not belongs to Broido or Coat-redferns method (iPP), and poly(butylene succinate-co-adipate) (PBSA) have and S. citreus, respectively. The poly(NPEMA) tolerated, 175, 101, 220.57, and 159.9 kJ/mol of activation energies, respectively, 35, 42, and 52% growth for E. coli, B. subtilis, respectively. The activation energies of their nano compos- and S. citreus; poly(PCPMA) allowed, respectively, 10, 18, ites, respectively, with clay, ZnO, palladium (Pd), and organ- and 20% growth for the species indicated above. ically modified synthetic fluorine mica were higher than The effect of homo- and copolymers of NPEMA and neat polymers. These suggest that the stronger interaction PCPMA on the growth of different fungi is demonstrated between polymer matrix and inorganic nano particles than in Fig.  8b. It is seen that the hindrance to growth by the polymer nano composites has higher value of activation poly(NPEMA) was less than their corresponding copoly- energy than the corresponding neat polymers [63, 66–68]. mers with PCPMA. The effect of poly(NPEMA) on the The activation energies of neat poly(3-hydroxy butyrate) fungi has already been indicated in the preceding section. (PHB), polyvinyl ester and nylon 6 were, respectively, 136.8, Growths of A. niger, S. pulverulentum, and T. lignorum, 186.3, and 276 kJ/mol, while the activation energies of their respectively, were 30, 20, and 34% in poly(PCPMA). The nano-composite, respectively, with Ag S, O-montmorillon- copolymers allowed 52–28, 48–28, and 58–40% growth of ite (O-MMT), and Glass fibers were found lower than neat A. niger, S. pulverulentum, and T. lignorum, respectively. polymers. This is due to the weak interaction between poly- The poly(NPEMA-co-PCPMA) and poly(PCPMA) mer matrix and inorganic nano particles [64, 65]. The lower were more effective than the poly(NPEMA) to reduce the value of kinetic and thermodynamic parameters suggests the growth of yeast (Fig. 8c). The poly(NPEMA) permitted catalytic effect arises in polymer nano composites. 40, 50, and 58% growth of S. cerevisiae, C. utilis and P. stipitis, respectively; poly(PCPMA) allowed, respectively, Antimicrobial screening 18, 32, and 28% growth of the same. The copolymers tol- erated 38–22, 50–38, and 56–40% growth of S. cerevisiae, The functional polymers having chlorine and fluorine groups C. utilis, and P. stipitis, respectively. were mostly used for antimicrobial properties. The effective- In general, poly(PCPMA) hindered the growth of all ness of homo- and copolymers of NPEMA and PCPMA to the microorganisms effectively, while the poly(NPEMA) hinder the growth of microorganisms is shown in Fig. 8. It was less effective than poly(PCPMA) and their copoly - appears that compared to poly(NPEMA) and poly(NPEMA- mers. This may be traced to the presence of chlorine in co-PCPMA), the poly(PCPMA) more effectively hinders the poly(PCPMA) and poly(NPEMA-co-PCPMA). It was microorganism’s growth. The copolymers (Fig. 8a) allowed observed that increasing the concentration of PCPMA in growth of 30–20, 32–25, and 50–38% for E. coli, B. subtilis, copolymers resulted in increase of antimicrobial properties 1 3 International Journal of Industrial Chemistry (2018) 9:153–166 163 Table 8 Activation energies for other polymer nano composites No. Polymer/polymer nano-composite Method name Activation energy References E (KJ/mol) 1. Polyamide 6 Kissinger 175 [63] Polyamide 6/clay 199 2. Poly(3-hydroxy butyrate) (PHB) Kissinger 136.8 [64] 0.05% Ag S/PHB 110.2 2 2000 0.12% Ag S/PHB 95.1 2 1000 0.5% Ag S/PHB 91.8 2 250 1.28% Ag S/PHB 94.5 2 100 2.6% Ag S/PHB 99.1 2 50 3. Polyvinyl ester Coats–Redfern 186.3 [65] Polyvinyl ester/1% O-montmorillonite (O-MMT) 173.4 Polyvinyl ester/5% O-MMT 154.9 4. Polyvinyl ester Briodo 190.2 [65] Polyvinyl ester/1% O-montmorillonite (O-MMT) 185.2 Polyvinyl ester/5% O-MMT 166.7 5. Polyethylene oxide (PEO)/polyvinyl alcohol (PVA) Coats–Redfern 101 [66] PEO-PVA/1% ZnO 122 PEO-PVA/5% ZnO 130 5. Polyethylene oxide (PEO)/polyvinyl alcohol (PVA) Briodo 159 [66] PEO-PVA/1% ZnO 164 PEO-PVA/5% ZnO 169 6. Isotactic polypropylene (iPP) Flynn-Wall 220.57 [67] iPP/0.27% Pd 227.85 7. Nylon 6 Coats–Redfern 264 [40] Nylon 6/Glass fiber 181 Nylon 6/3 5% crysnano nano-clay 219 Nylon 6/5% crysnano nano-clay 247 8. Nylon 6 Briodo 276 [40] Nylon 6/glass fiber 193 Nylon 6/3 5% crysnano nano-clay 231 Nylon 6/5% crysnano nano-clay 259 9. Poly(butylene succinate-co-adipate) (PBSA) Kissinger 159.9 [68] PBSA/OSFM (organically modified synthetic fluorine mica) 168.9 and vice versa. It was further seen that the homo- and Conclusion copolymers of PCPMA effectively hindered the growth of bacteria, while the growth of yeast and fungi was moder- The homo- and copolymers (with different monomer feeds) ately hindered. of NPEMA and PCPMA were prepared via free radical solu- Overall, the percentage of NPEMA in the copolymers tion polymerization technique. The relative intensity of dif- increased, the effectiveness of the copolymers to inhibit ferent bands (i.e., C=O group, –CH rocking vibration) in the growth of microorganisms decreased, while increase FT-IR spectra of copolymers was increased or decreased. in the percentage of monomers which have active groups This reveals that the composition of monomers in copoly- (i.e., –Cl) will increase the ability of polymers to inhibit mers was well matched. The polydispersity of homo- and the growth of microorganisms. This investigation indicates copolymers varied between 1.45 and 1.67. Nano-CdS-doped that monomers containing chlorine can be used to pre- polymer composite was prepared via in  situ technique. pare polymers which can be used as general antimicrobial The nano-CdS-doped polymer composite is characterized agents in water purification systems and food packaging by XRD and FT-IR. The XRD pattern confirms the cubic materials. structure of CdS nano particles with three reflection planes (111), (222), and (311). The FT-IR spectra of polymer nano 1 3 164 International Journal of Industrial Chemistry (2018) 9:153–166 composites confirm the weak interaction between inorganic nano particles and polymer matrix. The TGA analysis of polymers confirms that the poly(PCPMA) was more stable than poly(NPEMA-co-PCPMA) and poly(NPEMA). The values of activation energy, ∆S, ∆H, and ∆G, confirm the stability of poly(PCPMA). The values of activation energy for polymer nano composites were found lower than the neat polymers. 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