American International Journal of Research in Formal, Applied & Natural Sciences

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1 American International Journal of Research in Formal, Applied & Natural Sciences Available online at ISSN (Print): , ISSN (nline): , ISSN (CD-RM): AIJRFANS is a refereed, indexed, peer-reviewed, multidisciplinary and open access journal published by International Association of Scientific Innovation and Research (IASIR), USA (An Association Unifying the Sciences, Engineering, and Applied Research) Synthesis and Characterization of Copoly (Azo-Maleimide Acrylonitrile / Vinyl Acetate) and Terpoly (Azo-Maleimide Acrylonitrile Vinyl Acetate): Studies on Influences of Reaction Feed Compositions on Thermal and Microbial Behavior Jyoti Chaudhary 1, Suman Jinger 1, Swati Purohit 2 Department of Polymer Science, Mohan Lal Sukhadia University, Udaipur (Rajasthan), India Abstract: Polyvinyl and acrylates are the common stars of mostly synthesized polymers but their glass transition temperature (Tg) occupied in range of 30 o C to 100 o C, which are leads to limits their applications. In this paper, improvement of their Tg was done via increases of their chain interaction to redesigned with chain flexibility in basic structure via copolymerization and terpolymerization using free radical as a reaction propagator in THF solvent at suitable temperature. Furthermore, the polymerization was studied in the context of different feed ratios of comonomers and analyzed influences of the thermal conditions on copolymers and terpolymer on the basis of in merged comonomer units, respectively. The synthesized polymer compounds were also subjected to in vitro antimicrobial studies with selective bacterial and fungal microorganisms. The synthesized monomer and polymers were characterized by elemental, physical and spectral analysis techniques such as C/H/N analysis, density, viscosity analysis and molecular weight by GPC, FTIR and 1 H-NMR spectral analysis. The thermal stability, glass transition temperature and Reactivity Ratios of polymers were also determined by TGA, DSC techniques and by N% analysis respectively. Keywords: Glass transition temperature (Tg), Copolymer, Terpolymer, TGA, Thermal stable, Reactivity Ratios. I. Introduction High performance polymers with high glass transition temperature are paid strong attraction in polymer industries because of their great economic rewards that may arise from their wide and potential applications [1]. As intimate above two important and lead factors, one is Tg of polymers and second is, chain flexibility revealed by copolymerization or terpolymerization and that is the best route to change both of the factors [2], [3]. In this sequence, polymerization of maleimide moiety with hetero-comonomer units used as base frame which is existed with high Tg value but maleimide and their polymers, itself limits their wider applications due to their rigidness property [4],[5],[6]. To overcome this limitation, addition typed N-substituted maleimide and their derivatives were used in polymerization with different comonomer units to establish flexibility in rigid-structure and to achieved better polymers with desired features included antimicrobial specialties [7-11]. In the present study, we are mainly focused on the synthesis of thermally stable, microbial resist and flexible copolymers and terpolymer of N- substituted maleimide having comonomers such as acrylonitrile and vinyl acetate and to investigate their applicability s, will used as high performing materials in related areas. In this paper, we are reported the preparation of homopolymer 4-N-Phenylethanamide azo-3-n-(4-nitrophenyl)maleimide [HPAMI], copolymers [4-N-Phenylethanamide azo-3-n-(4-nitrophenyl)maleimide-co-acrylonitrile] [C 1PAMI], [4-N- Phenylethanamide azo-3-n-(4-nitrophenyl)maleimide-co-vinylacetate][c 2PAMI] and terpolymer [4-N- Phenylethanamideazo-3-N-(4-Nitrophenyl)Maleimide-Acrylonitrile-Vinyl acetate] [TPAMI] using AIBN as a free radical initiator and THF as organic polar solvent. II. Experiments Material and Methods: P-amino acetanilide, maleic anhydride were supplied by Loba Chemei with AR grade, THF, DMF and methanol were used as solvents provided by Sigma Aldrich, AR graded. AIBN (Fisher Scientific) was used as initiator and purified by recrystallization in methanol and dried under vaccum before use. In all experiments, distilled and deionized water was used. Synthesis of N-(4-N-phenyl ethanamide) maleimide [PEMI] monomer and Polymers: The N-(4-N-phenyl ethanamide) maleimide PEMI (I) was prepared by the reaction of 4-amino acetanilide (0.1 mol) and maleic anhydride (0.1 mol) according to reported method [12].The monomer N(4-N- phenyl ethanamide azo 3-N-(4-nitro phenyl)maleimide [PAMI] (II) was synthesized by diazotization reaction followed two steps mechanism [Scheme 1]. Polymerization for preparation of homopolymer, Copolymer(s) and terpolymer were AIJRFANS ; 2015, AIJRFANS All Rights Reserved Page 70

2 carried out by using THF as a solvent and AIBN as an initiator at o C [Scheme 2, 3, 4]. btained polymers appearance are brick red/ reddish-brown color. Scheme 1: Synthesis of Monomer [PAMI] Synthesis of monomer: 4 -N -Phenylethanamide azo -3 -N -(4 -nitrophenyl) maleimide [ PAMI ] Step 1: DMF, Stirr. + 4 hrs. CH 3 CHN NH 2 NH CH DMF, C conc.h 2 S 4, P 2 5 N NHCCH 3 NHCCH 3 Maleic anhydride 4 -Aminoethanamide Maleamic acid 4- N - Phenylethanamide Maleimide [ PMI ] Step 2: N + NH 2 HCl / C N NaN 2 N 2 N N N 2 NHCCH 3 NHCCH 3 [PMI] 4 - Nitro aniline Scheme 2: Synthesis of Homopolymer [HPAMI] [PAMI] Scheme 3: Synthesis of Copolymers: [C1PAMI] and [C2PAMI] Scheme 4: Synthesis of Terpolymer:[TPAMI] AIJRFANS ; 2015, AIJRFANS All Rights Reserved Page 71

3 Yield of Polymerization: The percentage yield was depends on the providing chemical environment. To get maximum yield of polymer products, applied different solvent-initiator pairs. Resultant, It was observed that the percentage yield in THF- AIBN system is high as compared to DMF, 1,4- Dioxane solvents and BP initiator. Characterization: III. Results and Discussion The synthesized compound s structures were confirmed by Infrared spectral analysis (FTIR). The spectral data of synthesized monomer, homopolymer, copolymers and terpolymer were recorded on a FTIR Perkin Elmer spectrometer mode RX-I using KBr pellets for sample preparation. The spectrum information was collected in the range of cm -. In contemporary, 1 H-NMR spectral technique was also used to confirm structures of monomer, homopolymer, copolymer and terpolymer. The 1 H- NMR spectral data was recorded in DMS-d6 with TMS as an internal standard reference. Spectra and Spectral values are shown in [Table 1] and [Fig.1-4]. The peak of double bonded carbons in five membered heterocyclic imide ring was disappear in homopolymer, copolymers and terpolymer pervasive the polymerized and unpolymerised units and enable to polymerization in concern compounds at double bonded carbon atoms. Table 1: FT-IR and 1 H-NMR spectral data of PAMI, HPAMI, C1PAMI, C2PAMI and TPAMI Technique PAMI HPAMI C1PAMI C2PAMI TPAMI Characteristics FT-IR (CM -1 ) 1 H-NMR (ppm) N-H Stretch of amide C= Sym. & Asym. stretch of imide C-C stretch of CH=CH C= Stretch of amide C-N-C stre. of N Subs. maleimide C-H stretch of aromatic CH=CH N=N stretch in aromatic 1407, , , , ,1314 -N 2 Asym. And sym. Stretch P-substituted Ar rtho- substituted Ar 7.69, , , , ,7.09 Phenyl proton of rtho to N of imide Phenyl proton of Meta to N of imide Azo Subs. Phenyl proton of rtho to N=N-C Azo Substituted Phenyl protons of Meta to N=N-C CH (CH=CH) [CH-CH] n CNH AIJRFANS ; 2015, AIJRFANS All Rights Reserved Page 72

4 Fig. 1 FT-IR Spectra of (a) PAMI monomer (b) H-PANMI Fig. 2 FT-IR Spectra of (a) C1PAMI (b) C2PAMI (c) TPAMI Fig. 3 1 H-NMR spectra of (a) PAMI monomer (b) HPAMI Fig. 4 1 H-NMR spectra of (a) C1PAMI (b) C2PAMI (C)TPAMI Physical properties: Physical properties of synthesized products were examined on the bases of various parameters such as solubility, viscosity, density and melting point etc. Solubility of homopolymer, copolymers and terpolymer was examined in our laboratory by using various polar organic solvents such as acetone, toluene, CCl 4, chloroform, methanol, ethanol, THF, DMF, DMS, 1,4-dioxane, ethyl acetate, acetic acid etc. Result was seems that these were perfectly soluble in THF, DMF, DMS and partially soluble in acetone, 1, 4 dioxane and ethyl acetate. Viscosity and density were determined and the result are illustrated in Table [2]. Molecular weight was also measured by Gel Permeation Chromatography (GPC) technique. The molecular weight distribution in polymers varies from very low to very high range of molecular weight. Polydispersity index of all polymers were also determined by same technique. Terpolymer reveals high molecular weight due to presence of three comonomer units to create dense molecular structure. The number average molecular weight (M n), weight average molecular weight (M w) and Polydispersity (M w/m n) are given in [Table 2] Table 2: Density, IntrinsicViscosity, Molecular Weight of HPAMI, C1PAMI, C2PAMI, TPAMI Polymer Code ρ(g/cm 3 ) ɳ(dl/g) M n M w PDI(Poly Dispersity Index) HPAMI C1PAMI C2PAMI TPAMI IV. Copolymer composition and reactivity ratios Free radical copolymerization of two monomer compositions are usually described in term of reactivity ratios. Monomer reactivity ratios r 1 and r 2 were determined by preparation of different feed ratios of comonomers and the measurement of N% which is calculated by experimentally to finding monomer composition, which is used as the measurement of the tendency to form sequences of a particular monomer to alternate in a regular pattern or to be statistically random. The copolymer composition were calculated according to the Fineman Ross (FR) AIJRFANS ; 2015, AIJRFANS All Rights Reserved Page 73

5 method. The FR parameters for PAMI monomer and acrylonitrile (AN) were calculated by plotting the relation between X1 2 (F1-1)/F1 (1-X1) 2 and X1(1-2F1)/ (1-X1)F1 [Table 3]. As r 2 value is less than r 1, the results indicates that PAMI monomer is more reactive than AN comonomer and r 1r 2 = , are not close to zero, this is implies that monomers tend to form random distributed copolymers. From the resultant value of the experiments r 1r 2 value, shown the pattern of copolymer is random in polymer chain [Table 4]. Table 3: Parameters for Fineman-Ross Methods to Determine Reactivity Ratios in Copolymer of C1PAMI Code Mole Ratio Feed W% of C1PAMI Mole Fraction of C1PAMI Finemann Ross Method x 1:x 2 % N Feed X 1 Copolymer X 2 1 (F1-1) / F1 (1-X1) 2 X1(1-2F1) / (1 - X1)F1 F 1 C1PAMI-1 1: C1PAMI-2 3: C1PAMI-3 5: C1PAMI-4 7: C1PAMI-5 9: Table 4: Reactivity ratios of Monomers Polymer Code Reactivity Ratios(Finemann-Ross Method) r 1 r 2 r 1.r 2 C1PAMI V. Thermal Studies The thermograms of homopolymer, copolymers and terpolymer are shown in [Fig.-5] and the TG data are presented in Table [5]. The thermal analysis has done on perkinelmer pyrisl TGA with thermal range of 30 o C to 1000 o C. The analysis was accelerated by heating rate of 10 o C / min. in static inert atmosphere of nitrogen. The results of percentage weight loss suffered from 200 o C to 700 o C at 100 intervals are furnished in [Table 5]. All polymer decomposed by continuous degradation mechanism according to the resultant thermograms and shown excellent stability towards high temperature. [Table 5][Fig. 5]. DSC analysis was also performed on NETZSCH DSC 204. The Tg-value for homopolymer, copolymers and terpolymer were summarized in [Table 6]. The Tg value also concluded the terpolymer having significance glass transition point with following flexibility in polymeric rigid backbone due to mixing of acrylonitrile and vinyl acetate. A comparison of Tg-values of the present terpolymer [TPAMI] and copolymers [C1PAMI], [C2PAMI] showed significant observation in thermal behavior. It was intimated that incorporation of synthesized N-substituted maleimide unit in vinyl acetate (VA) and acrylonitrile (AN) has increased Tg value of copolymer of maleimide-vinyl acetate from 30 o C (polyvinyl acetate) to o C and copolymer of maleimide-acrylonitrile from 95 o C (Polyacrylonitrile) to o C according to literature. maleimide itself tinted the flexibility due to the addition of soft-behaved comonomers VA / AN and it was significantly demonstrated a valuable changes in low temperature stable objects to revealed good thermal stability and also create flexibility in highly rigid spine of maleimide polymers. Resultant, flexibility/softness of vinyl acetate and acrylonitrile and the thermal susceptibility of maleimide, collaborated to each other s and supported against individual drawbacks of rigidity of maleimide groups and low thermal stability of VA/AN to tailored high performing copolymer and terpolymer than their homopolymers comparatively. Table 5: Percentage weight loss of HPAMI, C1PAMI, C2PAMI and TPAMI at Various temperature range from the TGA Polymer Code Weight loss (%) C C C C C C HPAMI C1PAMI C2PAMI TPAMI Table 6: Thermal Behavior of HPAMI, C1PAMI, C2PAMI and TPAMI Polymer Code HPAMI C1PAMI C2PAMI TPAMI Tg in o C Delta Cp* in J/g*K AIJRFANS ; 2015, AIJRFANS All Rights Reserved Page 74

6 Zone of inhibition in mm Zone of inhibition in mm Jyoti et al., American International Journal of Research in Formal, Applied & Natural Sciences, 13(1), December, 2015-February, 2016, Fig. 5 TGA Thermograms of (a) HPAMI (b) C1PAMI (c) C2PAMI (d) TPAMI VI. Microbial Activity In sequence to examine the microbe s activity of the synthesized homopolymer, copolymers and terpolymer were tested by disc diffusion technique involving the cultures of selected organisms such as Esherichia aerogenes, Staphylocous aureus bacteria for 24 h and the cultures also designed for fungi as Aspergillus nizer, Alternaria solani using DMS as solvent with 500 μg/ml sample concentration. Synthesized Polymers revealed good antibacterial and antifungal activities against used bacteria and fungi. The antimicrobial activity of homopolymer, Copolymers and terpolymer were shown due to presence of heteroatom matrix in polymers. [Table 7, 8] [Fig.6, 7]. Table 7: Antibacterial activity of HPAMI and C1PAMI, C2PAMI and TPAMI against bacteria Esherichia aerogenes, Staphylococus aureus Code 500(μg/ml) Concentration of compound taken Zone of Inhibition For E.coil(mm) Zone of inhibition for P.aerogenosa(mm) HPAMI C1PAMI C2PAMI 7 8 TPAMI Table 8: Antifungal activity of HPAMI, C1PAMI, C2PAMI and TPAMI against fungus Aspergillus nizer, Alternaria solani Code 100(μg/ml) Concentration of compound taken Zone of Inhibition For A. nizer(mm) Zone of Inhibition For A. solani (mm) HPAMI C1PAMI C2PAMI 9 10 TPAMI HPAMI C1PAMI C2PAMI TPAMI Type of Bacteria E.coil P.aerogenosa HPAMI C1PAMI C2PAMI TPAMI Type of Fungi A. nizer A. solani Fig. 6 Antibacterial activity of polymers Fig. 7 Antifungal activity of polymers VII. Conclusion Monomer and all polymers were prepared successfully using a free radical polymerization technique followed by addition polymerization mechanism. The structures of HPAMI, C1PAMI, C2PAMI and TPAMI were confirmed by various spectral, elemental, physical analyses such as FTIR, 1 H-NMR, C/H/N-elements detections, GPC, solubility, viscosity and density measurements. The thermal properties were also investigated by TGA and DSC techniques. C1PAMI, C2PAMI and TPAMI exhibited good thermal stability and Tg value with sustain flexibility AIJRFANS ; 2015, AIJRFANS All Rights Reserved Page 75

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