In this work, we synthesized a new octafunctional epoxy resin: Octaglicydil tetra p-aminophenol of bisphenol A (Bis para phosphoric ester) (OGTPAPBABPPE). This resin was synthesized in three steps. The first step is intended to condense the phosphorus trichloride and the bisphenol A; the second step was to introduce an aromatic spacer arm between the major epoxide functions and the nucleus of bisphenol A, by reacting p-aminophenol in the precursor dichloride phosphorus bisphenol A; in the third step, we functionalized the latter by the epichlorohydrin.The obtained resin was very viscous and brownish. The latter was characterized by infrared Fourier transform spectroscopy (FTIR), and its chemical structure was also confirmed by proton nuclear magnetic resonance of 1H, 13C atoms and phosphorus 31P (1H NMR, 13C NMR, 31P NMR). The study of viscosi-metric properties was carried out by the viscometer of Ubbelohd type

Dagdag, O.

EL Harfi, A.

Hsissou, R.

English

Revues Scientifiques Marocaines

Hsissou & al. / Mor. J. Chem. 3 N°4 (2015) 791-797  791     Synthesis and characterization of a new octafunctional epoxy resin (Octaglicydil tetra p-aminophenol of bisphenol A (Bis para phosphoric ester)). Viscosimetric study.  R. Hsissou, O. Dagdag and A. EL Harfi   Laboratory of  Agroresource, Polymer and Process Engineering (LAPPE), Team of Organic and Polymer Chemistry (TOPC), Faculty of Science, University Ibn Tofail, BP133, 14000, Kenitra, Morocco.  *Corresponding author. E-mail:  r.hsissou@gmail. com  Received 15 Jul 2015, Revised 03 Oct 2015, 01 Nov 2015  Abstract   In this work, we synthesized a new octafunctional epoxy resin: Octaglicydil tetra p-aminophenol of bisphenol A (Bis para phosphoric ester) (OGTPAPBABPPE). This resin was synthesized in three steps. The first step is intended to condense the phosphorus trichloride and the bisphenol A; the second step was to introduce an aromatic spacer arm between the major epoxide functions and the nucleus of bisphenol A, by reacting p-aminophenol in the precursor dichloride phosphorus bisphenol A; in the third step, we functionalized the latter by the epichlorohydrin. The obtained resin was very viscous and brownish. The latter was characterized by infrared Fourier transform spectroscopy (FTIR), and its chemical structure was also confirmed by proton nuclear magnetic resonance of 1H, 13C atoms and phosphorus 31P (1H NMR, 13C NMR, 31P NMR). The study of viscosi-metric properties was carried out by the viscometer of Ubbelohd type.   Keywords: Epoxy polymer; precursor; viscosi-metric properties; aromatic spacer arm.  1. Introduction  The epoxy thermoset polymers are widely used as hyperliants macromolecules in the formulation of composite materials because they represent the best compromise for an operating temperature which is about 150 ° C continuously [1-2] .The most widely used method for the preparation of epoxy pre-polymers is done by glycidylation via the condensation of epichlorohydrin to structures containing at least two mobile hydrogens of the type: diacids [3], diamines [4], polyphenols [5-6]. The epoxy resins (ER) are important in the industry thanks to the many properties they offer and the implementation they facilitate. Their use touches several areas especially electronics, sport, leisure, coatings (paints, varnishes, adhesives...) And composites, etc…[8]. The knowledge of the rheological properties of thermoset materials on a wide range of temperature is necessary for understanding and mastering the conditions of storage [9], and to link the performance and the product quality to the conditions of implementation and properties of the material. The rheological properties can directly be related to the chemical structure or the degree of conversion of polyepoxy prepolymers [10]. In this study, we are mainly interested in the rheological property of viscosity Hsissou & al. / Mor. J. Chem. 3 N°4 (2015) 791-797  792  since it plays a crucial role in the flow phenomenon of the organic matrix. The synthesized resin was characterized by IR and NMR and we subjected it to a viscosi-metric study based on the influence of temperature on the system of resin / solvent [11].          2. Materials and methods  2.1. Materials 2.1.1. Products used In this work, we used various products among which we have bisphenol A, phosphorus trichloride, p-aminophenol, epichlorohydrin and triethylamine. These products have been marketed by Aldrich Chemical Co.  2.1.2. Synthesis The synthesis of OGTPAPBABPPE epoxy resin was performed in three steps:  2.1.2.1. The first step The condensation of Phosphorus trichloride on bisphenol A in the presence of ethanol under magnetic stirring at room temperature for 48h. CCH3CH3OHHO 2 POCl348 hCCH3CH3OO PPOOClClClCléthanol(I)  Figure 1. Synthesis of Bis dichloride of phosphorus oxide of Bisphenol A  2.1.2.2. Step two We activated the spacer arm which is p-aminophenol in the compound (I) at room temperature for 24h. By the arm of the amino para phenol (2), we performed a reaction of condensation of 4 mol of the latter on 1 mol of the compound (I) obtained in the first step. In order to obtain tetra para amino phenol (bis para phosphoric ester) (II), we have the following reaction: CCH3CH3OO PPOOClClClCl24 h NH2HO4CCH3CH3OO PPOOOOOOH2NH2NNH2NH2(I)(II)  Figure 2. Synthesis of tetra para amino phenol of bisphenol A (bis para phosphoric ester)  Hsissou & al. / Mor. J. Chem. 3 N°4 (2015) 791-797  793  2.1.2.3. Third step  During the third step, we functionalized the compound (II) by épichlorydrine under magnetic stirring at 70 ° C for 4 hours. The final product octaglycidil tetra para amino phenol of bisphenol A (Bis para phosphoric ester) is obtained by adding the base of triethyl aminesous with magnetic stirring for 4 h at 40 ° C. CCH3CH3OO PPOO8 H2C CH ClONEt3 T=40°C 4 hOO OOT=70°C4 h2) 1)NNNNCH2CH2CH2CH2H2CH2CH2CH2COOOOOOOO(II)   Figure 3. Synthesis of octaglycidil tetra para amino phenol bisphenol A (Bis para phosphoric ester)  2.2. Methods used We used several methods among which we quote:  2.2.1. Infrared Spectroscopy of Fourier Transform (FTIR) The IR spectrometer used is a Fourier Transform Spectrometer (FTIR) BRUKER. The light beam passes through the sample to a thickness of about 2 microns. The analysis is performed between 4000 cm-1 and 600 cm-1.  2.2.2. Nuclear Magnetic Resonance (NMR) The analyses 1H NMR, 13C and 31P have been obtained using an apparatus of 300 MHz Bruker AVANCE, the solvent CDCl3 and the Chemical displacements are expressed in ppm.  2.2.3. Viscosimetric analysis Viscosity measurements were made using a Ubbelohd type viscometer. The selected measurement conditions are:  The viscometer of 1b size for a series of dilution, capillary tube, constant k = 0.051493.  The measure’s temperature in ° C: 30; 35, 40,45, 50, 55, 60, 65 and 70  Number of measurement: 3 each time  Solvent: Ethanol  Hagenbach correction was calculated using the formula specified in DIN 51562 standard 1January1999 (Measurement of kinematic viscosity by means clustering of the Ubbelohd viscometer). Hsissou & al. / Mor. J. Chem. 3 N°4 (2015) 791-797  794   Dissolubility of epoxy resin pre-polymers in ethanol was done at 20 ° C with magnetic stirring.  2.2.3.1. Sample preparation To determine the viscosi-metric behavior of the standard (OGTPAPBABPPE) epoxy resin, we dissolved the resin in ethanol at different concentrations (5%, 10% and 15%). Next, we studied their viscosities using a capillary viscometer of Ubbelohd types at varying temperatures going from 30 ° C to 70 ° C.   3. Results and Discussions  3.1. Spectral characterization of the synthesized epoxy resin We performed structural analysis of the resin synthesized by Fourier Transform Infrared spectroscopy (FTIR) and confirmed the results by proton nuclear magnetic resonance (1H NMR), carbon (13C NMR) and phosphorus (31P NMR ). The letters s, d, t, q and m mean singlet, doublet, triplet, quadruplet and multiplet. The results of structural analyzes, given below, confirmed the structure of the synthesized epoxy resin.  3.1.1. Fourier Transform Infrared Spectroscopy (FTIR)   Figure 4.  IR spectrum of the resin synthesized octaglycidil tetra para amino phenol of bisphenol A (Bis para phosphoric ester).  The band 2980 cm-1 corresponds to the C-H bond, 1650 - 1450 cm-1 confirms the existence of C = C of aromatic compound by consulting the region of = C-H beyond 3000 cm-1, between 1400 - 1450 cm -1 which corresponds to the C-H bond of CH3, 1050 cm-1 which corresponds to the C-O bond, 1220-1150 cm-1 corresponds to the CN bond, 840-950 cm-1 which corresponds to the epoxy group and 2600-2480 cm-1which Corresponds to P = O.  3.1.2. Nuclear Magnetic Résonance NMR: Octaglicy diléther p-aminophenol phosphorus trichloride bisphenol A.   Hsissou & al. / Mor. J. Chem. 3 N°4 (2015) 791-797  795  3.1.2.1. NMR 1H  Figure 5. Proton NMR spectrum of the synthesized resin octaglycidil tetra para amino phenol of bisphenol A (Bis para phosphoric ester)  1.4 (s, 6Ha; CH3); 6.5-7 (s, 24Hb, c, d, e, aromatic H); 2.9 (m, 8HF, H oxirane); 2.4 (d 16Hg, CH2 oxirane) 3.1 (d, 16Hh, CH2 linked with oxirane).  3.1.2.2. NMR 13C  Figure 6. NMR spectrum of Corbone 13 of the resin synthesized octaglycidil tetra para amino phenol of bisphenol A (Bis para phosphoric ester)  46.2 (s, CH2 oxirane); 47 (s, CH2 linked with oxirane); 34.5 (s, CH3); 50.7 (s, tertiary carbon); 155.9 (s, aromatic tertiary carbon linked  to oxygen), 51.8 (s, oxirane CH); 130 (s, aromatic CH).  3.1.2.3. NMR 31P  Figure 7. NMR spectrum of the Phosphor of the synthesized resin octaglycidil tetra para amino phenol of bisphenol A (Bis para phosphoric ester).  Hsissou & al. / Mor. J. Chem. 3 N°4 (2015) 791-797  796  2.4 (s, O = P (OR) 3).  3.2. Viscosimetric behavior 5% 10% 15%0,00,51,01,52,02,5Viscosity (Pa.s)Concentration (Pourcentage massique) 30°C 35°C 40°C 45°C 50°C 55°C 60°C 65°C 70°C Figure 8. Variation of viscosity as according to different concentrations  In the different viscosity curves of the epoxy resin in ethanol, tetra octaglycidil para amino phenol of bisphenol A (Bis para phosphoric ester), we found that the viscosity values increase with the mass concentration. This demonstrates the progress of the homopolymerization reaction since the viscosity increases with increasing molecular weight of the solute. This may be related to chemical transformations of the [12-13-14] resin. The following causes might be cited: • The addition of epichlorohydrin was not complete because of the steric hindrance of NH2 groups; • The intervention of opening reactions of regenerated epoxide cycles; An abnormality of addition of epichlorohydrin on the amine which can be represented schematically by the following reaction:  Figure 9. The addition of the epichlorohydrin on the amine. All these factors, can influence the functionality of the obtained product, therefore, we would have residual and hydroxyl amines presenting labile protons which may be responsible to a self-crosslinking of the prepolymer by acting as a hardener   4. Conclusion In this work, we have synthesized a new octa-functional epoxy resin. The  microscopic characterization of the synthesized epoxy resin was confirmed by themicrostructure study (infrared spectroscopy of Fourier transform (FTIR), and nuclear magnetic resonance (NMR)). The viscosimetric study of the obtained octa-functional resin was determined by the Ublond viscometer type. This viscosimetric study allowed us to have a clear idea on the rheological properties involved during the rise in temperature of the epoxy resin. It must still be noted that the rheological characterization of the epoxy resin is made difficult by the reactive chemical structure of the prepolymer. However, through the knowledge of the structure of the resin initially performed by IR and NMR, the rheological properties are correlated to the chemical structure of the epoxy resin.  Hsissou & al. / Mor. J. Chem. 3 N°4 (2015) 791-797  797  References  [1] L. S. Penn and T. T. Chiao. Hand Book of Composites (Ed G. Lubin), Van Nostrand Reinhold, New York, 57 (1982). [2] G. Christian. Composite Materials, Technology and Docummentation (Lavoisir), Paris, (1986) 107. [3] Schrade P. Brevet allement no. 1,176,122, (1965). [4] Bruneau, Lesec J. Brevet francais no. 1,562,200, (1969). [5] Castan P. Brevet anglais no. 518,057, (1933). [6] Castan, P. Brevet anglais no. 579,698, (1934). [7] R. Hsissou, Y. El rhayam & A. El harfi. Inter. J. of Innov. and App. Stu. 7 (2014) 674-682. [8] S. Fetouaki, A. Elharfi, L. Belkebir, Eur. Polym. J., 38 (2002) 787-793. [9] M. A. 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Synthesis and characterization of a new octafunctional epoxy resin (Octaglicydil tetra p-aminophenol of bisphenol A (Bis para phosphoric ester)). Viscosimetric study.

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Synthesis and characterization of a new octafunctional epoxy resin (Octaglicydil tetra p-aminophenol of bisphenol A (Bis para phosphoric ester)). Viscosimetric study.

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