synthesis and inVestiGatiOn OF PentaGLyCidyL etheR ... · The study reported aims at synthesis, characterization, development, a viscosimetric and a rheological study of the new pentaglycidyl

Rachid Hsissou, Mohamed Berradi, M’hammed Grich, Hanane Bahaj, Mehdi El Bouchti, Mohammed Khudhair, Hicham Es-sahbany, Mohamed Rafik, Ahmed Elharfi

893

synthesis and inVestiGatiOn OF PentaGLyCidyL etheR PentaPhenOXy PhOsPhORiC POLyMeR

and FORMULatiOn OF nanOCOMPOsite (PGePPP/Mda/tiO2)

Rachid Hsissou1, Mohamed Berradi1, M’hammed Grich1, Hanane Bahaj1, Mehdi El Bouchti2, Mohammed Khudhair1, Hicham Es-sahbany3, Mohamed Rafik1, Ahmed Elharfi1

aBstRaCt

The study reported aims at synthesis, characterization, development, a viscosimetric and a rheological study of the new pentaglycidyl ether pentaphenoxy phosphoric (PGEPPP) polymer. The initial step refers to the identification of the polymer by Fourier Transform Infrared Spectroscopy (FTIR) and its chemical structure verification by proton (1H NMR) and carbon (13C NMR) nuclear magnetic resonance. The evolution of the viscosimetric behavior of PGEPPP/methanol system is followed during the second step of the investigation. Finally the rheological behavior of PGEPPP/MDA/TiO2 crosslinked by methylene dianiline and formulated by titanium oxide of different percentages is studied.

Keywords: characterization, elaboration, viscosity, rheology, polymer, nanocomposite, FTIR, NMR.

Received 02 April 2018Accepted 05 February 2019

Journal of Chemical Technology and Metallurgy, 54, 5, 2019, 893-901

1 Laboratory of Agricultural Resources, Polymers and Process Engineering (LARPPE) Team of Polymer and Organic Chemistry (TPOC), Department of Chemistry Faculty of Sciences, Ibn Tofail University, BP 133, 14000, Kenitra, Morocco 2 Laboratory REMTEX, ESITH (Hight School of Textile and Clothing Industries) Casablanca, Morocco 3 Laboratory of Materials Engineering and Environment: Modeling and Application Department of Chemistry, Faculty of Sciences Ibn Tofaïl University, B.P. 133 Kenitra, Morocco

intROdUCtiOn

Currently, the most widely used process for prepara-tion of epoxy polymers refers to condensation of epichlo-rohydrin on structures containing at least two mobile hydrogens like diacids, diamines, polyphenols and/or by oxidation of unsaturated compounds in presence of per-acids [1 - 3]. The epoxy polymers have very interesting physicochemical properties and varying viscosimetric and rheological properties [4 - 5]. This determines their wide applications in aeronautics as well in automotive, inhibition and coating industries [6 - 11]. Today, there are a large number of composite materials that are generally classified into three families depending on the nature of the matrix: organic, ceramic and metal matrix composites. The viscosimetric and rheological properties of the poly-mers and their nanocomposites have to be known for the understanding and the storage conditions control [12 - 13].

The aim of the present investigation is to synthesize, characterize and identify the viscosimetric and rheologi-cal behavior of a new pentaglycidyl ether pentaphenoxy phosphoric (PGEPPP) polymer.

eXPeRiMentaLsynthesis of pentaglycidyl ether pentaphenoxy phosphorus

The synthesis of the new macromolecular phos-phoric architecture, pentaglycidyl ether pentaphenoxy phosphorus (PGEPPP), was carried out in two steps:

First step1.818 10-3 mol of phosphorus pentachloride were

condensed with 9.090 10-3 mol of hydroquinone in presence of methanol at 100°C within 48 h C under magnetic stirring conditions. The reaction scheme is shown in Fig. 1.

second stepDuring the second step, 7.418 10-3 mol of epichlo-

rohydrin were added to pentahydroxy pentaphenoxy phosphorous at 70°C in the course of 4 h using a magnetic stirrer. The final product pentaglycidyl ether pentaphenoxy phosphorus was obtained by adding 12.787 10-3 mol of the triethylamine base at 40°C within 3 h keeping the mixture well stirred. The reaction scheme is illustrated in Fig. 2.

Journal of Chemical Technology and Metallurgy, 54, 5, 2019

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Crosslinking of PGePPP resin with methylene di-aniline

The new epoxy polymer can be converted into a thermosetting resin by adding methylene dianiline which acts as a bridging agent during the process. Methylene dianiline has a very good thermal stability and provides very good mechanical properties to the polymer [14]. It finds high technology applications. Methylene dianiline has two amine groups whose four hydrogen atoms can be substituted. The formation of a three-dimensional network usually involves condensation reactions be-tween the oxirane rings of the polymers and the amine groups of the hardener (Fig. 3). The protocol consisted of preheating the approximately stoichiometric amounts of the resin and the hardener. The methylene dianiline was placed in an oven at 120°C, while PGEPPP resin was heated to 60°C.

Calculation of the stoichiometric coefficients of PGePPP resin

Aiming to obtain optimal properties, the new pen-tafunctional phosphorus epoxy macromolecular resin was hardened in presence of methylene dianiline as a hardener at approximately stoichiometric amounts [11].

Calculation of the epoxy equivalent Weight (eeW) EEW was calculated on the ground of:

(1)( )PGEPPMwEEW = (1)

f

P

where f designated the functionality of the pentafunc-tional phosphoric epoxy resin.

(2)856EEW = (2)

5

Fig. 2. Pentaglycidyl ether pentaphenoxy phosphorus (PGEPPP).

P(Cl)5 OHHO5+ POO

OO

OOH

OH

OH

HO

HO

Methanol

48 h, 100 °C

Fig. 1. Pentahydroxy pentaphenoxy phosphorus.

POO

OO

OOH

OH

OH

HO

HO

4 h, 70 °C

3 h, 40 °C

POO

OO

OO

O

O

O

O

H2C

H2C

CH2

H2C

CH2

O

O

O

O

O

OCl5

5 N(Et)3


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Fig. 3. Crosslinking of pentaglycidyl ether pentaphenoxy phosphorus with methylene dianiline.

H2CH2N

POO

OO

OO

O

O

O

O

H2C

H2C

H2C

CH2

POO

OO

OO

O

O

O

O

H2C

H2C

CH2

H2C

CH2

O

O

O

O

O

NH2

H2C NHOH2C N

H2C N

OH

H2C N

CH2

CH2OHN

CH2

N

H2C

HO

N

CH2

OH

N

H2C

CH2

N

N

+


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EEW = 171.2 g/eq (3) (3)

Calculation of the amine hydrogen equivalent Weight (aheW)

AHEW was evaluated using the relation:

(4)M (MDA)wAHEW = (4)f

AHEW = 49.5 g/eq (5) (5)

Calculation of the weight ratio The weight of the hardener (methylene dianiline)

which was relative to that of the pentafunctional phosphorus pentepoxide resin (pentaglycidyl ether pentaphenoxy phosphorus) was calculated in majority of the cases per 100 parts of resins or PHR (Parts per Hundered of Resin).

(6)AHEWPHR (Amine) = ×100 (6)

EEW

49.5PHR (Amine) = ×100 (7)

171.2 (7)

PHR (Amine) = 29 g/eq (8) (8)

29 g of methylene dianiline reacted per 100 g of the pentaglycidyl ether pentaphenoxy phosphorus (PGE-PPP) in accordance with the calculated epoxy and amine equivalents.

Fourier transform infrared spectroscopyBRUKER Fourier transformed infrared spectrom-

eter (FTIR) was used. The light beam passed through the sample at a depth of 2 μm. The analysis was carried out in the range from 4000 cm-1 to 600 cm-1.

nuclear magnetic resonanceThe proton (1H NMR) and carbon (13C NMR) nu-

clear magnetic resonance analyzes were obtained by BRUKER AVANCE 300 MHz apparatus. Deuterated DMSO (DMSO-d6) was used as a solvent. The chemical displacements were expressed in ppm.

Properties behaviorThe viscosimetric properties of the pentafunctional

PGEPPP resin were monitored using Ubbelohd VB-1423 capillary viscometer.

Rheological propertiesThe rheological properties of the new macromo-

lecular architecture (PGEPPP) and its nanocomposites (PGEPPP/MDA/TiO2) were monitored using RHM01-RD HAAKE type rheometer.

ResULts and disCUssiOnstructural characterization of PFePPP polymerFTIR results

The structural identification of the synthesized PGEPPP is carried out by FTIR. The polymer is exposed in its vis-cous state to infrared radiation in ATR mode (Fig. 4). The allocation of the different bands of PGEPPP is pointed out in Table 1.

Fig. 4. IR Spectrum of PGEPPP polymer.


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NMR investigationThe spectrum of the proton nuclear magnetic reso-

nance of the epoxy pentaglycidyl ether pentaphenoxy phosphorus resin is shown in Fig. 5. The letters s, d, t,

Table 1. IR spectrum bands of PGEPPP polymer.

Bands υ (cm-1) Bands Allocation

3251 Variation of valence of Csp2 (aromatic C-H)

2902- 2987 Aliphatic CH2 bond elongation

1507 Variation of valence of Csp2 (aromatic C=C)

1228 Variation of binding valence C-O of aromatic ethers (Ph-O)

1040 Variation of binding valence C-O of aliphatic ethers (CH2-O)

743-829 Elongation of epoxy group

Fig. 5. Proton NMR spectrum of PGEPPP polymer.

q, and m signify a singlet, a doublet, a triplet, a quad-ruplet, and a multiplet, respectively. The assignment of the different chemical shifts of the synthesized polymer is summarized in Table 2.

Chemical shifts (ppm) Protons and interpretations

1.2 Solvent

3.1 (t ; 10H ; CH2 of oxirane)

3.5 (m ; 5H ; CH of oxirane)

4.1 (t ; 10 H ; CH2 related to oxirane)

6.8 (d ; 20 H ; aromatic CH)

Table 2. Chemical shifts of PGEPPP polymer proton NMR.


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The carbon nuclear magnetic resonance spectrum (13C NMR) of the synthesized epoxy pentaglycidyl ether pentaphenoxy phosphorus resin (PGEPPP) is shown in Fig. 6. The chemical transfer assignments of PGEPPP polymer different carbons are given in Table 3.

Viscosimetric propertiesFigs. 7 and 8 show the variation of the viscosity as

a function of the concentration and the temperature, re-spectively. The viscosimetric properties of PGEPPP are evaluated after the dissolution of the latter in methanol

reaching different concentrations (5 %, 10 % and 15 %). The viscosity of PGEPPP/methanol system is followed at temperatures ranging from 30°C to 70°C.

Fig. 7 shows that the viscosity increases with increase of the percentage mass of the polymer in PGEPPP/methanol system. This is explained with the progress of the homopolymerization reaction, since the viscosity increases with increase of the molecular weight of the solute [15 - 16].

Fig. 8 shows that the viscosity decreases with tem-perature increase. This implies that the heat released by

Fig. 6. 13C NMR Spectrum of PGEPPP Polymer.

Chemical shifts (ppm) Carbons and interpretations

46 (s; 5C; CH2 of oxirane)

53 (s ; 5C ; CH of oxirane)

68 (s; 5C; CH2 linked to oxirane)

113 (s ; Ortho aromatic C of the glycidyl group)

117 (s ; Ortho aromatic C of the O-P group)

144 (s ; aromatic C linked to phosphorus)

155 (s ; Aromatic C linked to oxygen)

Table 3. Chemical shifts of carbon NMR spectrum of PGEPPP polymer.


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the device abates the interactions between the bonds. It can be concluded that pentafunctional epoxy pentaglycidyl ether pentaphenoxy phosphorus can be transferred from a viscous to a liquid state with temperature increase [17 - 18].

storage and loss modulusFigs. 9 and 10 illustrate the storage modulus G’ and

the loss modulus G’’ of the nanocomposite (PGEPPP/MDA/TiO2) of different formulations as a function of the angular velocity. The analysis of the rheological behavior of the prepared nanocomposites is carried out at 80°C.

Fig. 9 shows the dependence of the storage modulus G’ of PGEPPP/MDA/TiO2 different formulations on the angular velocity applied. The elastic behavior increases with increase of the angular velocity and the amount of

titanium oxide incorporated in PGEPPP/MDA/TiO2 [19 - 20]. The elastic properties observed are in agreement with those observed by Lim et al. [21] for the dispersion of the charge, and by Bekhta et al. [22] who show that the rheological behavior depends on the dispersion method.

Fig. 10 shows the loss modulus G’’ of PGEPPP/MDA/TiO2 different formulations. It is evident that the vitreous behavior increases with increase of the angular velocity and the charge of titanium oxide introduced to PGEPPP/MDA/TiO2. Indeed, very interesting rheologi-cal properties are obtained upon addition of titanium oxide to PGEPPP/MDA/TiO2 [23 - 25]. The rheologi-cal (storage and modulus) behavior data is in accord with that referring to the concentration dependence of viscosity.

Fig. 7. Viscosity of PGEPPP/methanol system as a function of the polymer concentration.

Fig. 8. Viscosity of PGEPPP/methanol system as a function of the temperature.

Fig. 9. Storage modulus of PGEPPP/MDA/TiO2 different formulations as a function of the angular velocity.

Fig. 10. Loss modulus of PGEPPP/MDA/TiO2 differ-ent formulations as a function of the angular velocity.


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COnCLUsiOnsThe synthesis of a new phosphoric epoxy polymer

(PGEPPP) is described in this paper. The structure of this macromolecular binder is identified by FTIR. Its chemical structure is confirmed by 1H NMR and 13C NMR. The viscosimetric and rheological properties are studied. The viscosity decreases with temperature increase providing a transfer from a viscous to a liquid state, while the elastic behavior increases with increase of the angular velocity and the amount of titanium oxide incorporated in PGEPPP/MDA/TiO2.

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Synthesis, Structural, Viscosimetric, and Rheological Study, of a new trifunctional phosphorus epoxyde prepolymer, tri-glycidyl ether tri-mercaptoethanol of phosphore (TGETMEP). Mediterranean Journal of Chemistry, 6, 1, 2016, 665-673.

2. R. Hsissou, O. Dagdag, A. EL Harfi, Synthesis and characterization of a new octafunctional epoxy resin (Octaglicydyl tetra p-aminophenol of bisphenol A (Bis para phosphoric ester)). Viscosimetric study, Mor. J. Chem., 3, 4, 2015, 791-797.

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8. K. Selvarani, R. Mahalakshmi, A Review on Physical and Chemical Properties of L-Phenylalanine Family of NLO Single Crystals; Inter. J. ChemTech Resea., 9, 1, 2016, 113-120.

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13. Q. Chen, R.H. Colby, Linear viscoelasticity of oligo-meric sulfonated styrene near the sol-gel transition, Korea–Aust. Rheol. J., 26, 2014, 257-261.

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synthesis and inVestiGatiOn OF PentaGLyCidyL etheR ... · The study reported aims at synthesis, characterization, development, a viscosimetric and a rheological study of the new pentaglycidyl