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Advances in Environmental Biology, 8(8) 2014, Pages: 2709-2713

AENSI Journals

Advances in Environmental Biology

Journal home page: http://www.aensiweb.com/AEB/

Corresponding Author: Razif Nordin, University Technology MARA, Department of Chemistry, Faculty of Applied

Science, 40450. Shah Alam, Selangor and 02600 Arau, Perlis, Malaysia.

Phone numbers (+6019-5665348) e-mail address: [email protected]

Synthesis and characterization trihydroxyl polybenzoxazine precursor for Post-Polymer Modifications 1,2Razif Nordin, 1M.B.Mohd Nazir, 3M.Z.Ahmad Thirmizir, 1,2A.M. Md. Jani

1Department of Chemistry, Faculty Applied Sciences, University Technology MARA, 02600 Arau, Perlis, Malaysia. 2Department of Chemistry, Faculty Applied Sciences, University Technology MARA, 40450 Shah Alam, Selangor,Malaysia. 3Science and Engineering Research Centre, Engineering Campus, University Sains Malaysia, 14300 Nibong Tebal, Pulau Pinang,

Malaysia.

A R T I C L E I N F O A B S T R A C T

Article history:

Received 28 February 2014

Received in revised form 25 May 2014 Accepted 6 June 2014

Available online 20 June 2014

Keywords:

Benzoxazine, Fourier transform-infra

red, Nuclear magnetic resonance

Owing to the great advancement in technology, the input/output terminals in electronic

packaging have greatly increased resulting to a proportional increase in solder

interconnection joints of electrical components. Therefore, in order to work in line with the mission and vision of the electronic industries which are the production of more

powerful, efficient and miniaturized gadgets, it is imminent to introduce alloying

elements to the existing lead free conventional solders which will possibly lead to the enhancement of electrical and mechanical properties of the interconnection joints. An

attempt has been made to reveal an element of desirable properties which can meet the

demands of the micro systems and electronics industries. A documentation of the benefits that the carbon nanotubes CNTs can yield has been presented in previous

studies which therefore serve as the primary reason for embarking on this review report.

© 2014 AENSI Publisher All rights reserved.

To Cite This Article: T.T. Dele-Afolabi, M.A. Azmah Hanim, M. Norkhairunnisa, H.M. Yusoff., Physical and Mechanical Properties

Enhancement of Lead Free Solders Reinforced with Carbon Nanotubes: A Critical Review. J. Appl. Sci. & Agric., 8(8), 2709-2713, 2014

INTRODUCTION

Nowadays, much research works have been concentrated on synthesized benzoxazine derivatives [2]

Benzoxazine monomers are heterocyclic compounds which may be synthesized by reacting a primary amine,

phenolic compound and formaldehyde. These monomers are polymerized by ring opening polymerization in the

absence of a catalyst leading to complex polybenzoxazine compounds.

Polybenzoxazine is very attractive phenolic resins because of its mechanical and thermal properties suitable

for high performance applications [1]. However, benzoxazine had some shortcomings such as brittleness, poor

shelf life and some formation of micro voids or holes during curing process. Nevertheless, they offer greater

flexibility than conventional phenolic resins in terms of molecules design.

Polybenzoxazine with complex network formation can be simply synthesized by introduce silane coupling

agents as a monomer [3,6,5]. An Amino–silane coupling agent is selected in this work as polyfunctional

monomer to enable formation silanol groups with better flexibility of network to overcome the brittleness of

polybenzoxazine based on aniline. Furthermore, silane coupling agents exhibit outstanding thermal stability,

mechanical strength and unique chemical properties.

In this work, benzoxazine aminepropyltrihydroxylsilane (B-z(OH)3) monomer were synthesized based on

classical benzoxazine system using on bisphenol A and paraformaldehyde. The chemical structure of (B-

z(OH)3) was investigated with proton magnetic resonance spectroscopy (1H NMR) and Fourier transform-infra

red (FT-IR).

Methodology:

Materials:

Bis(3-phenyl-3,4-dihydro-2H-1,3-benzoxazinyl)isopropane or Bisphenol-A as a standard benzoxazine

monomer, paraformaldehyde (99%), Tetrahydrofuran (THF), aniline (99%) and 3-aminopropyltrimethoxysilane

(98%) were obtained from Sigma Aldrich Co. Anhydrous Sodium sulfate A.R. was purchased from Bendosen

Lab. Chem.

2710 T.T. Dele-Afolabi et al, 2014


Synthesis of monomer benzoxazinel aminepropyltrihydroxylsilane:

Into 250 mL round-bottom flask containing 80 mL chloroform, bisphenol-A (9.1316 g, 100.0 mmol), 3-

aminopropyltrimethoxysilane (13.9661 g, 200 mmol), paraformaldehyde (5.1051 g, 400 mmol) were added. The

mixture was gradually heated to reflux with stirring, which became homogenous within ca. 30 min. The

transparent solution was kept under reflux for 5 h at the temperature of 85oC. The reaction mixture was allowed

to cool down to room temperature to afford transparent solution. The solution was washed with 4L distilled

water. Sodium sulfate was added and kept for 24 h as a drying agent. After the drying agent was filtered, it was

followed by evaporation of chloroform under vacuum to afford pale yellow transparent liquid (20.52g, 72.6%).

Fig. 1: Schematic representation of the synthesis and curing of B-z (OH)3.

Proton Nuclear Magnetic Resonance (1H NMR) Spectroscopy:

H NMR spectra were recorded on a Bruker Avance 300 MHz NMR operating at a proton frequency of 300

MHz. The relaxation time used in this study was 2 s. Chemical shifts are reported in part per million. deuterated

chloroform was used as a solvent and tetramethylsilane was used as an internal standard.



Fourier Transform Infrared Spectroscopy:

Chemical characterization was performed using a NICOLET-380 Fourier transform infra-red SMART

PERFORMANCE spectrometer with 32 scans at resolution of 4cm-1

and a frequency range of 4000 – 600 cm-1

.

Each B-z(OH)3 was finely ground with KBr powder and pressed into a disk and scanned by FTIR spectrometer.

Results:

Fig. 1: IR spectra of B-z(OH)3 monomer.

Fig. 2: 1H NMR result of monomer B-z (OH)3



cm-1

100015002000250030003500

Tra

nmit

tanc

e (%

)

1499

1499

1499

1499

1086

1086

1235

1235

1235

927

927

927

1634

1031

a

b

c

d

Fig. 3: IR spectra of B-z(OH)3 monomer after each cure stages: 50 (a), 100 (b) , 150 (c) and 230

oC (d)

Discussion:

Characterization Monomer B-z(OH)3:

The chemical structure of the B-z(OH)3 monomer was confirmed by FT-IR and 1H NMR.

FT-IR analysis:

Fig. 1 shows the FTIR spectrum of synthesized B-z(OH)3. The characteristic free stretching of hydroxyl

group of silane structure region can be found around 3600 – 3200 cm-1

. The C-H stretching of CH3 is shown by

strong band around 3000 – 2800 cm-1

. The antisymmetric and symmetric CH2 bands can be found in the region

of 1490 – 1460 cm-1

and 1370 – 1250 cm-1

, respectively. The band around 1497 – 1495 is attributes to the tri-

substituted benzene ring mode in the oxazine structure. The antisymmetric and symmetric C-N-C stretching

modes can be found in the regions 1240 – 1020 cm-1

and 830 – 740 cm-1

, respectively. However, the

antisymmetric C–N–C band cannot be resolved due to its overlapping with the absorbance band of Si-CH2

stretching around 1270 – 1200 cm-1

, C-O-C stretching (1240 – 1020 cm-1

) of oxazine structure and formation of

hydrogen-bond within silanol (Si–OH) group (1100 – 1000 cm-1

) (Ignatyev et al., 2004). Furthermore, the Si–O

in plane stretching vibrations of Si–OH groups appeared around 900 cm-1

. These results are indicative of the

presence of silanol-terminated benzoxazine groups.

NMR analysis:

The 1H NMR spectra of the synthesized B-z(OH)3 monomer is shown Fig. 3. The characteristic signals of

oxazine ring structure assigned to–Ph–CH2–N– and –O–CH2–N–protons appeared as two singlet at 3.83 ppm

(6H) and 4.71 ppm (6H), respectively. The chemical shift (ppm) at 1.57 – 1.62 ppm and 6.53 – 6.96 ppm are

assigned to the aliphatic methyl and aromatic protons, respectively. The peaks assigned to the protons of –Si-O-

H appeared as singlet at 3.63 ppm. In addition, the signals 2.7 and 0.5 ppm are assigned N-bonded and Si-

bonded methylene protons, respectively.

Curing and polymerization of B-z(OH)3:

Fig. 3 shows the FTIR spectra of B-z(OH)3 monomer after each cure stages. The typical characteristic of

absorption band corresponding to C-O-C of oxazine at 1229 cm-1

, CH2 at 1319 cm-1

, tri-substituted benzene ring

at 1496 cm-1

and C–H at 927 cm-1

decreased [9,6,2,10]. By the end of 230oC

cure, the characteristic absorption

bands for oxazine ring and tri-substituted benzene ring disappeared, suggesting the completion of the ring

opening polymerization at the temperature. Furthermore, the strong absorption bands corresponding to water

molecules hydrogen bonded to silanol groups at 1634 cm-1

[7,5] and Si-CH2 vibrations at 1260 cm-1

[8] indicate

3-aminopropyltrimethoxysilane were hydrolyzed and participated in the formation of poly B-z(OH)3 network.



Conclusion:

A new benzoxazine (B-z(OH)3) monomer containing aminepropyltrihydroxylsilane in the main chain was

successfully synthesized and characterized. The chemical structure of B-z(OH)3 was confirmed by FT-IR and 1H-NMR. The structure of B-z(OH)3 during curing and polymerization was verified with FT-IR.

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