SYNTHESIS AND CHARACTERIZATION OF POLYSILOXANE ...

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SYNTHESIS AND CHARACTERIZATION OF POLYSILOXANE COMPOUND AS PRECURSOR OF SILICON DIOXIDE SHEHU ISAH DANLAMI A Thesis Submitted in Fulfillment of the Requirements for the Award of the Degree of Master of Science Faculty of Science, Technology and Human Development Universiti Tun Hussein Onn Malaysia JANUARY, 2 0 1 5

Transcript of SYNTHESIS AND CHARACTERIZATION OF POLYSILOXANE ...

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SYNTHESIS AND CHARACTERIZATION OF POLYSILOXANE COMPOUND AS

PRECURSOR OF SILICON DIOXIDE

SHEHU ISAH DANLAMI

A Thesis Submitted in

Fulfillment of the Requirements for the Award of the

Degree of Master of Science

Faculty of Science, Technology and Human Development

Universiti Tun Hussein Onn Malaysia

JANUARY, 2 0 1 5

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ABSTRACT

Polymethylvinylsiloxane . (PMVS) was successfully synthesized by

prehydrolysislcondensation of methylvinydichlorosilane (MVDCS) and

dimethyldichlorosilane (DMDCS) followed by catalyzed equilibrium copolymerization

with sulphuric acid (H2S04) and dibutyltin dilaurate (DBTDL). Then PMVS was photo-

chemically converted to silicon dioxide films by UVIOzone exposure at room

temperature in the presence of atmospheric oxygen. All procedures in the experiment

were performed under ambient condition. The PMVS samples were characterized by

Fourier Transform Infrared Spectroscopy (FTIR), Nuclear Magnetic Resonance (13c and

2 9 ~ i NMR), thermal properties by Differential Scanning Calorimetry (DSC) and

Thermogravimetric analysis (TGA). The results obtained from DSC were 7.5 "C and 33 o C indicating that the polymethylviny'lsiloxane samples have low glass transition

temperature (T,) while TGA result showed low thermal decomposition temperatures at

50 OC and 110 "C with low residue yields as a result of oxidation or degradation of

methyllvinyl groups. The thin film was then characterized by FESEM and XRD for its

surface morphology characteristic and by ATR-FTER spectrometry for its molecular

change investigation. It was observed that SiOz film was significantly changed at 30

minutes of UVIozone exposure while increased in the time of exposure made the film

surface smoother which enhanced its chemical properties. ATR-FTIR spectra of

wavelength around 960 cm-', 1408 cm-I and 1598 cm-' correspond to vinyl group totally

disappeared under the UVIozone exposure whereas those at around 791 -795 cm-', 1258-

1260 cm", and 2962-2963 cm-' which correspond to methyl group have not been

significantly changed. From the XRD, SiOz film was found to be amorphous in nature

while from UV-Visible, the unmodified PVMS absorbed UV radiation at 230 nm and

upon increasing the UVIozone exposure time, the peak extends to a wavelength of 300

nrn.

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ABSTRAK

Polimetilvinilsiloksana (PMVS) telah berjaya disintesis melalui pra-

hidrolisis/pemeluwapan metilvinildiklorosilana (MVDCS) dan dimetildiklorosilana

(DMDCS), diikuti oleh pengkopolimeran seimbang bermangkin dengan asid sulfurik

(H2S04) dan dibutiltimahdi'laurat (DBTDL). Kemudian, PMVS ditukarkan kepada filem

silikon dioksida menenlsi kaedah pendedahan fotokimia UV/ozon pada suhu bilik

dengan kehadiran oksigen dari atmosfera. Kesemua prosedur dalam eksperimen ini

dilakultan di bawah keadaan ambien. Sampel PMVS dicirikan dengan menggunakan

spektroskopi inframerah transisi fourier (FTIR), resonan rnagnetik nuklear (NMR 13c dan 2 9 ~ i ) , sifat-sifat terma dikaji menggunakan kalorimetri pengimbas pembezaan (DSC)

dan analisis termogravimetrik (TGA). Keputusan yang diperolehi daripada DSC adalah

7.5 OC dan 33 OC masing-masing, menunjukkan bahawa sampel-sampel PMVS memiliki

suhu peralihan kaca (T,) yang rendah, manakala keputusan TGA menunjukkan suhu

penguraian haba rendah, iaitu pada 50 "C dan 110 OC, serta menghasilkan sisa yang /'

sedikit akibat daripada proses pengoksidaan atau penurunan kumpulan vinil/metil.

Kemudian, filem nipis ini dicirikan menggunakan FESEM dan XRD untuk mengkaji

morfologi permukaannya dan spektrometri ATR-FTIR untuk kajian pelrubahan pada

molekulnya. Perbezaan morfologi permukaan filem nipis ini dapat diamati dengan jelas

apabila berada di bawah pendedahan UV/ozon selama 30 minit dan perlanjutan masa

pendedahan membuatkan perrnukaan kepingan menjadi lebih licin dan meningkatkan

sifat-sifat kimia. Puncak spektra ATR-FTIR yang berada pada nombor gelombang antara

960 cm-', 1408 cm-' dan 1598 cm-' yang merujuk kepada kumpulan vinil didapati

menghilang apabila didedahkan kepada UV/ozon manakala puncak spektra pada nombor

gelombang 791-795 cm-', 1258-1260 cm-' dan 2962-2963 cm-' yang merujuk kepada

kumpulan metil pula tidak menunjukkan perubahan ketara. Keputusan XRD

menunjukkan filem Si02 bersifat amorfbs secara semulajadi, manakala melalui W-

nampak PMVS didapati tidak terurai menyerap gelombang UV pada panjang gelombang

230 nm, dan apabila masa pendedahan UV/ozon dilanjutkan, puncak berlanjut ke

panjang gelombang berkadar 300 nm.

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REFERENCES

Ackemann, H., Mania, D. J., Kirkpatrick, R. L., & Coffey, M. (20 13). US. Patent No.

8,4 70,949. Washington, DC: U.S. Patent and Trademark Office.

Agirre, I., Arias, P. L., Castricum, H. L., Creatore, M., ten Elshof, J. E., Paradis, G. G. &

Vente, J. F. (2014). Hybrid organosilica membranes and processes: Status and

outlook. Separation and Pur$cation Technology, 121, pp. 2-12.

Ahmad Z. & Mark J. E. (1998). Biomimetic materials: Recent developments in organic-

inorganic hybrids. Materials Science and Engineering. C 6. pp 183-196.

Anagnostopoulos, T., Eliades, G., & Palaghias, G. (1993). Composition, reactivity and

surface interactions of three dental silane primers. Dental Materials. 9(3), pp.

Andrianov, K. A,, Haiduc, I., & Khananashvili, L. M. (1963). Inorganic cyclic silicon- /

containing compounds and their organic derivatives. Russian Chemical Reviews.

32(5), pp. 243-268.

Auner, N. & Weis, J., (2005): Organosilicon Chemistry VI-From Molecules to

Materials Eds.; Wiley-VCH: Weinheim,

Auner, N., & Weis, J., (2008). Organosilicon Chemistry 111: From Molecules to

Materials. John Wiley & Sons.

Baradie, B., Lai, P. H., & Shoichet, M. S. (2005). Synthesis and characterization of

novel polysiloxane-grafted fluoropolyrners. Canadian Journal of Chemistry.

83(6-7), pp. 553-558.

Barnes, K. A., Tascarella, D. S., Julian, D. J., & Liles, D. T. (2013). U.S. Patent No.

8,580,862. Washington, DC: U.S. Patent and Trademark Office.

Bauer, J., Hiising, N., & Kickelbick, G. (2004). Tunable block copolymers based on a

polysiloxane backbone by anionic ring-opening polymerization. Journal of

Polymer Science Part A: Polymer Chemistry. 42(16), pp. 3975-3985.