POLYMER BEADS WITH EPOXY GROUPS - SYNTHESIS & MODIFICATION

 

Ksiezniak K.

Maria Curie-Sklodowska University,

Lublin, Poland.

second-year PhD student.

kateksiezniak@gmail.com

Scientific adviser: Gawdzik B.

 

1. INTRODUCTION

In the recent years a family of polymer materials was intensively developed. Polymers have become the backbone of a modern industry [1]. Advances in the field of polymer science have paved the way for many pharmaceutical and cosmetic technologies [2]. Following these trends my research resulted in synthesis of variety of copolymer materials differing in size, shape and ordering of the pores. Properties of these polymers make it attractive for diverse industrial applications [3, 4]. In my work I present the study on characteristic of various new materials of glycidyl methacrylate (GMA) series.

2. EXPERIMENTAL

Polymer beads were produced by suspension polymerization process.
The organic phase contained glycidyl methacrylate (GMA) as a base
monomer and one of the following cross-linkers: di-(methacryloyl-oxymethyl) naphthalene (DMN), trimethylolpropane trimethacrylate (TRIM), ethylene glycol dimethylacrylate (EGDMA) or divinyl benzene (DVB). The molar ratio of functional monomer to the cross-linker was varied from 1:1 to 1:5. Monomers, initiator (dimethylazodipropiononitrile-AIBN) and a porogenic solvent was dispersed with stirring in de-ionized water/aqueous mixture containing a dioctyl sulfosuccinate, sodium salt (DAC) as a surfactant. As a porogen were used toluene, mixture of toluene and poly(styrene) in ratio 1:1 or poly(styrene). Conditions of polymerization were constant. The mixture was stirred at 370 rpm for 16 hours in 80^oC. The resulting particles were filtered, washed with hot de-ionized water, methanol and acetone, purified with acetone, filtered and dried at room temperature for 12 hours, then dried in vacuum dryer at 70^oC for 48 hours. In the end of the procedure white beads of GMA copolymer family of highly developed porous surface, desirable sizes and shapes which contain epoxy groups in their chemical structures were obtained. In the next step chemical modification of the synthesized new materials consist on the reaction with pyrrolidone and hydroxyethyl pyrrolidone (HEP) was carried out. The reaction of the epoxy polymer lasted 6 hours in 150^oC. As an initiator for reaction with pyrrolidone sodium hydroxide was used whereas for that with HEP it was tin (IV) chloride. Subsequently the obtained particles were filtered, washed with hot de-ionized water and dried as in earlier case.

3. RESULTS

Properties of the synthesized polymer beads were characterized using standard methods: nitrogen adsorption/desorption and laser diffraction with Mastersizer 2000. Pore size distribution was calculated from the N₂ adsorption isotherms using BJH method. Particle sizes were defined using innovative laser diffraction technology. For GMA copolymer series the surface area were in the range of 0.14-333 m²/g. The lowest value was obtained for polymer which was synthesized using poly(styrene) solution. The use of the poly(styrene) as a porogen lowers the porous properties of polymer. The best results were acquired for pure toluene. The amount of epoxy groups was measured by titration with sodium hydroxide. The highest value of epoxide content was 4.2 mmol/g for GMA-TRIM (in 5:1 ratio) sample. The results of the research are satisfactory and the characteristics of the new polymers indicate that they can be used in drug and cosmetics delivery systems.

 

References:

[1] Qiu W., Zhang K., Liu J., Koros W.J., Sun Q., Deng Y. Polymer 51,
3793-3800 (2010)

[2] Kandavilli S., Nair V., Panchagnula R. Pharmaceutical 5, 62-80 (2002)

[3] Hradil J., Benes M.J., Plichta Z. Reactive & Functional Polymers 44,
259-272 (2000)

[4] Ferreira A., Bigan M., Blondeau D. Reactive & Functional Polymers 56, 123-136 (2003)