SYNTHESIS AND CHARACTERIZATION OF URETHANE–ACRYLATE GRAFT COPOLYMERS By Abubaker Alshuiref Thesis presented for the degree of Master of Natural Sciences (Polymer Science) at the University of Stellenbosch Promoter: Prof. R.D. Sanderson Stellenbosch Mentor : Dr. S. Seboa December 2006 http://scholar.sun.ac.za DECLARATION I, the undersigned, hereby declare that the work contained in this thesis is my own original work and has not previously in its entirety or in part been submitted at any university for a degree. Signature:…………………………. Date:…………………… ii http://scholar.sun.ac.za ABSTRACT Polyurethanes (PUs) are finding increasing application and use in many industries due to their advantageous properties, such as a wide range of flexibility combined with toughness, high chemical resistance, excellent weatherability, and very low temperature cure. PUs do however have some disadvantages, for instance, PU is considered an expensive polymer, especially when considered for solvent based adhesives. A motivation for this study was to consider a largely unstudied area of PU chemistry by combining PUs with polyacrylates. Polyacrylates are well known adhesives and can carry specific functionality, but have the disadvantage that their flexible backbones impart limited thermal stability and mechanical strength. In this study PU was incorporated into acrylates in an effort to obtain acrylate-g-urethanes with good properties. The mode of incorporation chosen was urethane macromonomers (UMs), a hardly mentioned substance in literature, yet one deserving investigation. UMs having different urethane chain lengths (X) were synthesized by the polyaddition polymerization of toluene diisocyanate (TDI) and ethylene glycol (EG) by the pre- polymer method, which was terminated by 2-hydroxy ethyl methacrylate (HEMA) and isopropanol. The UMs were characterized by Fourier-transform infrared spectroscopy (FTIR), proton NMR (1H NMR), carbon NMR (13C NMR), gel permeation chromatography (GPC), thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA). Various percentages of the respective UMs (0-40 wt % according to acrylate monomers) were then incorporated into methyl methacrylate (MMA) and into normal butyl methacrylate (n-BMA) backbones via solution free radical copolymerization. The resulting methyl methacrylate-urethane graft copolymers (PMMA-g-urethane) and normal butyl methacrylate-urethane graft copolymers (n-PBMA-g-urethane) were characterized by GPC, 1H NMR and 13C NMR, FTIR, TGA, and DMA. Phase separation between the urethane segment and acrylate segment in the yield of graft copolymerization products was investigated by DMA and transmission electron microscopy (TEM). As the concentration of the UMs in the free radical copolymerization feed increased, lower yields of both graft copolymers PMMA-g-urethane and n-PBMA-g-urethane were iii http://scholar.sun.ac.za observed and more UM was incorporated into the PMMA and n-PBMA backbones. It also was found that the thermal stability of the PMMA-g-urethane and n-PBMA-g- urethane copolymers increased with increasing UM concentration. DMA results showed that in most graft copolymer products the two respective component parts of PMMA-g-urethane or n-PBMA-g-urethane were completely compatible as only one T was observed. Two glass transitions, at temperatures of 22.0 g and 76.0 oC, corresponding to the n-PBMA and urethane moieties, were observed when the chain length of the UMs was increased from X=4 to X=32 [the amount of this UM used in the copolymerization feed was increased to 40%, and microphase separation was indicated]. iv http://scholar.sun.ac.za Opsomming Poli-uretane (PUs) bevind ’n toename in applikasies en gebruike in baie industriee as gevolg van hul goeie inherende eienskappe, soos ’n wye reeks van buigbaarheid wat gekoppel is aan sterkheid, hoë chemiese weerstand, uitstekende weer-bestandheid, en ’n lae kruissings temperatuur. PUs het ook ’n paar negatiewe eienskappe, byvoorbeeld, poli-uretane word beskou as ’n baie duur polimeer, veral in konsederasie vir die gebruik in oplosmiddel gebaseerde gomme. ’n Motivering vir hierdie studie was om ’n groot ongestudeerde area van PU chemie in ag te neem deur PUs met poli-akrielate te kombineer. Poli-akrielate is wel bekende gomme met spesifieke funksionalitiete, maar het die negatiewe eienskap waarin hul buigbare ruggraat beperkte termiese stabiliteit en meganiese sterkte meebring. PU was in hierdie studie in akrielate geinkorporeer in ’n poging om akrielaat-g-uretaan ko-polimere met goeie eienskappe te verkry. Die tipe van inkorporasie wat gekies was is die van uretaan makro-monomere (UMs), ’n min bekende skrifstuk in die literatuur, hoewel een wat van meer opvolging toekomstig is. UMs met verkillende uretaan kettinglengtes (X) was gesintetiseer deur die poli-addissie polimerisasie van tolueendiisosianaat (TDI) en etileenglikol (EG), wat met 2-hidroksie etiel metakrilaat (HEMA) en isopropanol getermineer was. Die UMs was deur middel van Fourier-transformasie infrarooi (FTIR) spektroskopie, kern magnetiese resonansie (KMR) spektroskopie, gas-fase permeasie chromatografie (GPC), termogravimetriese analise (TGA) en dinamiese meganiese analise (DMA) gekarakteriseer. Verskeie persentasies van die gesintetiseerde UMs (0-40 wt%) was met MMA en n-BMA geko-polimeriseer. Hierdie gevormde ko-polimere, naamlik PMMA-g-uretaan en n- PBMA-g-uretaan, was ook deur middel van GPC, KMR, FTIR, TGA en DMA gekarakteriseer. Fase-seperasie tussen die uretaan en akrilaat komponente was deur middel van DMA en Transmissie elektron mikroskopie (TEM) gekarakteriseer. Daar was bevind dat die ko-polimeer opbrengste afneem met ’n toename in massa UMs wat geinkorporeer was tydens ko-polimerisasie, asook met ’n toename in die kettinglengte van die UMs. Daar was ook bevind dat die termiese stabiliteit van die ko- polimere toeneem met ’n toename in UM inkorporasie. v http://scholar.sun.ac.za DMA resultate het bevestig dat die meeste ko-polimeer produkte net een Tg wys, wat daarop aangedui het dat die twee akrilaat en uretaan komponente heeltamaal mengbaar met mekaar is. Daar was egter twee Tg’s in die n-PBMA-g-uretaan ko-polimeer teenwoordig toe die UMs met UM kettinglengte van X=32 se konsentrasie tydens ko- polimerisasie na 40% verhoog was. Die twee Tg’s van 22.0oC en 76.0oC wat ooreenstem van die n-PBMA en uretaan komponente, was wel ’n indikasie van mikrofase seperasie. vi http://scholar.sun.ac.za Acknowledgements I would like to thank the following people for contributing to this study. Prof. R.D. Sanderson, my promoter, for his fruitful advice, guidance and encouragement throughout this study. Dr. S. Seboa, for his advice and guidance throughout this study. Dr. Margie Hurndall, for taking the time to edit my thesis. Centre of Macromolecules and Materials Science (Libya) for the financial support of this research. Plascon Research Centre, for the use of their analytical laboratory. All the staff and students at Polymer Science for their assistance and encouragement. vii http://scholar.sun.ac.za Dedicated to my wife and my parents viii http://scholar.sun.ac.za TABLE OF CONTENTS CHAPTER 1: INTRODUCTION 1.1. INTRODUCTION 1 1.2. OBJECTIVES 3 1.3. REFERENCES 4 CHAPTER 2 HISTORICAL AND THEORETICAL BACKGROUND 2.1. INTRODUCTION 5 2.3 POLYURETHANE APPLICATIONS 6 2.3.1 POLYURETHANE THERMOPLASTIC ELASTOMERS 6 2.3.2 POLYURETHANE COATINGS 8 2.3.3 POLYURETHANE ADHESIVES 9 2.3.4 POLYURETHANE FOAMS 9 2.4 METHODS OF PREPARATION OF POLYURETHANES 9 2.4.1 THE SOLUTION PROCESS 9 2.4.2 THE MELT-DISPERSION PROCESS 10 2.4.3 THE PRE-POLYMER PROCESS 11 2.4.4 KETIMINE AND KETAZINE PROCESS 11 2.5 RAW MATERIALS 12 2.5.1 ISOCYANATES 12 2.5.1.1 Introduction 12 2.5.1.2 Reactivity of the isocyanate group 12 2.5.1.3 Aromatic isocyanates 13 2.5.1.4 Aliphatic isocyanates 14 2.5.1.5 General reactions of isocyanates 14 i) Reaction with alchol 15 iii) Reaction with water 16 iv) Reaction with carboxylic compounds 16 i) Dimerization 17 ii) Trimerization 18 ix http://scholar.sun.ac.za 2.5.2 POLYOLS 18 2.6. POLYACRYLATES 19 2.6.1 INTRODUCTION 19 2.6.2 PREPARATION OF POLYACRYLATES 20 2.6.2.1 Free radical polymerization 20 2.6.3 Polymerization techniques 22 2.6.3.1 Solution polymerization 22 2.6.3.2 Emulsion polymerization 22 2.6.4 APPLICATIONS OF POLYMETHACRYLATES 23 2.7 URETHANE ACRYLATE OLIGOMERS 23 2.8 GRAFT COPOLYMERIZATION 24 2.8.1 SYNTHETIC ROUTES TO GRAFT POLYMERS 26 2.8.1.1 “Grafting from” 26 2.8.1.2 "Grafting onto" 27 2.8.1.3 "Grafting through" 27 2.9 MACROMONOMERS 28 2.9.1 INTRODUCTION 28 2.9.2 SYNTHESES OF MACROMONOMERS 29 2.9.2.1 The initiation method 29 2.9.2.2 The termination method 30 2.9.2.3 Functional end-group transformation 30 2.9.2.4 Macromonomer by polyaddition polymerization 30 2.9.3 FREE RADICAL POLYMERIZATION OF MACROMONOMERS 31 2.10 GRAFT AND BLOCK COPOLYMERIZATION OF POLYURETHANE 31 2.11 REFERENCES 32 CHAPTER 3 EXPERIMENTAL WORK 3.1 INTRODUCTION 37 3.2 SYNTHESIS OF URETHANE MACROMONOMERS 37 3.2.1 RAW MATERIALS 37 3.2.2 EXPERIMENTAL SETUP 38 3.2.3 POLYURETHANE MACROMONOMER FORMULATIONS 38 3.2.4 EXPERIMENTAL PROCEDURE 39 x