Synthesis and characterization of two novel urethane macromonomers and their methacrylic/urethane graft copolymers

Alshuiref, Abubaker (2010-03)

Thesis (PhD (Chemistry and Polymer Science))--University of Stellenbosch, 2010.

Thesis

ENGLISH ABSTRACT: Polymethacrylates are well known adhesives and can carry specific functionality, but have the disadvantage that their flexible backbones impart limited thermal stability and mechanical strength. 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 and excellent weatherability. PUs do however have some disadvantages, for instance, PU is considered an expensive polymer, especially when considered for solvent based adhesives. the focus of this study was to consider a largely unstudied area of PU chemistry, namely combining PUs with polymethacrylates. Two types of linear urethane macromers (UMs) UM1 and UM2 were synthesized by the polyaddition polymerization of 4,4'-methylenediphenyl diisocyanate (MDI) with ethylene glycol (EG), and MDI with neopentylglycol (NPG), via a pre-polymer method, followed by termination with 2-hydroxy ethylacrylate (2-HEA) and methanol (MeOH) to yield UMs having specific urethane chain lengths, and which have to be predominantly monofunctional. Structural identification of the UMs was verified by MALDI-TOF-MS, FTIR, 13C-NMR and 1HNMR spectroscopy.Various percentages of the respective UMs (0_55 wt % of methacrylate monomers) were then incorporated into polymethyl methacrylate (PMMA) and poly n-butyl methacrylate (PnBMA) backbones via solution free-radical copolymerization. The resulting methyl methacrylate-g-urethane and n-butyl methacrylate-g-urethane copolymers were characterized by 1H-NMR,13C-NMR, FTIR, SEC with double detectors (UV and RI), light scattering, UV-Vis, HPLC, TGA, DSC, DMA and TEM. Weight percentages of UM incorporated into the methyl methacrylate-g-urethane copolymers were calculated using FTIR, UV-Vis and 1H-NMR techniques. Phase separation which occurred between the urethane segment and methacrylate segment in the graft copolymerization products was investigated by DMA, DSC and TEM analysis. Microphase separation occurred in all PMMA-g-UM1 and PnBMA-g-UM1 copolymers: two glass transitions temperatures corresponding to the PMMA or PnBMA and UM1 fractions, respectively, were observed. On the other hand, DMA and DSC results showed that in most graft copolymer products the two respective component parts PMMA-g-UM2 or PnBMA-g- UM2 were compatible, because only one Tg was observed. Two glass transitions occurred for PMMA or PnBMA and UM2 when the amount of UM was increased to 55 wt % during copolymerization and microphase separation was evident in DSC, DMA and TEM measurements. Thermal stability and storage modulus (stiffness) of all the synthesized PMMA-g-urethane and PnBMA-g-urethane copolymers increased as the concentration of urethane macromonomer in the copolymerization feed increased, as confirmed in TGA and DMA results. The surface and adhesive properties of the synthesized graft copolymer were studied by measuring the static contact angle and peel strength. Adhesion increased as the content of UMs increased in the graft copolymer. The graft copolymers prepared using a high UM2 feed for both PMMA and PnBMA showed improved in adhesion compared to the pure methacrylate polymers. The adhesion was better for both leather and for vinyl.

AFRIKAANSE OPSOMMING: Polimetakrilate is bekende kleefstowwe. Hulle het egter die tekortkoming dat hulle buigbare ruggraat beperkte termiese en meganiese stabliteit besit. Poliuretane (PUs) word deesdae al hoe meer gebruik in baie nywerhede as gevolg van hulle baie voordele, insluitend hul wye buigsaamheid tesame met sterkte, hoë chemiese weerstand en uitstekende weerbaarheid. PUs het egter ’n paar nadele: hulle is baie duur, veral wanneer hulle gebruik word in oplosmiddel-gebaseerde kleefstowwe. Die doel van hierdie studie is om die kombinering van PUs met polimetakrilate te bestudeer, 'n onderwerp wat tot dusver baie min aandag-getrek het. Twee tipes liniêre uretaanmakromere (UMs), UM1 en UM2, is gesintetiseer deur gebruik te maak van poliaddisiepolimerisasie van 4,4'-metileendifeniel diisosianaat (MDI) met etileenglikol (EG), en MDI met neopentielglikol (NPG), via ‘n prepolimeermetode, gevolg deur terminering met 2-hidroksiëtielakrilaat (2-HEA) en metanol (MeOH). Die produk hiervan is UMs met spesifieke kettinglengtes (hoofsaaklik monofunksioneel). Die samestelling van die UMs is met behulp van die volgende gevorderde analitiese tegnieke bepaal: MALDI-TOFMS, FTIR, 13C-NMR en 1H-NMR. Verskillende hoeveelhede van die UMs (0_55 gewIing% metakrilaatmonomere) is dan in die polimetielmetakrilaat (PMMA) en poli-n-butielmetakrilaat (PnBMA) ruggrate geïnkorporeer deur middel van oplossing-vryradikaalpolimerisasie. Die samestelling van die kopolimeerprodukte, metiel-metakrilaat-g-uretaan en n-butiel-metakrilaat-g-uretaan, is met behulp van die volgende gevorderde analitiese tegnieke bepaal: 1H-NMR, 13C-NMR, FTIR, SEC met dubbele detektors (UV en RI), ligverstrooiing UV-Vis, HPLC, TGA, DSC, DMA en TEM. Die hoeveelheid UM geïnkorporeer in die metielmetakrilaat-g-uretaan kopolimere is bereken deur gebruik te maak van FTIR, UV-Vis en 1H-NMR data. Die faseskeiding wat plaasgevind het tussen die uretaansegment en die metakrilaatsegment in die produkte van die entpolimerisasie is met behulp van DMA, DSC en TEM ondersoek. In alle PMMA-g-UM1 en PnBMA-g-UM1 kopolimere het mikrofaseskeiding plaasgevind: twee verskillende glasoorgangstemperature vir die PMMA of PnBMA en UM1 fraksies is waargeneem. Hierteenoor het DMA en DSC resultate getoon dat in die meeste entkopolimeerprodukte (PMMA-g-UM2 of PnBMA-g-UM2) was die twee komponente verenigbaar, aangesien net een Tg waargeneem is. In die geval van die kopolimere waar die hoeveelheid UM in die kopolimerisasiereaksies tot 55 gew% verhoog is, is twee glasoorgangstemperature vir PMMA of PnBMA, en UM2 waargeneem. Mikrofaseskeiding is met behulp van DSC, DMA en TEM bewys. Termiese stabiliteit en stoormodulus (styfheid) van alle gesintetiseerde PMMA-g uretaan en PnBMA-g-uretaan kopolimere het toegeneem namate die uretaankonsentrasie in die kopolimerisasiereaksie toegeneem het soos deur middel van TGA en DMA resultate bewys is. Die oppervlakte- en kleefeienskappe van die bereide entkopolimere is bestudeer deur die statiese-kontakhoek en skilkrag te meet. Adhesie het toegeneem namate die UMinhoud toegeneem het. Die entkopolimere berei met hoë PMMA en PnBMA inhoud het uiteindelik beter adhesie getoon as die suiwer metakrilaatpolimere. Die adhesie was beter vir beide leer en viniel.

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