Synthesis of UV-curable Phosphorous-containing Flame Retardants and Flame Retardant Finish of PET Fabrics Yong Kyun Jeung Department of Textile & Fashion Engineering, Graduate School, Kumoh National Institute of Technology Abstract Tris(2-methacryloyloxy)ethyl phosphate(TMEP), Bis[2-(methacryloyloxy...
Synthesis of UV-curable Phosphorous-containing Flame Retardants and Flame Retardant Finish of PET Fabrics Yong Kyun Jeung Department of Textile & Fashion Engineering, Graduate School, Kumoh National Institute of Technology Abstract Tris(2-methacryloyloxy)ethyl phosphate(TMEP), Bis[2-(methacryloyloxy) ethyl] phosphate(DMEP) and 2-(Methacryloyloxy)ethyl phosphate(MMEP) were synthesized from phosphorus oxychloride and 2-Hydroxyethyl methacrylate, which were used as flame retardant monomers for UV-curable coating systems. FT-IR was used to characterize the synthesized monomers and its polymers obtained by UV-curing. P=O and P-O-C stretching vibrations of the phosphate were observed at 1250cm-1, 1033cm-1, and 989cm-1 respectively, while C=O, C-C-O and O-C-C stretching of methacrylates located at 1716, 1170 and 1060cm-1 were shifted to 1720, 1160, 1050cm-1 after photopolymerization. Also the ethylenic unsaturation band of the synthesized monomers located at 1635cm-1 disappeared after photopolymerization. According to functionality, the intensity of methacrylate and hydroxyl band in IR spectra were changed, Monofunctional MMEP gave the lowest intensity of methacrylate band but highest intensity of hydroxyl band. While trifunctional TMEP showed the highest methacrylate but lowest hydroxyl band. In 1H-NMR spectrum of synthesized monomers, methylene(CH2), methyl(CH3) and ethylene(CH2CH2) of methacrylate group in the molecular structure were observed at 6.3 and 5.6, 1.9, 4.3ppm respectively, while hydroxy peak in MMEP and DMEP located at 9.5 and 11.5ppm, respectively. The UV-cured TMEP, DMEP and MMEP films have limited oxygen indexes of 28.5, 30.3 and 35.1, respectively. Their thermal behaviours were studied by thermogravimetric analysis and showed two characteristic degradation temperature regions which attributed to the decomposition of phosphate, thermal pyrolysis of methacrylate side chains, respectively. But MMEP film has one more degradation temperature region that was due to the decomposition of unstable crosslinking structures in the char. Add-on and add-on efficiency of the coating on PET fabrics with the synthesized monomers by UV irradiation increased with increasing monomer functionality. Compared with untreated PET fabric, UV-cured PET fabric showed a large change in microscopic structure on the surface. And the changes were more apparent with increasing monomer functionality. Thermal degradation behavior of the UV-cured PET followed a condensed phase mechanism as indicated by the lowered decomposition temperature, the increased residual char amount as well as the apparently lowered decomposition rate with increase in the monomer concentration and P-content in the monomers. Flame retardant property up to a LOI of 25.9 was achieved by the UV curing. The synthesized monomers were blended with Ammonium polyphosphate(APP) at different ratios to obtain a series of UV-curable flame-retardant formulations. The results showed that the monomers/APP blends formulations have the highest LOI of 28.5. but the blends have lower slightly UV-curing efficiency and laundering durability. The treated and untreated PET fabrics were dyed with disperse dyes. Color change on PET fabrics after dyeing were changed when the sequence of dyeing and flame retardant finish were different. (1) When PET fabrics were frist finished with flame -retardants and dyeing was then carried out, b* value have slightly decreased. (2) When PET fabrics were frist dyed and then treated with flame retardant formulation, b* increased on the contrary. The decrease of b* may be due to the photoxidation effect of UV light and apparent yellowing by the synthesized monomers. Also the increased color fastness and durability of the dyed UV-cured flame retardant PET fabrics compared with untreated and heat-treated ones may be due to the protection effect of the polymer layer covered on the colored fiber surface.
Synthesis of UV-curable Phosphorous-containing Flame Retardants and Flame Retardant Finish of PET Fabrics Yong Kyun Jeung Department of Textile & Fashion Engineering, Graduate School, Kumoh National Institute of Technology Abstract Tris(2-methacryloyloxy)ethyl phosphate(TMEP), Bis[2-(methacryloyloxy) ethyl] phosphate(DMEP) and 2-(Methacryloyloxy)ethyl phosphate(MMEP) were synthesized from phosphorus oxychloride and 2-Hydroxyethyl methacrylate, which were used as flame retardant monomers for UV-curable coating systems. FT-IR was used to characterize the synthesized monomers and its polymers obtained by UV-curing. P=O and P-O-C stretching vibrations of the phosphate were observed at 1250cm-1, 1033cm-1, and 989cm-1 respectively, while C=O, C-C-O and O-C-C stretching of methacrylates located at 1716, 1170 and 1060cm-1 were shifted to 1720, 1160, 1050cm-1 after photopolymerization. Also the ethylenic unsaturation band of the synthesized monomers located at 1635cm-1 disappeared after photopolymerization. According to functionality, the intensity of methacrylate and hydroxyl band in IR spectra were changed, Monofunctional MMEP gave the lowest intensity of methacrylate band but highest intensity of hydroxyl band. While trifunctional TMEP showed the highest methacrylate but lowest hydroxyl band. In 1H-NMR spectrum of synthesized monomers, methylene(CH2), methyl(CH3) and ethylene(CH2CH2) of methacrylate group in the molecular structure were observed at 6.3 and 5.6, 1.9, 4.3ppm respectively, while hydroxy peak in MMEP and DMEP located at 9.5 and 11.5ppm, respectively. The UV-cured TMEP, DMEP and MMEP films have limited oxygen indexes of 28.5, 30.3 and 35.1, respectively. Their thermal behaviours were studied by thermogravimetric analysis and showed two characteristic degradation temperature regions which attributed to the decomposition of phosphate, thermal pyrolysis of methacrylate side chains, respectively. But MMEP film has one more degradation temperature region that was due to the decomposition of unstable crosslinking structures in the char. Add-on and add-on efficiency of the coating on PET fabrics with the synthesized monomers by UV irradiation increased with increasing monomer functionality. Compared with untreated PET fabric, UV-cured PET fabric showed a large change in microscopic structure on the surface. And the changes were more apparent with increasing monomer functionality. Thermal degradation behavior of the UV-cured PET followed a condensed phase mechanism as indicated by the lowered decomposition temperature, the increased residual char amount as well as the apparently lowered decomposition rate with increase in the monomer concentration and P-content in the monomers. Flame retardant property up to a LOI of 25.9 was achieved by the UV curing. The synthesized monomers were blended with Ammonium polyphosphate(APP) at different ratios to obtain a series of UV-curable flame-retardant formulations. The results showed that the monomers/APP blends formulations have the highest LOI of 28.5. but the blends have lower slightly UV-curing efficiency and laundering durability. The treated and untreated PET fabrics were dyed with disperse dyes. Color change on PET fabrics after dyeing were changed when the sequence of dyeing and flame retardant finish were different. (1) When PET fabrics were frist finished with flame -retardants and dyeing was then carried out, b* value have slightly decreased. (2) When PET fabrics were frist dyed and then treated with flame retardant formulation, b* increased on the contrary. The decrease of b* may be due to the photoxidation effect of UV light and apparent yellowing by the synthesized monomers. Also the increased color fastness and durability of the dyed UV-cured flame retardant PET fabrics compared with untreated and heat-treated ones may be due to the protection effect of the polymer layer covered on the colored fiber surface.
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