A reactive melt modification of polyethylene terephthalate

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ABSTRACT REACTIVE MELT MODIFICATION OF POLYETHYLENE TEREPHTHALATE by Rahul Ramesh Dhavalikar This work investigates the structural and chemorheological modification of polyethylene terephthalate in the melt phase with low molecular weight multifunctional glycidyl compounds as reactive additives. Polyethylene terephthalate undergoes chain extension and/or branching reactions with the additives that result in modified rheological properties suitable for certain polymer processing operations such as extrusion blow molding or extrusion foaming to low densities. Among five different low MW difunctional and trifunctional epoxy compounds, triglycidyl isocyanurate is shown to be an efficient reactive melt modifier for commercially available polyethylene terephthalate polymers. Its stability at the polyethylene terephthalate melt temperatures is confirmed offline through thermogravimetric and FT-IR techniques. Melt modification of polyethylene terephthalate is followed in an intensive batch mixer by torque changes, analyzing the products for residual carboxyl content, insoluble content, and by dynamic mechanical analysis. The importance of undesirable melt degradation reactions occurring simultaneously with the branching/extension reactions is analyzed. Valuable information is obtained from the designed batch mixer experiments regarding the effects of various process parameters on the kinetics of the reactive modification. The melt-modification reaction products from the batch mixer are evaluated offline for melt viscoelastic properties using a dynamic mechanical analyzer.
Page 1: Copyright Warning & Restrictions Th
Page 5 and 6: REACTIVE MELT MODIFICATION OF POLYE
Page 7 and 8: BIOGRAPHICAL SKETCH Author: Rahul R
Page 9 and 10: Copyright © 2003 by Rahul Ramesh D
Page 11 and 12: ACKNOWLEDGEMENTS I always considere
Page 13 and 14: TABLE OF CONTENTS Chapter Page 1 IN
Page 15 and 16: TABLE OF CONTENTS (Continued) Chapt
Page 17 and 18: LIST OF FIGURES Figure Page 1.1 Mac
Page 19 and 20: LIST OF FIGURES (Continued) Figure
Page 21 and 22: LIST OF FIGURES (Continued) Figure
Page 23 and 24: Striation Thickness Time Diffusion
Page 25 and 26: tertiary amine terephthalic acid th
Page 27 and 28: CHAPTER 1 INTRODUCTION After its in
Page 29 and 30: 3 of 0.5-1.00 mm Hg (Sorenson 2001)
Page 31 and 32: where rib is the solution viscosity
Page 33 and 34: 7 are not suitable for most of the
Page 35 and 36: 9 In the case of sheet applications
Page 37 and 38: 11 operation (Dealy and Wissbrun, 1
Page 39 and 40: 13 During the cell growth phase of
Page 41 and 42: 15 suitability of extruders as cont
Page 43 and 44: 17 conditions and additive concentr
Page 45 and 46: 19 understand the effect of evolvin
Page 47 and 48: CHAPTER 3 LITERATURE REVIEW This ch
Page 49 and 50: 23 absence of modifiers is accompan
Page 51 and 52: 25 The primary objective while modi
Page 53 and 54:
27 Polypropylene resins with high m
Page 55 and 56:
29 initially the reaction with hydr
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31 A diglycidyl ether, often in the
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33 Characterizing the products of t
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35 5. Ease of mixing in the polymer
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37 Figure 3.4 Epoxy or 0xirane ring
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39 carbocation stability overrides
Page 67 and 68:
41 Figure 3.9 Anhydride — epoxy r
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43 Figure 3.12 Base catalyzed hydro
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45 activity to enhance the PET-epox
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47 4.1.2 Chain EDtenders The struct
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TGDDM was used in the batch mixer s
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51 4.2 Processing and Characterizat
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53 specimens as a function of freVu
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55 to the parallel plates). An addi
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57 background spectrum. It took app
Page 85 and 86:
CHAPTER 5 RESULTS AND DISCUSSION Th
Page 87 and 88:
61 molecular weight of MPET as also
Page 89 and 90:
63 rate expressions analogous to th
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Figure 5.5 Possible reactions betwe
Page 93 and 94:
67 taking place by the convective;
Page 95 and 96:
69 5.1.4 Comparison of Epoxides Fig
Page 97 and 98:
71 5.1.5 Reactions of TGIC with HPE
Page 99 and 100:
73 Figure 5.11 shows the vanation o
Page 101 and 102:
75 Figure 5.13 shows the effect of
Page 103 and 104:
77 to time. In a general sense, the
Page 105 and 106:
79 5.1.7 Study on Role of Catalysts
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81 groups adjacent to the tertiary
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83 overall less activity towards TG
Page 111 and 112:
85 5.2.1 Typical Batch MiDing Runs
Page 113 and 114:
87 It appears that the higher proce
Page 115 and 116:
89 injection (Dealy and Wissbrun, 1
Page 117 and 118:
91 rheological power scaling law fo
Page 119 and 120:
93 In the calculations, the freVuen
Page 121 and 122:
95 whereas H(?.) of the unmodified
Page 123 and 124:
97 However, the disintegration of t
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99 the Section 4.1.3. As evident fr
Page 127 and 128:
101 changes in dynamic moduli and m
Page 129 and 130:
103 In the case of 270 °C, the mod
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105 accessibility of unreacted grou
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107 believed to be charactenzed by
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109 increase in the melt elasticity
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111 In general, for crosslinked sys
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113 crosslinked gels in swelling eV
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115 formation of epoxy/PET reaction
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117 A seVuential reactive extrusion
Page 145 and 146:
CHAPTER 6 CONCLUSIONS AND RECOMMEND
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121 of PET by the selected tnepoxid
Page 149 and 150:
REFERENCES S. Abe and M. Yamaguchi,
Page 151 and 152:
125 L. M. Dossin and W. W. Graessle
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127 P. Huang, Z. Zhong, S. Zheng, W
Page 155 and 156:
129 J. Meissner and J. Hostettler,
Page 157 and 158:
131 T. Shiwaku, K. Hijikata, K. Fur
Page 159 and 160:
133 M. Xanthos and S. K. Dey, "Foam
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A reactive melt modification of polyethylene terephthalate

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