urvashi thesis
TRANSCRIPT
Synthesis of Phenolic Resin Blended Castor Oil Based Polyol for the
Preparation of UV Resistant Polyurethane Coating
A THESIS
Submitted to
DEPARTMENT OF CHEMISTRY
Chaudhary Devi Lal University, Sirsa
In partial fulfillment of the requirements
for the award of the degree
DOCTOR OF PHILOSOPHY
In
Chemistry
Supervisor: Submitted By:
Dr. VAZID ALI Urvashi VashishtAssistant professor
Department of Chemistry Regn.No: 616087510003
Chaudhary Devi Lal University
Sirsa 125055
Co Supervisor:
Dr. JYOTSNA KAUSHAL
Professor & HOD
Department of Applied science
Chitkara University (Punjab)
DEPARTMENT OF CHEMISTRY
Chaudhary Devi Lal University,
Sirsa-125055 (Haryana), 2012
TO WHOM IT MAY CONCERN
This is to certify that Ms. Urvashi Vashisht, student of Ph.D (Chemistry) of Chaudhary Devi Lal
University, Sirsa carried out her research work “Synthesis of Phenolic Resin Blended Castor
Oil Based Polyol for the Preparation of UV Resistant Polyurethane Coating”. She has been
regular, sincere and hardworking student during this period.
I wish her all success in her future endeavors.
Dr. VAZID ALI
Assistant professor
Department of Chemistry
Chaudhary Devi Lal University
Sirsa
DEPARTMENT OF CHEMISTRY
Chaudhary Devi Lal University,
Sirsa-125055 (Haryana)
Date:
SUPERVISOR’S CERTIFICATE
This is to certify that the research entitled “Synthesis of Phenolic Resin Blended Castor Oil
Based Polyol for the Preparation of UV Resistant Polyurethane Coating” is an original piece
of research work, carried out by Ms. Urvashi Vashisht, under my guidance. No part of this work
has been submitted to any other universities or institutions for any degree or diploma.
Dr. VAZID ALI
Assistant professor Department of Chemistry
Chaudhary Devi Lal University
Sirsa 125 055
Department of Applied Sciences
Chitkara University
Rajpura, Chandigarh
Date:
CO- SUPERVISOR’S CERTIFICATE
This is to certify that the research entitled “Synthesis of Phenolic Resin Blended Castor Oil
Based Polyol for the Preparation of UV Resistant Polyurethane Coating” is an original piece
of research work, carried out by Ms. Urvashi Vashisht, under my guidance. No part of this work
has been submitted to any other universities or institutions for any degree or diploma.
Dr. Jyotsna Kaushal Professor & HOD
Department of Applied Sciences
Chitkara University (Punjab) Rajpura.
ACKNOWLEDGEMENTS
Research work is undoubtedly teamwork. I put on record my compliments to all those who in one way or the other helped me in completing this piece of research.I acknowledge with immense pleasure my sincere and deep sense of gratitude to my esteemed
major advisor and mentor Dr. Vazid Ali for his invaluable guidance and constant encouragement
throughout the course of my doctoral research.
It was really a pleasure for me to work under his scholarly guidance and his unfailing dedication
in solving my problems during the entire investigation was a constant source of inspiration.
I am very thankful to my co-supervisor Dr. Jyotsna Kaushal, Department of Applied Sciences,
Chitkara University, Rajpura, for giving her innocent cooperation with great kindness for
completion of this research.
Heartful thanks to Vice-Chancellor (VC) Dr. K.C Bardhwaj for providing necessary facilities ,
Dr. Vikas singh(HOD) and Ms. Gita rani(Assistant Professor) for their valuable assistance and
help from time to time.
I would also like to acknowledge my indebtedness to Dr. G.D Tyagi, Dr. Rakesh Kumar and
my friends for their support and cooperation.
I truly express my feelings , which cannot be molded into words from the core of my heart to my
affectionate parents (Mr. Vijay Kumar Vashisht & Mrs. Sandhya Vashisht), my brother
(Nitin) and sister (Kanika), who guided me towards the right path with constant motivation
and their constant emotional support helped me a lot in completing this research work.
There are so many others whom I may have inadvertently left out and I sincerely help all of them
for their help.
Date: Urvashi Vashisht
\
CONTENTS
Sr. No. Chapter Page No.
1 INTRODUCTION .......................................... 1
1.1 Polymers .......................................... 2
1.2 Historical Background ........................................... 2
1.3 Classification of Polymers ........................................... 4
1.4 Engineering Plastics (Polymers) ........................................... 12
Epoxy ........................................... 13
Silicones ........................................... 14
High temperature Resistant Plastics ............................. 15
Conducting Polymers ............................. 17
1.5 Polyurethane ........................................... 18
1.6 Chemistry of Polyurethane ........................................... 19
1.7 Scope of Polyurethanes ........................................... 21
1.8 Raw Materials ........................................... 25
1.8.a Isocyanates ............................................ 25
1.8.b Hydroxyl Group Containing Compounds (Polyols) ................... 29
Polyether Polyols ............................................ 29
Polester Polyols ............................................ 30
Vegetable Oils ............................................. 30
Castor Oil based Polyols ............................................. 30
1.8.c Catalysts ............................................. 31
1.8.d Additives .............................................. 31
1.9 Brief Description of Coatings .................................................. 32
1.10 Polyurethane Applications .............................................. 33
1.11 References ............................................... 34
2 REVIEW OF LITERATURE ............................................... 39
2.1 Objective of the Work ............................................... 67
2.2 References ................................................ 68
3. EXPERIMENTAL ................................................. 76
3.1 Polyurethanes ................................................. 78
3.2 Apparatus/Instruments Used ................................................. 78
3.3 Chemical Used .................................................. 79
3.4 Distillation of Pyridine .................................................. 80
3.5 Methodology of Polyurethane Preparation .................. 80
3.6 Laboratory Synthesis ................................................... 81
3.7 Acid Value Measurement ................................................... 83
3.8 Hydroxyl Value Measurement ................................................... 83
3.9 Moisture Content Determination .................................................... 84
3.10 Chemical Resistance .................................................... 85
3.11 Spectroscopic Technique .................................................... 86
3.12 UV-Vis Spectroscopy .................................................... 87
Introduction .................................................... 88
Instrumentation of UV-Vis Spectrophotometer ................ 89
Applications of UV Spectroscopy ................ 90
3.13 FTIR Spectroscopy .................................................... 91
Instrumentation .................................................... 92
Applications of IR Spectroscopy ................ 93
3.14 Nuclear Magnetic Resonance Spectroscopy ................ 94
Instrumentation of NMR Spectrometers ............... 95
Applications of NMR Spectroscopy ............... 98
3.15 References ..................................................... 99
4. RESULTS AND DISCUSSION .................................................... 100
4.1 Synthesis, Physico-chemical Properties and Spectroscopic ........... 101
Characterization of Phenolic modified Castor Oil based Polyol.
4.2 Synthesis of Phenolic resin blended Castor Oil based modified ........... 114
Polyol for two Component Polyurethane Coating.
4.3 Synthesis of Castor Oil based phenolic resin blended Polyols for .......... 129
Two Component Polyurethane Coatings.
4.4 Synthesis of phenolic blended modified natural polyols for preparation ......... 144
of aliphatic two component polyurethane coatings. 4.5
Conclusion …………………………………… 170
4.6 Future of the Research Work …………………………………….. 170
LIST OF ACRONYMS
PU Polyurethane
FTIR Fourier Transform Infra red
UV Ultraviolet
NMR Nuclear magnetic Resonance
OH value Hydroxyl value
DEG Diethyleneglycol
DEA Diethanolamine
Ph.resin Phenolic resin
PhMP Phenolic modified polyol
PhMP+DEG Diethyleneglycol modified polyol
PhMP+DEA Diethanolamine modified polyol
TDI 2, 4'-toulene diisocyanate
MDI 4,4'-diphenyl methylene diisocyanate
IPDI Isophrone diisocyanate
BHT Butyl hydroxyl toluene
LIST OF SYMBOLS
α = Absorption Coefficient
h = Planck’s constant
ν = Frequency
Eg = Energy Band Gap
K = Extinction Coefficient
λ = Wavelength
π = Pi
cm = Centimeter
cm-1 = Wavenumber
0 = Degrees
0C = Degree Celcius
ml = millilitre
gm = gram
mol = moles
mol/L = moles per litre
LIST OF FIGURES
Figure 1.1 : Figure representing linear chain polymers. ……………………. 5
Figure 1.2 : Figure representing branched chain polymers. ……………………. 6
Figure 1.3 : Figure representing crosslinked polymers. ……………………. 6
Figure 1.4 : Showcasing Polyurethane production based on applications. ……………. 23
Figure 1.5 : Showcasing Polyurethane production based on types of polyurethane. …… 24
Figure 1.6 : Application of PUR by market sector in 2003. …………………….. 24
Figure 3.1 : Setup of reaction for synthesis of polyurethane. ……………………… 82
Figure 3.2 : Simple sketch of absorption measurement instruments. ………………….. 86
Figure 3.3 : UV-Vis Spectrophotometer. …………………….. 89
Figure 3.4 : Instrumental design of a double beam in-space UV-Visible Spectrophotometer.
………………………. 90
Figure 3.5 : Schematic diagram of a recording spectrophotometer. ………………….. 93
Figure 3.6 : Block diagram of an FT-NMR spectrometer. ………………………. 96
Figure 4.1a : FTIR spectra of PhMP. ………………………. 110
Figure 4.1b : FTIR spectra of PhMP+DEG. ……………………….. 110
Figure 4.1c : FTIR spectra of PhMP+DEA. ……………………….. 111
Figure 4.2a : NMR spectra of PhMP with highest concentration of phenolic resin. ……….. 111
Figure 4.2b : NMR spectra of PhMP+DEG with highest concentration of DEG. ………... 112
Figure 4.2c : NMR spectra of PhMP+DEA with highest concentration of DEA. ……….... 112
Figure 5.1a : FTIR spectra of polyol A2/A2*. ……………………….. 124
Figure 5.1b : FTIR spectra of polyol B2/B2*. ……………………….. 124
Figure 5.2a : NMR spectra of polyol A1/A1*. ……………………….. 125
Figure 5.2b : NMR spectra of polyol A2/A2*. ………………………. 125
Figure 5.2c : NMR spectra of polyol A3/A3*. ………………………... 125
Figure 5.2d : NMR spectra of polyol A4/A4*. ………………………………. 126
Figure 5.3a : NMR spectra of polyol B1/B1*. ……………………………….. 126
Figure 5.3b : NMR spectra of polyol B2/B2*. .………………………………. 126
Figure 5.3c : NMR spectra of polyol B3/B3*. ……………………………….. 127
Figure 5.3d : NMR spectra of polyol B4/B4*. ……………………………….. 127
Figure 6.1 : UV graphs for PU coatings with TDI and MDI after UV exposure. ……….. 139
Figure 6.2 : UV graphs for PU coatings with TDI and MDI after UV exposure. ……….. 142
Figure 7.1 : UV graphs for PU coatings with IPDI before and after UV exposure. ………. 155
LIST OF TABLES
Table 1.1 : A few polymers with year of their first appearance and the names of the Scientist. ................................ 3
Table 1.2 : Some engineering plastics and their applications. ............................... 16
Table 3.1 : Some of the commonly used solvents and minimum wavelength from which they may be used. ................................ 88
Table 4.1 : Physico-chemical properties of synthesized phenolic modified polyol (PhMP).
................................ 107
Table 4.2 : Optical properties of phenolic modified polyol (PhMP). ................................ 108
Table 5.1 : Composition of different coating formulations. ................................ 118
Table 5.2 : Physico-chemical properties of synthesized chemically modified polyols. ...... 121
Table 5.3 : Physico-chemical properties of two component (PU) coatings with 2,4’-toluene diisocyanate (TDI). ................................ 121
Table 5.4 : Physico-chemical properties of two component (PU) coatings with 4,4’- methylene diphenyl diisocyanate (MDI). ................................. 122
Table 6.1 : Composition of different polyol formulations. .................................. 133
Table 6.2 : Composition of different coating formulations. .................................. 133
Table 6.3 : Physico-chemical properties of synthesized chemically modified polyols. ........ 134
Table 6.4 : Physico-chemical properties of two component (PU) coatings with 2,4’-toluene diisocyanate (TDI). ................................... 135
Table 6.5 : Physico-chemical properties of two component (PU) coatings with 4,4’-methylene diphenyl diisocyanate (MDI). ................................... 136
Table 7.1 : Physico-chemical properties of synthesized chemically modified polyols. ...... 150
Table 7.2 : Composition of different coating formulations. ................................... 151
Table 7.3 : Physico-chemical properties of two component (PU) coatings made by phenolic resin modified polyols with IPDI. ..................................... 152
Table 7.4 : Physico-chemical properties of two component (PU) coatings made by DEG modified polyols with IPDI. ...................................... 153
Table 7.5 : Chemical resistance of the prepared aliphatic two component polyurethane coating.
...................................... 161
LIST OF EQUATIONS
Equation 1.1 : Ring opening polymerization reaction. ......................................... 12
Eqaution 1.2 : Esterification of unsaturated fatty acids; an example. .......................... 14
Equation 1.3 : Generalized reaction for polyurethane polymerization. .......................... 20
Equation 1.4 : Reversible reaction for polyurethane polymerization. .......................... 20
Equation 1.5 : Reaction for allophanate production. ........................................ 20
Equation 1.6 : Reaction for synthesis of isocyanate. ......................................... 25
Equation 1.7 : Reaction of isocyanate with alcohol. ......................................... 28
Equation 1.8 : Reaction of isocyanate with carboxylic acid. ......................................... 28
Equation 1.9 : Reaction of isocyanate with water. .......................................... 28
Equation 1.10 : Reaction of isocyanate with urethane. .......................................... 28
Equation 1.11 : Reaction of isocyanate with amine. .......................................... 28
Equation 1.12 : Reaction of isocyanate with isocyanate. ........................................... 29
Equation 3.1 : Formula used to calculate acid value. ............................................ 83
Equation 3.2 : Formula used to calculate hydroxyl value. ............................................ 84
Equation 3.3 : Formula for determination of volumetric water content. ........................ 85
Equation 3.4 : Formula for water per unit mass of moist specimen. ......................... 85
Equation 3.5 : Moisture content formula. ............................................. 85
Equation 3.6 : Formula for energy difference between two states. ......................... 88
Equation 3.7 : Total energy of a molecule. ............................................... 88
Equation 3.8 : Formula of absorbance. ............................................... 90
Equation 3.9 : Formula for determination of molecular weight. ......................... 91
Equation 3.10 : Example of tautomeric equilibrium. ............................................... 91
Equation 3.11 : Formula for determination of concentration of one functional group of compound. ................................................. 93
Equation 3.12 : Relation of absorbance and concentration. ........................................... 94
Equation 4.1 : Equation for Tauc relationship. ........................................... 103
Equation 4.2 : Equation for determination of extinction coefficient and absorption coefficient.
............................................ 104
Equation 7.1 : Proposed possible mechanism for polyurethane formation from phenolic modified polyol with aliphatic isocyanate (IPDI). ........................ 152
Equation7.2 : Proposed possible mechanism for polyurethane formation from phenolic resin alongwith DEG modified polyol with aliphatic isocyanate (IPDI).
............................................... 153