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