Synthesis, Characterization and Properties of Vinyl

Ester Matrix Resins

Hui Li

Dissertation submitted to the Faculty of the Virginia Polytechnic Institute and

State University in partial fulfillment of the requirements for the degree of

DOCTOR OF PHILOSOPHY
in
CHEMISTRY

Judy. S. Riffle, Chair

James. E. McGrath
Garth. L. Wilkes
Allen. R. Shultz
Harry W. Gibson

January 21, 1998

Blacksburg, Virginia

Keywords: Characterization, Copolymerization, Dimethacrylate, Kinetics, Network, Vinylster

Copyright 1998, Hui Li

 Synthesis, Characterization and Properties of Vinyl Ester Matrix Resins

Hui Li

(ABSTRACT)

Vinyl ester oligomers diluted with styrene are important matrix resins for thermosetting
polymer composites. A major objective of this work has been to study the chemistry and
kinetics of the cure reactions of vinyl ester resins at elevated curing temperatures, which are
consistent with typical composite processing conditions. The crosslinking reaction of vinyl
ester resins was studied by FTIR and the loss of the carbon-carbon double bonds of the
methacrylate (943 cm-1) and styrene (910 cm-1) were followed independently. A small
background absorbance overlapping the absorbance at 943 cm-1 was subtracted from all
spectra collected as a function of reaction time to quantify conversions. Copolymerization
reactivity ratios of styrene and terminal methacrylates on vinyl ester oligomers were calculated
to be rs = 0.36 ± 0.05 and rm = 0.24 ± 0.1 from early conversion data obtained at 140 oC on a
series of resins with systematically increasing levels of styrene. The composition data were
analyzed using the integrated form of the copolymerization equation and assuming a terminal
reactivity model to predict copolymer compositions throughout the reactions. These curves
agreed well with the experimental data even at high conversion levels.

Another important part of this research was to study structure-property relationships of vinyl
ester resins. Characteristics of vinyl ester resins and networks such as shrinkage, viscosity,
crosslink density, glass transition temperature, gel swelling, and toughness have been studied.
The shrinkage of vinyl ester resins during cure was calculated according to density
measurements to be 4% - 10% depending on styrene content. It was found that the chain
length of vinyl ester oligomers strongly affects the properties of the networks. For vinyl ester
resins with longer lengths (Mn = 1000 g/mol), crosslinked networks have higher fracture
toughness values and lower Tg’s.

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Finally, the synthesis, cure reactions and toughness of a new low viscosity vinyl ester resin
were also investigated in this work. The new oligomer has a structure with which the
hydroxyl groups on the backbone are replaced by methyl groups. They could be processed
without a diluent. The cure reactions of the new resin were studied by FTIR, DSC and 13C-
NMR.

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 Dedicated to

My daughter Melissa

and

My husband Jianye Wen

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 ACKNOWLEDGMENTS

I would like to thank Dr. Judy Riffle, my research advisor, for her guidance, encouragement,
and support throughout my graduate study. She acted as the driving force behind this
research. She provides the opportunity for each student to do his/her own research, yet when
asked, she is always willing to provide her knowledge and expertise to assist in understanding
the problem. Her professional and personable attitude has made my stay at Virginia tech a
very rewarding and memorable experience.

I would also like to thank my committee members, Dr. James E. McGrath, Dr. Garth L.
Wilkes, Dr. A. Shultz, Dr. H. Gibson, and Dr. R. Davis for serving on my committee, for
helpful discussions, and for reviewing my research program.

Also, I am grateful to acknowledge all of Dr. Riffle’s group members who provided not only
scientific, but also moral support, and most of all friendship, throughout my study and
research.

Special thanks are given to many faculty and staff members at Virginia Polytechnic Institute
and State University for their assistance during my graduate study.

My utmost appreciation and thanks are given to my husband, Jianye Wen, for his love and
support throughout my graduate career. I also thank my daughter, Melissa, for bringing so
much joy the moment she came into my life. My parents and mother-in-law have traveled
across the Pacific Ocean to give their support. Without them I could never have accomplished
my dream.

Finally, I would like to acknowledge the financial support provided by Dr. Riffle through
grants from the NSF S&T Center for High Performance Polymeric Adhesives and Composites
and the NIST ATP contract Composites for Surface Transportation Applications

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(Hexcel/Virginia Tech), and to the Chemistry Department of Virginia Polytechnic and State
University through graduate assistantships and scholarships.

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 TABLE OF CONTENTS

CHAPTER 1. LITERATURE REVIEW 1

1.1. Introduction 1
1.2. Preparation of vinyl ester resins 3
1.3. Crosslinking Reactions 7
1.3.1. Initiators 7
1.3.2. Crosslinking Reaction 9
1.3.3. Kinetic Studies on Cure Reactions 12
1.3.4. Characterization of Cured Networks 19
1.4. Toughening the Vinyl Ester Resins 22
1.5. Cured Networks and Properties 25
1.5.1. Mechanical Properties 25
1.5.2. Shrinkage Control During Cure 25
1.5.3. Thermal and Oxidative Stability 27
1.5.4. Chemical Resistance And Water Adsorption 27
1.6. Applications 28

CHAPTER 2. EXPERIMENTAL 30
2.1. Materials 30
2.2. Kinetics Study by FTIR 35
2.3. Sol and Gel analysis 37
2.4. Synthesis of Vinyl Ester Oligomers 38
2.4.1. Synthesis of [2,2-bis(4-(2-hydroxyprop-1-oxy)phenyl]propane
or Bisphenol A Propoxylate 38
2.4.2. Methacrylation of Bisphenol A Propoxylate 38
2.5. Preparation of Vinyl Ester Resin Samples 39
2.6. Vinyl Ester Resin Blends 39
2.7. Characterization 39

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 2.7.1. 1H Nuclear Magnetic Resonance Spectroscopy (1H NMR) 39
2.7.2. Differential Scanning Calorimetry (DSC) 40
2.7.3. Dynamic Mechanical Analysis (DMA) 40
2.7.4. Thermogravimetric Analysis (TGA) 40
2.7.5. Fourier Transform Infrared spectroscopy (FTIR) 41
2.7.6. 13C- Solid State Nuclear Magnetic Resonance Spectroscopy 41
2.7.7. Viscosity Measurements 41
2.7.8. Density Measurements 41
2.7.9. Fracture Toughness 42
2.7.10. Scanning Electron Microscopy (SEM) 43
2.7.11. Sizing/resin Miscibility Measurement 43
2.7.12. Swelling Experiments 44

CHAPTER 3. RESULTS AND DISCUSSION 45

3.1. Network Formation of Vinyl Ester/styrene Resins 45
3.1.1. Introduction 45
3.1.2. Cure Reactions Studied by FTIR 48
3.1.3. Sol/Gel Analysis 64
3.1.4. Conclusions 70
3.2. Characterization of Vinyl Ester/styrene Networks 74
3.2.1. Introduction 74
3.2.2. Crosslink Density of Cured Vinyl Ester Resins Determined by DMA 75
3.2.3. Glass Transition Temperatures of Cured Networks 83
3.2.4. Cure Shrinkage of Vinyl Ester Networks 90
3.2.5. Fracture Toughness Measurements 95
3.2.6. Swelling Experiments 98
3.3. Rheological Behavior of Vinyl Ester Resins 105
3.3.1. Introduction 105
3.3.2. Results and Discussion 106

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 3.3.2.1. Effect of Styrene Contents 106
3.3.2.2. Effect of Temperature 107
3.3.2.3. Effect of Molecular Weight 108
3.3.2.4. Relationship Between the Viscosity, Processing Temperature
And Glass Transition Temperature 111
3.4. Synthesis and Characterization of dimathacrylate of Bisphenol A
Propoxylated Oligomer 115
3.4.1. Introduction 115
3.4.2. Synthesis of Vinyl Ester Oligomers 115
3.4.3. Polymerization and Copolymerization 117
3.5. Blends of Thermoplastic Polymers with Vinyl Ester Resins 136
3.5.1. Introduction 136
3.5.2. Theory of Hydrogen bonded polymer blends 137
3.5.3. Miscibility of Vinyl Ester Blends 138

CHAPTER 4. CONCLUSIONS 150

CHAPTER 5. FUTURE WORK 152

VITA 154

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LIST OF TABLES

Table 1.1. Mechanical properties of vinyl ester resin castings. 22

Table 1.2. Fracture toughness K1c and Fracture energy G1c values of several
polymeric materials. 24
Table 1.3. Typical mechanical properties of vinyl ester resins 26
Table 3.1.1. Analysis of methacrylate conversion by 13C solid state NMR 54
Table 3.1.2. Feed and copolymer (slopes of d[S] vs. d[M] at early conversion) 57
Table 3.1.3. Composition of sols as a function of cure time 65
Table 3.1.4. Gel analysis by Differential Scanning Calorimetry 70
Table 3.1.5. Conversion data of Derekane441-400 at various cure temperatures
by FTIR(1.1 wt% benzoyl peroxide and 0.2 wt% t-butylperoxybenzoate) 71
Table 3.1.6. Conversion data of vinyl ester resins with various styrene contents cured at
140oC by FTIR (1.1 wt% benzoyl peroxide and 0.2 wt%
t-butylperoxybenzoate) 72
Table 3.1.7. Conversion data of vinyl ester resins with various styrene contents cured at
140oC by FTIR (1.1 wt% benzoyl peroxide and 0.2 wt%
t-butylperoxybenzoate) 73
Table 3.2.1. Dynamic viscoelastic properties and crosslink densities of cured vinyl
ester resins (cured at 140 oC). Mn=688 g/mol. 79
Table 3.2.2. Dynamic viscoelastic properties and crosslink densities of cured vinyl
ester resins (cured at 140 oC). Mn=1000 g/mol. 79
Table 3.2.3. Calculated Tgo of uncrosslinked vinyl ester/styrene copolymer 86
Table 3.2.4. Glass transition temperatures of cured vinyl ester/styrene
networks (DSC), Mn = 690 g/mol 89
Table 3.2.5. Properties of Derakane 411-400. 89
Table 3.2.6. Fracture toughness of vinyl ester resins. 97
Table 3.2.7. Swelling data of crosslinked vinyl ester/styrene networks

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 (Mn = 690 g/mol) 101
Table 3.2.8. Swelling data of crosslinked vinyl ester/styrene networks
(Mn = 1000 g/mol). 101
Table 3.2.9. δ and χ values and Mc determined by swelling measurements
(molecular weight of vinyl ester oligomer is 690 g/mol). 102
Table 3.2.10. Mc values determined by different methods. 104
Table 3.3.1. Constants A and B in Andrade equation for various vinyl ester resins 108
Table 3.4.1. Final conversion of double bonds for the dimethacrylate of the
propoxylated bisphenol-A By DSC. 127
Table 3.4.2. Comparison of K1c of of dimathacrylate of bisphenol A
propoxylate resins and other vinyl ester resins 134
Table 3.5.1. Miscibility of sizing materials with vinyl ester resins 139

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LIST OF FIGURES

Figure 1.1. Synthesis of vinyl ester by the reaction of a bisphenol-A glycidylether

with methacrylic acid. 5
Figure 1.2. Examples of components of vinyl esters 6
Figure 1.3. Preparation of toughed vinyl ester resins. 8
Figure 1.4. Schematic representation of free-radical crosslinking mechanism. 10
Figure 2.1. The structure of vinyl ester oligomer of Derakane 441-400 32
Figure 2.2. 1H-NMR spectrum of Derakane 411-400 (Mn=690g/mol, 28% styrene 33
Figure 2.3. Heated IR Cell for Monitoring Cure Reactions 36
Figure 2.4. Density determination kit. 42
Figure 3.1.1. Typical conditions for free radical addition copolymerization of vinyl ester
-styrene resins. 46
Figure 3.1.2. Styrene content effects on methacrylate conversion at 140 oC 49
Figure 3.1.3. Styrene content effects on conversion of styrene (140 oC) 50
Figure 3.1.4. Infrared spectra of a vinyl ester resin during cure (120 oC). 51
Figure 3.1.5. Infrared spectrum of a linear polyhydroxyether model with the same
chemical structure as the vinyl ester backbone. 52
Figure 3.1.6. 13C-NMR spectra of (a) fully cured vinyl ester resin and (b) the fully cured
resin with 9% unreacted methacrylate groups added. 53
Figure 3.1.7. Styrene consumption as a function of methacrylate consumption.
[S]o and [M]o: Concentration of feed. Copolymer compositions for
assessing the reactivity ratios were calculated from the early conversion
portions of the graphs. 58
Figure 3.1.8. Graphical determination of rs and rm 59
Figure 3.1.9. Comparison of copolymer compositions with feed composition
for the vinyl ester styrene thermoset relative to a linear methyl
methacrylate-styrene composition. 61
Figure 3.1.10. Cure reaction rate as a function of total double bond conversion

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 for Derakane 441-400 (1.1 wt% benzoyl peroxide plus 0.2 wt%
t-butyl peroxybenzoate). 62
Figure 3.1.11 Copolymer compositions calculated using rs = 0.36 and rm = 0.24 and the
integrated copolymer equation. Comparisons are made between
experiments and prediction. 63
Figure 3.1.12 Gel composition during cure (Derakane 441-400, Mn of the vinyl ester
oligomer equals 690 g/mol, 28 wt% styrene). 66
Figure 3.1.13. Reaction conversion at various cure temperatures 69
Figure 3.2.1. Crosslink density vs. weight percentage of styrene in the cured
vinyl ester resins 80
Figure 3.2.2. Conversions of cured vinyl ester-styrene resins calculated from both
FTIR and 13C-NMR. 82
Figure 3.2.3. Glass transition temperature vs. crosslink density. 87
Figure 3.2.4. Tg-Tgo vs. crosslink density. 88
Figure 3.2.5. DMA results of Derakane 441-400. 91
Figure 3.2.6. Reaction conversion at various cure temperatures. 92
Figure 3.2.7. Specific volume of vinyl ester resin as function of styrene. 94
Figure 3.2.8. Cure shrinkage of vinyl ester resin as function of styrene. 95
Figure 3.2.9. Typical dynamic properties of crosslinked vinyl ester-styrene resin
(28 wt% styrene, Mn=1000 g/mol). 99
Figure 3.2.10. Swelling index as a function of styrene content. 103
Figure 3.3.1. Viscosity of uncured vinyl ester resins at 25oC. (Mn = 690 g/Mol) 109
Figure 3.3.2. Plot of Log η vs 1/T for different vinyl ester resins. 110
Figure 3.3.3. Glass transition temperature of VER with Mn = 690 g/mol. 113

Figure 3.3.4. Plot Log η vs. T-Tg for 20 wt%, 25 wt% and 35 wt% styrene of vinyl

ester resin with Mn = 690 g/Mol. 114

Figure 3.4.1. Structure comparison of two vinyl ester resins. Top structure:
dimethacrylate of diglycidyl ether of bisphenol A; Bottom structure:

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 dimethacrylate of propoxylated bisphenol A. 116
Figure 3.4.2. 1H-NMR spectrum of [2,2-bis(4-(2-hydroxyprop-1-oxy)phenyl] propane or
bisphenol A propoxylate synthesized in our laboratory. 119
Figure 3.4.3. 1H-NMR spectrum of dimethacrylate of bisphenol A propoxylate.
Bisphenol A propoxylate was synthesized in our laboratory. 120
Figure 3.4.4. IR spectra of propoxylated bisphenol-A and dimethacrylate of
bisphenol A propoxylate. 121
Figure 3.4.5. IR spectra of dimethacrylate of bisphenol A propoxylate resins during
cure reaction (160 oC). 123
Figure 3.4.6. Double bond conversion of the dimethacrylate of bisphenol A
propoxylate resins at different cure temperature. 124
13
Figure 3.4.7. C-NMR spectrum of the dimethacrylate of bisphenol A
propoxylate network. 125
Figure 3.4.8. 13C-NMR spectrum of a network from the dimethacrylate of bisphenol A
propoxylate diluted with 30 wt% styrene. 126
Figure 3.4.9. Methacrylate conversion with time studied by FTIR at 140oc.
for the dimethacrylate of bisphenol A propoxylate diluted with
30 wt% styrene. 128
Figure 3.4.10. (a) Isothermal cure of the dimethacrylate of bisphenol A
propoxylate at various temperature; (b) dynamic scan after
the isothermal cure. 1% of t-BPB was used as initiator. 129
Figure 3.4.11. DMA of a network prepared by curing the dimethacrylate of
bisphenol A propoxylate resins. 130
Figure 3.4.12. DMA of networks prepared by co-curing the dimethacrylate of
bisphenol A propoxylate diluted with 10, 20, and 30 wt% styrene. 131
Figure 3.4.13. TGA of cured neat dimethacrylate of bisphenol A propoxylate resin
(A) and neat vinyl ester resin (B) (Mn = 690 g/mol ). 135
Figure 3.5.1. DSC diagrams of pure PVP, vinyl ester resin, and their blends. 140
Figure 3.5.2. Glass transition temperatures as a function of PVP percentage. 141

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Figure 3.5.3. Glass transition temperatures as a function of PEZO percentage. 142
Figure 3.5.4. FTIR spectra of vinyl ester resin and 50:50 blend of vinyl ester resin
with PVP in OH stretching region. 145
Figure 3.5.5. FTIR spectra of PEZO and 50:50 blend of vinyl ester resin with PVP
in carbonyl stretching region. 146
Figure 3.5.6. FTIR spectra of vinyl ester resin and 50:50 blend of vinyl ester resin
with PEZO in OH stretching region. 147
Figure 3.5.7. FTIR spectra of PEZO and 50:50 blend of vinyl ester resin with
PEZO in carbonyl stretching region. 148
Figure 3.5.8. FTIR spectra of PVP and 50:50 blend of Derakane 441-400 with
PVP in carbonyl stretching region. 149

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