u 1:, ,_ :

 

TH E813

23-: i

This is to certify that the
thesis entitled

PREPARATION AND COPOLYMERIZATION OF SOYBEAN
OIL BASED MONOMERS

presented by

Samantha K. Friedlander

has been accepted towards fulfillment
of the requirements for the

Masters of Science degree in Chemical Engineering

 

 

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5/08 K:/Proj/Aoc&Pres/ClRC/DateDue indd

PREPARATION AND COPOLYMERIZATION 0F SOYBEAN OIL BASED
MONOMERS

BY

Samantha K. Friedlander

A THESIS
Submitted to
Michigan State University
in partial fulfillment of the requirements
for the degree of
MASTER OF SCIENCE

CHEMICAL ENGINEERING

2010

ABSTRACT

PREPARATION AND COPOLYMERIZATION OF SOYBEAN OIL BASED
MONOMERS

BY
Samantha K. Friedlander
Society is pushing for a reduction in the use of
petroleum-based materials. Soybean oil is a renewable,
readily available, inexpensive resource that can be used in
the production of novel polymers. By using allyl alcohol
in the transesterification of soybean oil or fatty acid
methyl ester (FAME) a terminal double bond can be added to
the fatty acid chain. The methods for the conversion of
soybean oil and FAME were investigated. The equilibrium
kinetics for the transesterification of soybean oil was
also determined. The terminal double bond that was added
is then polymerized via free radical polymerization. A
copolymer of the fatty acid allyl ester with styrene was
produced with a random monomer configuration. A maximum of

30% ester was incorporated into the polymer.

ACKNOWLEDGMENTS

I would first like to thank my family for all of their
support and help. My parents have had to listen to all of
my exciting breakthroughs and all of the times when things
didn’t work out quite the way they were supposed to. My
grandparents and aunt have been supportive of all of my
endeavors, especially this one.

I would also like to thank Dr. Narayan for giving me the
chance to do the research and all the help along the way.
Dr. Dan Graiver, Ken Farminer and Gary Decker have also

been a huge help in this accomplishment.

iii

TABLE OF CONTENTS

LIST OF TABLES.......OOOOOOOOOOO......OOOOOOOOOOOVi
LIST OF FIGURES.........OOOOOOOOOOOOOO......OOOOVii

lCEAJflflfl! 1

BACMKHUNUNDN.........H.........H.........H.........H....1
1.1 Why use alternative fuels? ................. ...... ... 1
1.2 Biodiesel, what it is and how it is made ............ 5
1.3 Cloud Point and Pour Point of Biodiesel ............ 14

lCEAJHHHR 2

BIOBASED MONOMERS................................20
2.1 Literature Review'.................................. 20
2.1.1 Introduction ..... ......... ..... . ............ ... 20
2.1.2 Triglycerides .. ..... ....... ....... . ............ 21
2.1.3 Triglyceride Based Monomers .................... 22
2.1.4 Monomers from Fatty Acids ...................... 26
2 Transesterification of Soybean Oil ................. 29
2.2 1 Materials ................................ ...... 29
2.2.2 Experimental procedure ......................... 29
2 2.3 Characterization ............................... 30
2 2 4 Results ........................................ 31
2.3 Transesterification of Fatty Acid Methyl Esters
(

AMEs) ................................................ 39

2.

1 Materials ...................................... 39
.3 2 Experimental procedure .. .............. ......... 39
.3.3 Characterization ............................... 40
.3.4 Results ........................................ 40
Discussion of the two methods of production.u...... 47
Kinetics of transesterification .................... 49
.5.1 Experimental Equipment ......................... 49
.5.2 Experimental Conditions ........................ 49

5.3 Experimental Procedure ......................... 50

4

5

.3.

2
2
2
2
2 4
2.5
2
2
2
2
2

.5. Characterization ....... ............... . ....... . 51
5 Results and Discussion ..... ....... ............. 52

iv

CHAPTER THREE

COPOLMRIZATION 0F MONOMRSCOOOOO0.0.0.00000000057
3.1 Literature ROViW......OOOOOOOOOOOO......OOOOOOOOOOs7

3.1.1 Modified Triglycerides ................ ......... 57
3.1.2 Unmodified Triglycerides ....................... 58
3.1.3 Fatty Acid polymerization ...................... 59
3.2 Polymerization .............. ........... . ........... 61
3.2.1 Monomer synthesis .............................. 61
3.2.2 Polymer Synthesis .............................. 62
3.2.3 Materials ... ..... .............. ................ 63
3.2.4 Characterization ............................... 63
3.2.5 Results . ....................................... 64
CEUUHNER 4

CONCLUSIONS 0 O O O O O O O O O O O O O O O O O 0 O O O O O O O 0 O O O O O O O O O O O 7 1
4.1 Review of werk and Results ......................... 71
4 O 2 Future work 0 O O O O O O O O O O O O 0 O O O O O O O O O O O O 0 O O O O O O O O O O O O O 7 2

Appendix 1: Theoretical Iodine Value Calculation.73

Appendix 2: Equilibrium Constant Calculation Method

0.........-......OOOOOCOOC0.0...00.00.00.0000000076

Appendix 3: TGA Traces of the Copolymer Samples..81

Appendix 4: H-NMR Spectra of the Copolymer Samples

..................OOOOOOOOOOOOOO0.00.00.00.00000084

ReferenCBSOOOOOO.........OOOOOOOOOOOCOO0.00.00.0088

Table

Table

Table

Table

Table

Table

Table

Table

Table

Table

Table

LIST OF TABLES

1:Composistion of a Soybean Seed....................8
2:Composistion of Crude and Refined Soybean Oil.....9
3:Composistion of Soybean Oil and Similar 0ils.....13

4:Iodine Values for Soybean Oil and Allyl Ester
PrOductOO0.0......OOOOOOOOOOOO0.0.0.000000000000034

5:Retention Times and Percentage of Components in
Allyl Ester and Methyl Ester Produced from Soybean

OiIOOOO......OOOOOOOOOOOOO...0.0.0.0000000000000038

6:Average Iodine Values for Allyl Ester and the
Methyl Ester Used to Produced It.................43

7:Retention Times and Percentage of Components in
Allyl Ester and Methyl Ester Produced from Methyl

Ester...OO.......OOOOOO......OOOOOOOO0.00.00.00.044
8: Equilibrium Constant for Various Concentrations.56
9: Ratios of Allyl Ester to Monomer in the Feed....62

10: H-NMR Peak Heights of the Copolymers and the
Resulting Monomer Ratios in the Copolymer........69

11:Composistion of Soybean Oil Used in Expriments..73

vi

Figure

Figure
Figure
Figure

Figure

Figure

Figure

Figure

Figure

Figure

Figure

Figure
Figure
Figure
Figure

Figure

LIST OF FIGURES

1: World Energy Consumption and Top Energy Consumers
1997-2006..........OOOOOOOOOOOOOOOO00.0.0000000001

U.S. Petroleum Use 1970-2008....................4
Transesterification of Triglyceride to FAMEs....S
Triglyceride Components.........................6

Fatty Acids in Soybean Oil After
Transesterificaton................... ..... . ...... 7

6: Process Flow Diagrams for Batch (Top) and
Continuous (Bottom) Biodiesel Production.........12

7a: Chemical Pathways from a Triglyceride to
monomerSOOOO......OOOOOOOO......OOOOOOOOOOO0.0.0.23

7b: Chemical Pathways from a Triglyceride to
monomers (continueS)OOOOOOOOOO0.0.00000000000000024

8: Esterification of the Fatty Acid Using an Acid
catalyst...O......OOOOOOOOOCOO00.0.0...0.00.00.0027

9: Transesterification of Methyl Ester with Methanol

as a Byproduct...................................28

10: Transesterification of the Triglyceride to
PrOduceA11Y1 EsterSOOOO...0.0.00000000000000000028

11a: FTIR Spectrum of Allyl Ester.................31
11b: FTIR Spectrum of Soybean Oil.................32
12: Peak Characteristic of =C-H Stretch...........33
13: Peak Characteristic of C=O Stretch............34

14: H-NMR Spectrum of Soybean Oil.................36

vii

Figure

Figure

Figure
Figure
Figure
Figure

Figure

Figure

Figure

Figure

Figure

Figure

Figure

Figure
Figure
Figure

Figure

Figure

Figure

15: H-NMR Spectrum of Allyl Ester from Soybean

OiIOIOO0............OOOOOOOOOOOOOOOOO00.000.00.037

16a: FTIR Spectrum of Allyl Ester from Methyl
Ester...000............OOOOOOOOOOOOOOOIO... ...... 40

16b: FTIR Spectrum of Methyl Ester................41
17: Peak Associated with C=O Stretch..............42
18: Peak Associated with =C-H Stretch ............. 42
19: H-NMR Spectrum for Methyl Ester...............45

20: H-NMR Spectrum for Allyl Ester Produced from
nethYI EsterOOOOO.....OOOOOOOOOOOO...0.0.0000000046

21: Conversion of methyl Ester to Allyl Ester with
the Removal and Addition of Alcohol..............48

22: Step—wise Reaction for Allyl Ester Production
from SOYbean OiIOOOOOOOOOOOOOOOOOOO0.0.00.00.00.052

23: Reaction Scheme Used for Equilibrium
KinetiCSOOOOOOOOOOO......OOOOOICOO00.0.0.0...0.0.53

24: Percent Soybean Oil Conversion with Respect to

Time...O0............OOOOOOOOOOOOOO0......0......53

25: Effect of the Catalyst Concentration on the
convergionOOOOO0............OOOOOOOOOOOOOOOOO0.0.54

26: Molecular Weight as a Function of Monomer

FeedOOOOOOOOOOO......OOOOOOOOOOOOOOOO0...... ..... 65

27: TGA of Styrene/Allyl Ester Polymer............66

28. DSC Traces of the Four C0polymer Samples......67

29: Simulated H-NMR and Copolymer Structure.......68

30: Composition of Allyl Ester in the Monomer Feed
and the Resulting Copolymer......................7O

31: TGA Trace for COpolymer Sample 2..............81

32: TGA Trace for Copolymer Sample 3..............82

viii

Figure
Figure
Figure
Figure

Figure

33:

34:

35:

36:

37:

TGA Trace for Copolymer Sample 4..............83
H-NMR Spectrum for Copolymer Sample 1.........84
H-NMR Spectrum for Copolymer Sample 2.........85
H-NMR Spectrum for Copolymer Sample 3 ......... 86

H-NMR Spectrum for Copolymer Sample 4.........87

ix

CHAPTER 1

BACKGROUND

1.1 Why use alternative fuels?

The world has a dependence on fossil fuels; they are used
in all of our daily activities; from driving a car to
turning on the lights, most of the power that we use comes

from a fossil fuel. The world used approximately 469.4
quadrillion BTU in 2006.1 The energy use trend for the

world and the top two energy-consuming nations, as of 2008,

can be seen in figure 1.

 

500

 

 

 

 

World/
400
m 300
I:
O
«4
H
H
v!
% mm
3
United States
China ............
o T T
1997 1999 2001 2003 2005

Figure 1: World Energy Consumption and Top Energy Consumers

1997-20061

Although the United States energy use has remained
relatively constant in the past decade, most of the energy
was supplied by fossil fuels. Of the total energy used in
2008, approximately 7% was produced from renewable

resources, and more than 80% was produced from fossil

fuels, the remaining being from nuclear energy.1

There are four main sectors for energy use; transportation
being the second major use of energy in the United States
(the first is industrial usage), but only 3% of these fuels
were from renewable resources (in 2008). The two main

sources for renewable transportation fuel are ethanol and
biodiesel.1 So why use a renewable resource? There are
many reasons for one to use an alternative fuel, such as
biodiesel over the conventional petroleum diesel. One
reason is for the reduction of our carbon footprint. The
EPA's definition of a carbon footprint is ”the amount of
greenhouse gasses (GHG) that are emitted by one entity,
such as a personmor companyz)." A measurement of one's
carbon footprint will include both direct sources (such as
driving a car) and indirect sources (a consequence of an
activity, such as, purchasing electricity) and is reported
in units of 002.2 iBy using a renewable fuel like biodiesel,
one's carbon footprint is reduced because the carbon is

newly fixed carbon (soybeans for example) as opposed to

carbon that was fixed millions of years ago (any fossil
fuel).

Reducing GHG emissions is very important to the ecosystem;
it is believed to be the cause of recent climate change.
It's true that GHG's are important for life on Earth, as
they keep the planet warmer than it would be without them.
However, the massive influx of GHG's into the atmosphere is

the cause of a rise in global temperature.3 This rise in

temperature is causing damage to the ecosystem, rising sea
levels due to melting of ice caps and a change in rainfall
patterns across the globe are just two examples of these
effects.

A second and sometimes a more popular opinion for the
conversion to biodiesel and other renewable resources is a
reduction or elimination of the dependence on foreign oil.

As seen in figure 2, the United States imports over half of

the oil that is used in this country.4 This dependence will

only increase as the oil in this country is depleted.4 It is

also seen in figure 2, that the U.S. production of oil is

decreasing every year.

N
U'l

NJ
CD

    

 

 

>

rt:

C3

5—

a)

n. 15

% Netlmports

‘5 10

co

m

8 5 U.S. Oil Production

5 o

E .2 a s :3 a a s a
CD 0‘ 01 03 CA ON C) CD
r4 v4 r4 r4 r4 r4 cu cu

Figure 2: U.S. petroleum Use 1970-20084

As the need for oil grows, the dependence on foreign
countries also grows. Of the top five oil producing
countries (Saudi Arabia, Russia, United States, Iran and
China) only two of the countries have the tap proven oil

reserves (Saudi Arabia, Canada, Iran, Iraq, Kuwait).s

Unfortunately some of these oil rich countries have a
history of political unrest and disagreements with the
United States. If the United States can create a
sustainable fuel source contained within its borders, it
will not have to rely on other countries.

With the quest for a sustainable fuel, and the passage of
the Energy Independence and Securities Act of 2007(EISA)

another advantageous side effect can be found the creation

of green jobs. The EISA requires that 36 billion gallons
of motor fuel be produced from renewable sources. The
increased production of biofuels will help to create jobs
in all sectors of the economy; from farmers, seasonal
workers, train/truck drivers and construction workers, to

chemists and engineers all segments of the process will

need employees.6

1.2 Biodiesel, what it is and how it is made

The term ”biodiesel" was first used in a Chinese paper in

1988; however it was not used again until 1991.7 Biodiesel

refers to the fatty acid methyl esters produced from the
transesterification of vegetable oils and animal fats (more
specifically the triglycerides) and are also known as

FAMEs. This reaction is shown in figure 3.

R

0%
C) O HO
0 R
R Catalyst + /
3 //on + >—‘ 3 \TF/

0 HO
Methanol 0

on Fatty Acid
0 Methyl Ester

Glycerol (FAME)
0===<:

R

 

Triglyceride

Figure 3: Transesterification of Triglyceride to FAMEs

The major chemical component in the oils produced from
plant material and animal fats are triglycerides. Over 170
plants can be used for the production of biodiesel, the
main plant oil used in the U.S. is soybean oil.8

A triglyceride, as seen in figure 4, consists of ”3 fatty
acid chains joined at a glycerol juncture"9 (the glycerol
shown in hold). The ”R" on the fatty acid component of the

triglyceride is a carbon chain containing 14 to 22 carbons

and can contain 0 to 5 double bonds (depending on the
source of the triglyceridef10 Figure 5 shows the five

esters found in soybean oil.

0 0

H2 Hz A
C C
0/ ~Hi’ \O
0Y0

R2

R1 R3

Figure 4: Triglyceride Components
In a typical triglyceride, the fatty acids contribute 94-
96% of the total weight of the triglyceride.11 The chemical
and physical properties of the oil depend on the
stereochemistry of the double bonds, the degree of

unsaturation and the length of the chains.12

0
/// \\H//A\\V///\\\///\\\x//N\\v//A\\v//A\\~///\\\///\\\
Palmitic
O
0
//’ \\n//A\\C//x\\x///\\xx//\\xx//\\\o//~\\v//A\\C//A\\C//f\\\
0 Stearic
0 _
/\"/\/\/W—_\/\/W
Oleic
O
O __ __
//’ \\n//A\\C///\\\///\\xx//\\\x//F__T\\\///___\\\C//A\\C//”\\\
Linoleic
O

Linolenic

Figure 5: Fatty Acids in Soybean Oil After
Transesterificaton
Longer carbon chains are found in the temperate crops
(sunflower, soybean, and rapeseed oils) while shorter fatty
acid chains are found in the tropical crops, such as

3

coconut and palm oils.1 The average degree of unsaturation

(number of carbon-carbon double bonds) in the triglycerides
can be characterized by the iodine value. This is the

amount of iodine, in mg, that reacts with the double bonds
in a 1009 sample. There are three classifications of oils,

drying oils (iodine value>130), semi-drying oils (100<

iodine value >130) and non-drying oils (iodine value
(100) .11-13

The total distribution of the fatty acids varies between
types of crops and within each crop. Theses differences

are based on growing conditions, season and purification.11

Genetic engineering can be used to control the variation

within each crop.9

The production of biodiesel begins with the production of
soybean oil. The soybean (Glycine Max (L.) Merril) seed
consists of 2 cotyledons, a seed hull and the hypocotyl or

germ. The cotyledons make up 90% of the seed, and contain

essentially all of the protein and oil}14 This can be seen

in table 1 along with the composition of each element of

 

 

 

 

 

the seed.”' 15
Components Yield Protein Lipid Ash Carbohydrates
1%; (’3) (’3) (3'5) (‘3)
Cotyledon 90.3 42.8 22.8 5.0 29.4
Hull 7.3 8.8 1.0 4.3 85.9
Hypocotyl 2.4 40.8 11.4 4.4 43.4
5:33:21) 100.0 40.3 21.0 4.9 33.9

 

 

 

 

 

 

 

Table 1: Composition of a Soybean SeedL‘

Given that the interest is in the oil and not the meal, a

general overview of the oil extraction process will be

discussed; the refining of the crude oil will be in more

detail.

plant has two options for extraction of the oil; mechanical

After harvesting the soybean seeds, the production

 

extraction and solvent extraction. In both processes the
soybeans are dried, cleaned and flaked prior to extraction.

In mechanical operations the flaked soybeans are fed into a

15

screw press to squeeze out the oilfiu' Less than 1% of

14

the soybeans are processed by mechanical means, due to the

4, 15

4-5% oil left in the soy meal after extraction.1 In

solvent extraction, the oil is extracted from the flaked
seeds using hexane. The oil leaves the flakes and is
dissolved in the hexane. After extraction the hexane is
removed from the oil by flash evaporation, vacuum

14, 15

distillation or steam stripping. The crude oil then

has the properties seen in table 2.

 

 

 

 

 

Crude Oil (%) Refined Oil (%)
Triglycerides 95-97 0.99
Phospholipids 1.5-2.5 0.003-0.045
Unsaponifibles 1.6 0.3
Free Fatty Acids 0.3—0.7 <0.05

 

 

 

 

 

Table 2: Composition of Crude and Refined Soybean Oil14

There are four steps to the refining of soybean oil,
degumming, removal of free fatty acids, bleaching and
deodorization. The degumming stage of the process removes
the phospholipids and is generally carried out in the
extraction plant. A dilute phosphoric acid solution is
mixed with the oil to form gums; these gums then
precipitate and are removed by centrifugation. By removing

the phospholipids first a reduction in the oil loss is seen

in the following phases. The oil free phospholipids are

cleaned and sold as a byproduct known as soybean

lecithin..“'15

There are two methods for the removal of free fatty acids,
a chemical and a physical process. The chemical process
involves neutralization with an alkali to form a soap that
is soluble in water. This soap stock is removed in a
centrifuge and the oil is washed and dried and ready for
the next step. In physical refining, the fatty acids are
removed by steam distillation (this process also achieves

deodorization.).n'15

Bleaching and deodorization are two relatively simple

processes. Activated carbon is added to remove most of the
carotenoid pigments and chlorOphyll in the oil. The carbon
is then removed by filtration and the oil is deodorized by
steam distillation under high vacuum and temperature. The

final composition of the processed oil is shown in table 2.

14, 15

The production of biodiesel can begin using crude,
degummed, or completely refined oil, although the
processing changes slightly. The biodiesel reaction, seen
previously in figure 3 is a catalyzed reaction. The
catalyst can be an acid, base or an enzyme (lipase

catalyzed). In industry, the base reaction is primarily

10

used; this is due to the slow reaction speed of both the
acid and enzyme catalyst (as well as the cost of the

1"17'18 The base reaction is 4000 times faster

enzyme).
than the acid reaction (when using the same amount of
catalyst).18

The three main factors that affect the yield of the
production of biodiesel are the time, temperature and
amount of mixing. Given enough time the reaction will go
to completion at roomtemperature.18 This time, however, is
to long to make large scale production efficient.

Murugesan et al found that the most efficient reaction
temperature was between 60°C and 80°C, higher and lower
temperatures will give a lower yield. They also found that
a mixing speed of 360 rpm gives the best yield, any higher

mixing speed produces no increase in yield, although a
lower speed will decrease yield.18

There are two methods that can be used in the production of
biodiesel in industry (batch and continuous operations).17

In the batch reactor the residence times are longer,
usually 20 minutes to 1 hour. The continuous operation is
a series of plug flow reactors, with a separator between

each tank to remove the glycerol that is produced in each

11

tank to drive the reaction foreword.”' The residence time

in each reactor is 6-10 minutes.

 

 

 

 

   
 

 

 
  

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Water
Alcohol Water
—->
Biodiesel
Dryer
Ester
Alcohol Wash Water
Ester
Triglyceride
Alcohol
Catalyst <::=:::>
Batch Reactor
—-) Crude
‘ Glycerol
Alcohol
Triglyceride (TG) Glycerol
__"’ Heater Reactor 1‘
Alcohol T
CataIyst Alcohol
Separator
T yr? Ester
TG '
Ester

 

 

 

Alcohol '9 Reactor 2

 

 

 

 

 

 

 

 

 

1

Glycerol
Figure 6: Process Flow Diagrams for Batch (Top) and

Continuous (Bottom) Biodiesel Production17

12

After both the continuous and batch reaction the glycerol

and excess alcohol are removed and the base is neutralized.

A flow diagram of both the batch and continuous processes

are seen in figure 6.

The carbon chains produced from transesterification are

chemically similar to the ones found in petroleum diesel

(which are 10-15 carbon atom chains)19 and only have 10%

less energy than petroleum diesel.20

there are many other oils that can be used for the

As previously stated

production of biodiesel, table 3 shows the composition of

soy oil as well as other oils with similar composition.

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

veggfi‘ble 14:0 16:0 18:0 18:1 18:2 18:3 22:1
,. --
‘ Soybean __ 2.3.. 2.4.- 17.7— 40.. 2.. __
L .,., , t 13.3. ;5 30.8 ,57.1 .10.5
C°tt°nseed 1?; 2218.34. 2 .51 - 124177- 4568.72- " "
Rapeseed 10:5 1-6 35; 8-60 953' 1-13 5—56
“mm “ 1 ° 2'6 21:5 6562.; 1 63.11- 6154:11- '-
C°r n 0 ' ’ 3 12:5 31:3 2 ° '4 3 6329.5 1.35:5 "
peanut 0- . 5 6-14 1 '69“ 366724; 13-43 -- --

 

Table 3:Composistion of Soybean Oil and Similar Oils16

The two major differences between conventional diesel and

biodiesel are the internal double bonds and the oxygen

atoms found in the biodiesel chains.

strictly straight chain and single bonds.1

13

9

These two

Petroleum diesel is

 

differences produce advantages and disadvantages for the
biodiesel over the conventional diesel.

The oxygen in biodiesel leads to more complete combustion,
and therefore lower carbon monoxide and particulate
emissions. Being a bio-based fuel, its biodegradation is

faster than that of conventional diesel and it also has

higher lubricity and flash point.19 'There is an increase in
nitrogen oxide (NOx) emissions in biodiesel due to a higher

combustion temperature.”' The second difference, the

internal double bonds in the biodiesel, leads to a higher

oxidation rate.19

Although there are many advantages of biodiesel over
conventional diesel, one of the main limitations for using
biodiesel is the high cloud point and pour point

temperature associated with biodiesel.19"21"2""28

1.3 Cloud Point and Pour Point of Biodiesel

As previously mentioned one important concern with the
adoption of biodiesel into wide use is its high cloud point
(CP) and pour point (PP). This makes the use of biodiesel
difficult during the winter months in many states. The
ASTM definition for CP is ”the temperature at which the

smallest observable cluster of wax crystals appears upon

14

coolingzzu" This temperature is different from.the PP due

to the fact that the biodiesel can still flow and be used;
the PP is ”the lowest point at which movement of the
specimen is observedxt" The CP can still be a problem
though; the small crystals that form can clog the fuel
filter and fuel lines.

There are several commercial additives are known to improve
the properties of petroleum diesel. These additives,
however, only affect the PP of biodiesel, not the CP, even

when the amount used is more than the recommended amount.24

When four commercial additives were used on biodiesel from
four different sources (soybean methyl ester, mustard
methyl ester, mustard ethyl ester and used oil methyl
ester) the CP of each of the methyl esters was not

“statictically significant," the ethyl ester showed a

different result.24 The ethyl ester'was slightly more

effective, an average reduction of 3%L3‘ This difference

is thought to be related to the end methyl group's distance
from the carboxylic group. In the methyl ester the methyl
group has a slight polarity due to the carboxylic group,
this causes the crystals to easily form due to the polar
attractions. In the ethyl ester, the end methyl group is

farther from the carboxylic group, so there is less of a

15

polar effect on it, meaning it is less likely that there
will be any polar attraction.24

The PP of the biodiesel was lowered by the commercial

additives by approximately 3-Jmc in the methyl ester and by

19°C for the ethyl ester.24

A common commercial additive used for reducing the CP and
PP of petroleum based diesel fuel is a polymer. There are
various copolymers that are known to be effective. One of
these consists of a maleic anhydride alpha-olefin copolymer
(alpha olefins are carbon chains with a double bond in the
alpha, or end position)”’, another is a propionate/vinyl

30

branched carboxylate terpolymer. These polymers can work

in two ways, the first interrupts the formation of wax
crystals in the diesel fuel which limits the size of the
crystals produced and the second acts as a nucleating agent
which creates smaller crystals. Both of these methods
reduce the CP and the PP of the diesel fue1429'3°

Simply blending biodiesel with conventional diesel will
lower the CP and PP. Rushang and Pegg found that there is
a correlation between both these temperatures (CP and PP)
and the amount of biodiesel in the blend, by volume.25 1M1

equation can be calculated that will predict these

prOperties of the fuel, although each batch of biodiesel

16

will have different properties so these equations are not
universal.

The commercial additives mentioned previously will also
work on blends, where they have the most effect. The PP
could be depressed up to 36°C using the conventional
additives in a 5 to 20% blendfi24 The problem with using
blends to reduce the PP and CP of biodiesel is that most of
the wanted renewable fuel effects are gone. Some of the
effects can be appreciated, but not to the full extent.

It has also been found that using different alcohols in the
transesterification will change the properties of the fuel.
If the alcohol is branched such as isopropyl and 2-butyl
alcohol the CP and PP can be reduced more than using
straight chain alcoholsf26 Lee et al found that using these

two alcohols reduced the CP by 7°C and 10°C respectively.
This became even lower when low saturated oil is used.26
The drawback to using these branched alcohols is in the
cost. These alcohols are more expensive, have a lower
yield and an increase in impurities in the final product.26
“Winterizing" of biodiesel has also been considered for
lowering the cold flow pr0perties of biodiesel. The

wintering process is when the biodiesel is cooled until

crystals begin to form (the crystallization onset

temperature Tafl- At this point, the crystals are filtered

17

and the process is repeated until the intended CP is
reached.”' This removes the saturated esters from the

biodiesel. When regular soybean oil is used, this process

becomes lengthy (11 steps, each step being a cooling and

filtering of the liquid) to reach a Tco of -7.1°C.27 This

process was found to be shorter if one of two things was
done. The first was using a hexane solvent on the soybean
oil, the second to use a variety of soybean that has low
saturates. When either of these were employed, the CP was
reduced to 3 steps, however the yield for the low saturates

was better (86%) than the soybean oil and solvent (77%).27

This method does reduce both the PP and the GP for the
biodiesel, but problems still remain in the storage or
transportation of the saturates. Since the saturated
portion of the fuel cannot be used in the winter months in
the north they either need to be stored until warmer
weather or transported to warmer locations. Both the
storage and transportation will lead to an increase in
costs.27

Finally there are researchers who have used blend of
biodiesel with ethanol to improve these properties, and
have been successful. Park et a1 and Torres-Jimenez et al
have found that the addition of ethanol will decrease the

PP and CP. By using a blend of 15% ethanol the CP can be

18

decreased by 30C and the PP by the same amount.21 There are

two advantages to using ethanol; the first is the entire
fuel could potentially be renewable (if the ethanol is from

28

fermentation), the second being a reduction in viscosity,

which would bring the viscosity of biodiesel closer the

viscosity of petroleum diesel.2L m;

The disadvantage to doing this is a change in the flash

point. With only a 5% addition of ethanol the flash point
drastically decreases, to near the flash point of ethanol,
which is well below the required flash point standards for
biodiesel. This would mean that an additive is needed to

increase the flash point.”‘ A second disadvantage is the

affinity for ethanol and biodiesel to absorb water. The
storage and transportation could become difficult if
barriers from the atmosphere are needed to prevent the
absorption of water from the humidity in the air.21

There are many methods for reducing the CP and PP of
biodiesel, most of which are additives, but a few change
the chemical structure of the biodiesel itself. They all
have their advantages and their disadvantages. There is no

perfect method.

19

CHAPTER 2
BIOBASED MONOMERS

2 . 1 Literature Review

2.1.1 Introduction

There is an increase in the demand for renewable resources
in every industry. This includes the production of
polymers and the monomers from which they are produced.
Currently almost all polymers are produced from fossil fuel

sources;“'the most used is naphtha-a distillation fraction

of crude oil and natural gasf32 The production of polymers

consumes approximately 7% of the world’s fossil fuels.13

Another reason for decreasing the use of petroleum based
monomers and polymer is biodegradability. Petroleum based
polymers do not easily biodegrade, meaning there are few
(or no) microbes that will break them down. However, there

are many biobased polyesters, plastics and inks that have
proven to be biodegradable.3$d7 In addition to the

potential biodegradability, other advantages for production
of monomers and polymers from renewable resources are their

low cost, ease of availability, and the availability of the

feedstock in large quantities.“"31

Currently there are biopolymers produced from

13, 32, 38 13, 32,

polysaccharides (starch and cellulose), lipids

20

38 3

(plant and animal triglycerides), polyphenolsfl38 sugars,1

38

proteins“” and natural rubbers”. One of the first

industrially produced biobased polymers was linoleum,

developed in 1864 by F. Walton, the main component being

linseed oil.12 'Vegetable oils and animal fats, like linseed

oil, have been used in the production of coatings,1°'13'39'40

10, 39, 13, 39, 40 7, 39, 40

plasticizers, 4° lubricants,1m' inks,3

13, 39, 40 10, 39, 40

paints, and agrochemicals

2.1.2 Triglycerides

The previous chapter discussed the use of triglycerides in
the production of biodiesel and the structure of the
triglyceride. The same oils seen in Table 3 can also be
used in the production of monomers. Other oils are only
used in the production of monomers or for direct

polymerization; this is due to the added functional groups

on these triglycerides. These include Tung“” m,

Lesquerella Gracilis”, Veronia30 and Castor oils.1°' 3°

These oils contain natural epoxy, hydroxyl groups and

conjugated double bonds. Others are known to have triple

1

bonds and ether functions.1 These natural functional

groups allow these oils to be directly polymerized.

21

2.1.3 Triglyceride Based Monomers

There are many paths that can be taken to produce a monomer
using the triglyceride. These pathways, shown in Figure 7a
and 7b, are modifications made to the initial triglyceride.
The first of these is to functionalize the internal double
bonds of the fatty acid portion of the triglyceride

These functional groups are commonly epoxy groups,1m42'31'3L

32, 42-47 , 40

“0'41 hydroxyl groups,3L and maleates9 (paths 5-8

and 11).
Epoxy groups are generally produced by the reaction of the

triglyceride with molecular oxygen, hydrogen peroxide or
via a chemo-enzymatic reactionufi In situ epoxidation of
soybean oils has been studied extensively; this process
uses a two—phase system to safely achieve epoxidation.41

Epoxidation processes using peroxides and peracids have
been known to form mixtures, which will explode upon
heating, the in situ process avoids this by allowing low

concentrations of the peracid to form, resulting in a safer

process‘l.

22

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24

The epoxidized oils can be used in polymerization or they
can be converted into hydroxyl groups via alcoholisis of

32, 43, 45

the epoxy group. The oxirane ring will open in an

acidic environment to yield the hydroxyl group.47
Halogenated polyols can be achieved using hydrochloric acid
or hydrobromic acid.46 Polyols (a molecule with more than

one hydroxyl group) can be produces using another method as
well. This method uses the double bond and converts it to
an aldehyde in a process called hydroformulation with
carbon dioxide and hydrogen. The aldehyde is then

converted to a hydroxyl group using a catalystfn'44'45

9, 13, 40, 48

Using the epoxy group, acrylates can be added by

the reaction with acrylic acid. Maleate esters are also
produced from the reaction of the hydroxyl groups with

maleic anhydride.9'12’4o

The second method for producing a monomer from a
triglyceride is production of a monoglyceride through a
glycerolisis reaction or amidation reaction (path2 2, 3A

and 3B). The monoglycerides that are produced can also be

maleated to produce maleate half esters (path 9).9'4°

The final method is to do both types of reaction, produce a
monoglyceride and functionalize the double bond (path 4).

This can be accomplished using two methods. The first,

25

starts with a functionalized triglyceride then glycerolisis
is performed. The second begins with a monoglyceride and
functionalizing of the double bonds is done second. These
functionalized monoglyceride can also be reacted with

maleic anhydride if necessary (path 10).9"°"$51

There is a second method for producing the maleated
monoglycerides. Performing alcoholisis of the triglyceride
with pentaerythritol produces a monoglyceride and an oil
pentaerythritol glyceride, which can be reacted with maleic

anhydride . 52 ’ 53

2.1.4 Monomers from Fatty Acids

The internal double bonds of the unmodified triglyceride do
not easily polymerize because of their location. This is
the reason for modification of these double bonds. This is
also true for the fatty acid. Modification of the fatty
acid is necessary to achieve polymerization because the
double bonds are internal and cannot undergo free radical
polymerization.

One other method to produce a polymerizable monomer out of
the triglyceride is the production of a fatty acid with a
terminal double bond (although the internal double bonds of

a fatty acid can be epoxidizeds"'56 or hydroxyltedu' ‘7 as

seen in the previous section).

26

One method for the preparation of an allyl

Finkelstein transposistion.57"58

ester USES a

This method uses no allyl

alcohol and uses glycerol (a byproduct from biodiesel

production) as a feedstock.

Another reaction that can be used is the esterification of

the fatty acid (Figure 8). This method is

generally used

on a single species of fatty acidéfi'syfilhowever it has been

used on the fatty acids of soybean oils and linseed oilsez.

The reaction that occurs uses an acid catalyst to produce

water, the water is azetropically removed with excess allyl

alcohol until water is no longer produced.

Water
Fatty Acid Allyl Alcohol

Figure 8: Esterification of the Fatty Acid

Catalyst

0
WT

Fatty Acid Allyl
Ester

Using an Acid

The second method of production of allyl esters is the

transesterification of the methyl ester—producing methanol

as a byproduct (Figure 9). This reaction is also known as

alcoholisis and is generally not used due to low yields.

When alcohols such as methallyl and crotyl

27

alcohol are used

..-___ V
1 AU- _ I r

 

the yields are significantly lower than the esterification

method60 .
O R
/\/ \[r
0 R
on // ____.. on
/\/ + \n/ — / + O
O .
Fatty Ac1d
Methanol
Allyl Alcohol Fatty Acid Allyl Ester

Methyl Ester (FAME)
Figure 9: Transesterification of Methyl Ester with Methanol
as a Byproduct
Finally the direct transesterification of any vegetable oil
triglyceride can be used to produce allyl esters (Figure
10). This reaction is the same reaction that produces
biodiesel using allyl alcohol in the place of methanol.

This method has been shown to have high yieldssl“ 56

R

0:=:<D O OH
. >‘“ . A” R
:%—-0 0H 3 \\H//
O

 

3 W011

Allyl Alcohol

 

OH Fatty Acid
Allyl Ester

0 Glycerol

R
Triglyceride
Figure 10: Transesterification of the Triglyceride to

Produce Allyl Esters

28

 

2.2 Transesterification of Soybean Oil

2.2.1 Materials

Low saturated RBD (refined, bleached and deodorized)

soybean oil was obtained from Zeeland Farm Services in

Zeeland, Michigan and the allyl alcohol was purchased from

Fisher Scientific. Both the allyl alcohol and the soybean ;1
oil were stored at room temperature in a dark location to r
prevent the oxidation of the double bond in both. All
other chemicals were obtained from reliable resources and

were used as received.

2.2.2 Experimental procedure

Approximately .5g potassium hydroxide (KOH) was dissolved
in 50g (.86 mol) allyl alcohol to which 509 (.06 mol)
soybean oil was added. Prior to the addition of soybean
oil to the allyl alcohol the alcohol and soybean oil were
heated to 90%:. The oil and alcohol were mixed in a 150mL
three-necked batch reactor equipped with a reflux
condenser, magnetic stir bar and stopper for 1.5 hours at a
reflux temperature of 1059C. After cooling a stoichometric
amount of concentrated hydrochloric acid was added. The
neutralized reaction mixture was then transferred to a
separating funnel. The glycerol product and the salt

formed by neutralization were allowed to settle out of the

29

ester layer. After the salt and glycerol were removed, the
ester layer was washed with distilled water to remove any
residual salt, glycerol and some of the excess allyl
alcohol. Any remaining unreacted allyl alcohol was removed

under vacuum.

2.2.3 Characterization

Fourrier Transform Infrared Spectroscopy (FTIR) spectra
were obtained using a Perkins and Elmer instruments,
spectrum one FTIR spectrometer. All FTIR spectra were
normalized, this was done by dividing the difference
between absorbance and the minimum absorbance in the
spectrum by the difference between the maximum absorbance
and the minimum absorbance. Nuclear Magnetic Resonance (H-
NMR) spectra were obtained of the esters in CDCLU using a
Varian Inova-300 spectrometer operating at 300.103MHz. Gas
Chromatography (GC) analysis was done using a HP 5890
series II equipped with a Supelco PTA—5 column (30m x
0.25mm with a film thickness of lym). HPLC grade
dichloromethane was used as the solvent and methyl

undeconate was used as an internal standard. Finally,
iodine values were calculated using ASTM method D1959-9763.

The Wij's solution was purchased from Sigma—Aldrich corp.

and carbon tetra chloride was used as the solvent.

30

. 9".

2.2.4 Results

The normalized FTIR spectra for both the starting soybean
oil and the allyl ester product can be seen in Figures 11a
and 11b. At first glance, the two spectra look similar
however; there are differences that show a change in the

material.

 

 

 

 

 

 

 

 

Absorbance
O
0'!
—

O
o
b

 

 

 

m2 1 a“
on (_‘A ‘— ;__J\L_J

Ah. V'—
i

 

3650 3150 2650 2150 1650 1150 650
Wavelength (cl-‘1)

 

Figure 11a: FTIR Spectrum of the Allyl Ester

31

 

 

 

 

 

 

 

 

 

Abeorbence
0
0|

 

 

 

 

 

i

0.2 i
. 1 l i
o A ...... W l

3650 3150 2650 2150 1650 1150 650
Wavelength (and)

 

 

 

 

 

 

 

Figure 11b: FTIR Spectrum of Soybean Oil
The first of these is the peak from 2990cm‘1 to 3050cm“, the
peak characteristic of the =C-H stretching. This is more
clearly shown in Figure 12, which shows there is a change
in the amount of absorbance. The soybean oil has smaller
total absorbance than the allyl ester peak (meaning there
is a smaller area under the curve for the soybean oil

compared to the allyl ester).

32

 

 

0'2 " "Soy Oil

—Soy Allyl Ester i
0 . 1 8 // \\ ---..m- i
I \
’ \
I \

 

Absorbence
O
H
\
‘
I
I

 

 

 

 

 

’ ‘
--—-----" i

 

 

3050 3040 3030 3020 3010 3000 2990
Wavelength (01")

 

 

Figure 12: Peak Characteristic of =C-H Stretch
Since the peak intensity directly correlates to the number
of double bonds in the sample, this shows that the allyl
ester sample has a larger number of double bonds. The
second important peak is characteristic of the ester (C=O
stretching). This peak, from 1690cm’1 to 1790cm‘1 (see
Figure 13), shows a shift of the maximum absorbance from
1744cm"l to 1739cm’1. This shift is an indication of the
change in the chemical groups next to the C=O. Any groups
near the C=O alter the wavelength that this group will
absorb at. So the change from the glycerol backbone to the

allyl group shifted the absorbed wavelength.

33

 

 

1 ‘ ‘Soy Oil §
—Soy Allyl Ester 5

0 9 “.-.-.. -_ __- r- -... ...... ...—.7 .__,-___..._._._

 

 

Abeorbence
O O
U!
- ~ ~
\
a “‘ o
/l
l
i
i

 

0A.EE=EP=€FA?I H ““-—:-—~_=_-_Hr-‘_—=£j

o r Y . ‘ - 1’ . , r 1
1790 1770 1750 1730 1710 1690 1670 1650
Wavelength (cm'l)

 

 

 

Figure 13: Peak Characteristic of C=O Stretch

The iodine values, seen in Table 4, confirm the increase in
double bonds. By using a theoretical value of 216.00, (see

appendix 1 for calculations) a percent conversion of 83.72%

is found.
' ' ” ”"etaa‘aaia‘
. a 5.99.19 . a- _ V Mia??? _ . Deviatien I
..WSOYbeanroiAM rims ,.,, ”142:1N H .m 4:93_17
Allyl EsterOiflrom Soybean 204.54 2.96

Table 4: Iedine vaiuee for “soybean 011 and 'A'11y1' seter
Product

The H-HMR spectra also indicate the changes that occur when
the triglyceride is transesterified. The first H-NMR

spectrum, seen in Figures 14, is the spectrum for the

34

soybean oil. Peaks A, B and, C are the three most
important peaks. These peaks correspond to the protons in
the glycerol backbone of the triglyceride where A and C (at
4.1ppm and 4.3ppm) are the protons on the two and carbons
and B (5.2ppm) is the proton on the middle carbon.

When this is compared to the allyl ester spectra, the peaks
A B, and C are no longer present. This would indicate that
there is no longer glycerol present. The new peaks D and E
at 5.9ppm and 5.2 ppm are the indication of the terminal
group on the ester. Peak F, at 4.5ppm, is indicative of the
methylene protons in the allyl portion of the ester. These
three peaks (D, E, and F) indicate that the allyl groups
had been added to the ester chain. The remaining peaks at
5.3—5.4ppm and below 3.0ppm are the protons in the fatty
acid chain and do not change when the ester is produced

since they do not take place in the reaction.

35

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36

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37

Gas Chromatography was used to analyze the allyl ester.
This data, along with the data from a methyl ester produced
from the same soybean oil can be seen in Table 5. As this
Table shows, the residence times for the allyl product are

slightly longer than that of the methyl ester. This longer

residence time can be attributed to the additional

molecular mass of the allyl ester

 

 

 

 

 

 

 

. Percentage Percentage
III ResTiidneence Component in Methyl in Allyl

Ester Ester

15°21 Peggiziite 4'27

16'44 Unggiflggies 88'91

16.56 53:22::8 6.81

17'60 Unsitiiites 87°62

17.67 s:::§:e 9.93

 

 

 

 

 

 

Table 5: Retention Times and Percentage of Components in

Allyl Ester and Methyl Ester Produced from Soybean Oil

38

2.3 Transesterification of Fatty Acid Methyl Esters

FTUMES

2.3.1 Materials
The materials used for these reactions are the same as the

previous section.

2.3.2 Experimental procedure E1
Approximately lg KOH was dissolved in 50g (.86 mol) of I
allyl alcohol, 509 (.18 mol) of methyl ester was then added

after the KOH was completely dissolved. The reaction vessel

(a three-necked batch reactor) was equipped with a dean

stark trap/condenser a magnetic stirrer and a thermometer.

The reaction mixture was heated (maximum temperature of

1059C) until approximately 20mL of alcohol (a mixture of

methanol and allyl alcohol due to the azetrope) was

collected in the dean-stark trap. The reaction was allowed

to cool slightly and 20mL of allyl alcohol was then added

to the esters to ensure an excess of allyl alcohol is

maintained. The removal and addition of alcohol was

repeated four times.

39

2.3.3 Characterization
The same characterization techniques and equipment were
used on the allyl ester produced from methyl esters as the

allyl ester produced from soybean oil.

2.3.4 Results

The normalized FTIR spectra for both the allyl ester and

the methyl esters that it was produced from are in Figures i
16a and 16b. These spectra have even more similarities

than that of the soybean oil and its allyl ester product.

 

 

 

 

 

 

 

 

 

Abaorbance

0
M

T

i

l

i

i

i

I

i
—

 

 

 

 

 

 

 

M
UVV

 

 

1' 1 ‘1

3650 3150 2650 2150 1650 1150 650 I
Wavelength (end) i

 

 

Figure 16a: FTIR Spectrum of Allyl Ester from Methyl Ester

40

 

 

 

 

 

 

 

 

 

Abaorbance
0
UI
—

 

 

 

 

z: i ii
1 Y L, - -....JUV“

f

 

 

3650 3150 2650 2150 1650 1150 650
Wavelength (a’l)

 

 

Figure 16b: FTIR Spectrum of Methyl Ester
One of the main differences, like the soybean allyl ester
is the C=O peak (wavelengths 1690cm‘1 to 1790cm“). This
peak shows the same type of shift as the ester produced

from soybean oil, from 1742cm‘1 to 1740cm“, Figure 17. The

peak associated with the =C—H stretching (2990cm‘1 to

3050cm'1, Figure 18), does not show any change in the amount

of absorbance. As mentioned, the absorbance is proportional
to the number of double bonds in the sample. This would
suggest that there is no change in the number of double
bonds and therefore no addition of the allyl group to the
ester. This conclusion, however, is not supported by the

iodine values calculated.

41

 

Absorbance

 

1,.-.” ...- “* —Ally1 Ester
" “Methyl Ester ‘

 

 

 

 

 

 

 

 

 

‘57

 

 

Her” u...—

a.

 

 

 

 

 

 

0 r T . r 1 r -111

1790 1770 1750 1730 1710 1690 1670 1650
Wavelength (cm'l)

 

Figure 17: Peak Associated With C=O Stretch

 

 

Abaorbance

-...

 

 

 

 

 

 

 

 

 

 

 

 

 

 

°°217_ ' __ 7“- 7 "7 " '_"“ ""I " "”"‘“"”‘”‘ "*--A11y1 Ester
" 'Methyl Ester _
0.18 -1 . ;
0.16 -_ -1 g
0.14 , g
0.12 t \\ ’
04 .MMWWMWWW. i
0.08 1-.-- ~---~~-—-—— ~ 1.11 t _ 11_-11_wfir__ I
0.06 ‘
m04 i
0.02

3050 3040 3030 3020 3010 3000 2990 l
Wavelength (cm'l) 1

 

Figure 18: Peak Associated With =C—H Stretch

42

 

The iodine values 141.93 and 188.57 were calculated for the
methyl ester and the allyl ester respectively (Table 6).
This is one conformation that there is an addition of the
allyl group to the ester, since there is an increase in the
number of double bonds. Using the same theoretical value
for one hundred percent conversion (216.00), a conversion

of 62.16% is found for this reaction.

 

 

 

 

 

 

 

Sample Average Standard
Dev1ation
Methyl Ester 141.93 2.95
Allyl Ester 188.57 3.74

 

Table 6: Average Iodine Values for Allyl Ester and the

Methyl Ester Used to Produced It

The GC analysis also confirms conversion to the allyl
ester. The residence times and area percents for the final
allyl ester product are seen in Table 7 (the results shown
are after the final removal of allyl alcohol). As this data
reinforces the conclusion that there is not complete
conversion, since there is still methyl ester in the
product even though the allyl alcohol was maintained in
excess and methanol was removed during the reaction (Pure

methyl ester residence times can be seen in Table 5).

43

 

 

 

 

 

 

 

Residence Component Percentage in
Time Reaction mixture
16°44 Unggflfiggies 30°41
16.56 5:23; 3.74
17.67 823:; 1.88

 

 

 

 

 

Table 7: Retention Times and Percentage of Components in

Allyl Ester and Methyl Ester Produced from Methyl Ester

Finally the H-NMR spectra also (Figures 19 and 20) confirm
the conversion of the methyl ester to the allyl ester and
that there is not complete conversion of the methyl ester.
The peak, labeled H, is indicative of the protons of the
methyl group. Since this peak is present in both spectra
it can be concluded that the product is a mixture of
esters. The three peaks, K, L and M indicate the protons
attached to the three carbons in the allyl group that is
added to the ester. The C=C at 5.2ppm and 5.9ppm and the
methylene group at 5.2ppm. The remaining peaks at 5.3-
5.4ppm and below 3.0ppm are the protons on the remaining

fatty acid chain.

44

 

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, r a _
_ . i _
r mODMH5#MmGD
k HMGHOHCH
1
m
m o
M
\\0m

 

45

umumm Hugues Scum pmosooum umpmm Hmaaé Mom Esupommm mEZIm "om musmflm

 

 

SN 33
3.3 SE 3:: 3.3 SE 8.3 8.2 8.0 8.3 max Gem
lie] , .ll. ,w|_l .iliirilJ alliili ilk]. ll. .|.J 11'. Liqliilll II. J
and a4 m4 9n mé ea ....n .

o v mlv o.m m.m o.m

 

 

 

 

 

. W ._ J. i.
_ i a e m T ._ 4i i.
1 A i, *__ - _ _ = 11 fl
_ ,4 n, 1 * M 1 .H
_ - , _.
.1 z . /
A a . _ mmecuspnmcb
_ m Hmcuwch
a\
1 2
O .IJF K\\M
am can
m o\ /m\

46

2.4 Discussion of the two methods of production

The data discussed previously indicates that there is a

reaction of both the soybean oil and the methyl ester, but

do both methods produce the same product? The data

suggests that they do. The first confirmation is in the GC

analysis of each product. The residence times for the W
product from both methods are the same. This indicates
that the two products must be similar since they elute at
the same time under the same conditions. The second
confirmation is the shift of the ester peak in the FTIR

spectra. The maximum of the peaks shifted to approximately

the same place (1740cm'1 vs. 1739cm'1). Finally, both

product H-NMR spectra have peaks at 4.5ppm (methylene
protons), 5.2ppm and 5.9ppm (terminal double bond protons).
Since the peaks fall at the same location, it can be
concluded that there is the same material is in both
product.

As shown there are two methods for producing the allyl
ester from soybean oil, direct transesterification and
transesterification of the methyl ester. The direct
transesterification seems to be the more efficient method
of production. The conversion of the soybean oil is

significantly higher than the methyl ester conversion.

47

 

 

 

 

 

 

 

 

Conversion
0
U"
U"

 

0 o 5 1r- ~ "-7 — ..... 7 uAvAfiy‘“‘meiw i.._ .-.

 

 

 

 

 

 

 

 

 

Allyl Alcohol Addition

 

Figure 21: Conversion of Methyl Ester to Allyl Ester with

the Removal and Addition of Alcohol

Although it may be possible for the methyl ester reaction
to reach the same conversion as the soybean oil reaction
the soybean oil uses less allyl alcohol. Figure 21 shows
with each addition and subsequent removal of alcohol the
conversion increases, but this process will use more allyl
alcohol as well as time and energy than the soybean oil

process.

48

2.5 Kinetics of transesterification

2.5.1 Experimental Equipment

Reaction for kinetic data was carried out in a 250mL three-
necked batch reactor, where the total volume of reactants
was 140g. The reactor was equipped with a reflux condenser,
magnetic stirrer, and a stopper to remove samples. The
temperature of the reactor was maintained at 105%2.

The set of equilibrium reactions were carried out in
Erlenmeyer flasks. A magnetic stirrer was used for stirring

the chemicals.

2.5.2 Experimental Conditions

The experiments were planned to determine the reaction rate
constants, effect of the catalyst concentration, and the
temperature on reaction rate. The first experiment was
carried out over 1 hour using potassium hydroxide as the
catalyst at atmospheric pressure with a 6:1 molar ratio of
allyl alcohol: soy oil.

Experiments were also conducted changing the potassium
hydroxide concentration (0.25, 0.5, 0.75, l, and 1.25 wt %
of soy oil), and the mol ratios (1:2.4, 1:3, 1:3:6, 1:4.2,

1:4.8) for 6 hours.

49

 

2.5.3 Experimental Procedure

Experiment A: The reactor was initially charged with the
amount of soybean oil, heated to 909C. The potassium
hydroxide was dissolved in the allyl alcohol and also
heated to 903C. Once both reached the temperature, the allyl
alcohol solution was added to the stirred reactor. The
reaction was timed as soon as the potassium hydroxide/allyl
alcohol solution was added to the reactor, and it continued
for 1 hour. During the reaction, samples of 1mL were taken
at the following reaction times: 1, 2, 3, 4, 5, 7, 9, 11,
13, 15, 17, 19, 30, 40, 50 and 60 minutes. The samples were
quenched immediately by cooling in 4mL of water that had
been cooled in an ice bath and were then centrifuged to
remove glycerol and water. For capillary gas
chromatography, the known amount sample and internal
standard was mixed and diluted with approximately 1mL of
dichloromethane and then analyzed.

Experiment B: Various molar ratios (soybean oil: allyl
alcohol) with different potassium hydroxide concentrations
as described earlier were used for the reactions and

samples were analyzed as described above.

50

 

2.5.4 Characterization

To ascertain the change in the reaction product composition
over time samples were analyzed by capillary gas
chromatography, which allowed for the simultaneous
quantification of fatty acid methyl esters. The analyses

were performed on a Hewlett-Packard 5890 series II

chromatograph connected to a Hewlett-Packard 3396SA
integrator, using a Supelco pta-5 30m x 0.25mm column with
a film thickness of lum and FID detector. Methyl Undeconate
was used as the internal standard. The glycerol
concentration was determined, through the material balance
of the reaction, from the previously calculated
concentrations and the initial concentrations of

triglyceride and allyl alcohol.

51

2.5.5 Results and Discussion

The mechanism for the given reaction is shown in Figure 22.

W03 +

Allyl Alcohol

W011 +

Allyl Alcohol

/\/°H

Allyl Alcohol

Triglyceride
=< R
0 0%
O
OH =
0
R

Diglyceride

Monoglyceride

R
0%
0
= OH
O
0%
R
Diglyceride
OH
OH
Monoglyceride
OH
= OH
OH
Glycerol

0
WT

Fatty Acid
Allyl Ester

o
¢¢“\¢/‘\H/

Fatty Acid
Allyl Ester

/\/°\”/

0
Fatty Acid
Allyl Ester

Figure 22: Step-wise Reaction for Allyl Ester Production

from Soybean Oil

For calculation purposes this reaction is considered as one

step (Figure 23).

52

 

R

 

Allyl Ester
O

o=<
() O OH
>F—R o R
3 W08 + éio __ on + 3 /\/ T
O
Allyl Alcohol 0 OH Fatty Acid

Glycerol

R
Triglyceride

Figure 23: Reaction Scheme Used for Equilibrium Kinetics

 

 

 

 

25 ,

2 o ...... ...-.-r,...._“.. ... .. .... .. . .. . .. .. ,. .. . .. “....uixuilunw .. ..........i._~..........._..... ..i.._...-..,.. ...“ . .. ....‘mr..rwrm_- 1.1:... . . _. «um»... V.

 

 

 

 

1 5 _ .‘___. -i-~-.. .. -....me, M

Conversion (t)

 

1 0 +~-~~- » ———-— w—ufl-H “.-...-

 

 

 

0 10 20 30 40 50 60 70
Time (min)

 

L

 

 

Figure 24: Percent Soybean Oil Conversion with Respect to

Time

Figure 24 shows that for a given mole ratio of soybean oil,

allyl alcohol, and catalyst concentration, the conversion

53

of soybean oil does not change with respect to time. Also
the conversion is not 100% at a mole ratio higher than
theoretical. This means both the reactants and products
are present in the system in a definite amount. So the
system can be considered reversible. Equilibrium had been
reached as soon as the samples were mixed. An important
fact for this system is both of the reactants are miscible.
At given potassium hydroxide concentration, the reaction is
not kinetically controlled but mass transfer controlled. As
both the reactants are miscible, only the mixing time is

the time required to reach the equilibrium.

 

 

100
901
80*

70*

 

60+
sol

40*

8 conversion

 

30‘

 

 

20 - *1.25

 

10‘

 

 

 

 

0 —Y I I I V
2 2.5 3 3.5 4 4.5 5

Mole ratio (Allyl Alcohol: Soybean Oil)

 

 

 

Figure 25: Effect of the Catalyst Concentration on

Conversion

54

 

Figure 25 shows the effect of potassium hydroxide
concentration for various molar ratios of soybean oil and
allyl alcohol. Potassium hydroxide, as per the

literature“, was considered as a catalyst for the

transesterification. If it is considered a catalyst, then
the conversion for the same reactant mole ratios with
different potassium hydroxide loading should remain
constant. But Figure 25 shows increased conversion with
increase in the potassium hydroxide loading. The
theoretical mole ratio of the reactants is 1:3 (soy oil:
allyl alcohol). The effect is more pronounced at higher
than theoretical mole ratios. Based on the data available
the equilibrium constant is calculated (see appendix 2 for
calculation method). The equilibrium constant changes with
respect to the mole ratios of soy oil and allyl alcohol as
well as potassium hydroxide. The range of the equilibrium
constant calculated is 0.68 to 1974.89. In this case the
number of moles of reactants and products are same so the
equilibrium constant has no units. Table 8 shows the
equilibrium constant (K) for various soy oil, allyl alcohol

and sodium hydroxide composition.

55

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Mole ratio Percent
(Soy oil: Potassium Percent Equilibrium
allyl hydroxide soy oil constant (K)
alcohol) (Based on. conversion
soy oil)
2.50 33.75 0.68
3.13 41.55 1.23
3.79 0.25 48.06 1.11
4.42 54.43 0.89
5.03 58.26 0.98
2.46 41.72 8.72
3.10 51.55 9.86
3.72 0.50 58.48 7.11 _fi
4.37 63.02 5.32
4.99 68.65 4.43
2.40 49.28 19.59
3.11 54.90 15.15
3.69 0.75 61.57 11.80
4.32 75.23 26.65
4.95 96.52 179.64
2.38 45.33 42.74
2.95 53.61 33.89
3.64 1.00 89.99 503.95
4.28 98.55 1714.78
4.92 99.18 1105.43
2.35 44.83 56.84
3.02 55.71 49.91
3.61 1.25 91.39 818.19
4.23 98.27 1974.90
4.88 95.25 152.90

 

Table 8: Equilibrium Constant for Various Concentrations

56

 

CHAPTER THREE

COPOLYMERIZATION OF MONOMERS

3.1 Literature Review

3.1.1 Modified Triglycerides

As discussed previously, there are many modifications that
can be made to a triglyceride (some natural triglycerides
have the same modifications) in order to produce a monomer
to be used in polymerization. Epoxidized oils have been
used to improve the processing of PVC (Polyvinyl chloride).

It acts as both a stabilizer and a plasticizer.9'11'32"°

This is not the only use for epoxidized oils; they have

10-12

been used in the production of UV cureible and

thermosetting coatingsflh Some of these systems have been
known to be biodegradable33 and have moderate glass

transition temperatures (Tg) and thermal properties.12 The

acrylated epoxidized oils have been used to produce

pressure sensitive adhesives48 and polymers with a high Tg

and a high modulus.9’4O

Hydroxylated oils and polyols are generally used in the

31, 42, 43, 45, 46

production of polyurethanes. The polyurethanes

57

are produced using a condensation reaction with an

isocyanate.43 IPolyurethanes from vegetable oil polyols can

have properties ranging from a hard rubber to a rigid

plastic; some are also rigid to soft foams.31

The maleates soybean oil monoglycerides have also been used

to make polymer resins by copolymerizing them with styrene“’ I“

and by maleation mixtures of the monoglyceride and

neopentyl glycol then copolymerizing the resulting mixture ,1

9, 40, 50

 

with styrene. The cured thermoset copolymer of the

maleate with styrene was a clear rigid solid with a slight

1

yellow hue.5 With the addition of the neopentyl glycol the

Tg of the resulting thermoset was increased, where as the

tensile strength and modulus decreased over previous

polymer.50

3.1.2 Unmodified Triglycerides

One method for polymerizing triglycerides without
modification to the double bonds is by using a cationic
initiator. These initiators are usually Lewis acids or

13, 38, 39

protonic acids. The most common copolymers produced

are a triglyceride with divinylbenzene or a

39, 64, 65

divinylbenzene/styrene mixturefin' Cationic

polymerization is possible due to the stability of the

58

intermediate carbocation (a positively charged ion of
carbon) of the internal double bondsf38 By this method high

molecular weight polymers could be produced because the
triglyceride itself has a high molecular weight and since
each of the fatty acids of the triglyceride can react
(meaning it is multifunctional) longer chains can be

3: E

produced.LL Conjugation of the internal double bonds

.3

(which is natural in some oilsfiiand can be produced by a

catalyzed reactionmw produces a higher molecular weight.

Its intermediate carbocation is more stable than that of

38, 46

the nonconjugated double bonds. The copolymers

produced from triglycerides, divinylbenzene and styrene

have been found to be soft rubbers to hard thermosets

13, 38, 39

depending on the reaction conditions. Many of these

polymers were found to be good damping materialsrhiwv39iém

69 13, 38, 65, 68

and have shape memory. When the reaction was

completed with dicyclopentadiene as the comonomer tough and

ductile materials to very soft materials were the

result.”'70

3.1.3 Fatty Acid polymerization
Allyl esters are polymerized via free radical

polymerization. The three typical process; initiation,

59

propagation and termination; all occur during these

1

polymerizations.7 Chain transfer, also a normal process in

free radical systems, occurs in the polymerization of allyl
systems. However, in the allyl systems the chain transfer
leads to a termination of not only the growing chain, but

59, 60, 71, 72

the chain reaction itself. The radical produced

in the degradative chain transfer is very stable; it is

Pfie.l.l' nae-M
.al

stabilized by the resonance and is therefore less active —

essentially terminated."' This is why many allyl

polymerizations are characterized by little polymerization

and low molecular weights.5% ““ ”'72

A method for reducing the degradative chain transfer in an
allyl polymerizations has been described by Shigetomi et

al. This method retards the degradative chain transfer by

inhibiting the “abstraction of the allylic hydrogennh"

This means that it would prevent the chain transfer to a
stable resonance. By adding an electron-attracting group
(such as an ester) to the allyl compound, the electron
density of the double bond in the allyl group will be

affected and assist in retarding the degradative chain

transfer.72

Copolymerizations of some allyl undecanoates with styrene,

methyl acrylates, and vinyl chloride have been attempted.

60

The polymerizations with styrene and methyl acrylates had
very little of the ester intergraded in to the polymer

matrix. The vinyl chloride was the exception, the allyl
ester readily polymerized with it.73

When allyl esters of long chain fatty acids were

9 5

polymerized (soybean,5 cottonseed,S and palm estersfl‘as

well as other long chain estersaU little of the esters were

fine-usual..."

able to homopolymerize. If sufficient initiator was used
to achieve high yields, the polymers geled.56 Gan et al.
found that if the fatty acid was epoxidized before
polymerization the yield could be increased. The oxirane
group did not participate in the polymerization and remains

intact36. The copolymerization of the long chain fatty acid

esters with diallyl pthalate yielded materials ranging from

tough to soft colorless.6°

3.2 Polymerization

3.2.1 Monomer synthesis

The biobased monomer (allyl ester) used in the
copolymerization was produced by transesterification of
soybean oil. Please refer to the chapter 2 for this

procedure.

61

3.2.2 Polymer Synthesis

Approximately 6g of monomer was mixed with .29 2,5-
Bis(tert-butylperoxy)-2,5-dimethylhexane (trade name
Luperox 101). The ratio of allyl ester to styrene used in

each sample can be seen in Table 9.

 

V—_——w

 

 

 

 

 

. Styrene Allyl Allyl Molar ratio
vifl Styrene (M) Ester Ester (M) Styrene/
(g) MW=104 (g) MW~325 Ester
1 5.041 0.04847 1.001 0.003080 100: 6.4
2 4.000 0.03846 2.008 0.006178 100:16.1
3 3.074 0.02956 3.005 0.009246 100:31.3
4 2.014 0.01937 4.001 0.012317 100:63.6

 

 

 

 

 

 

 

Table 9: Ratios of Allyl Ester to Monomer in the Feed

20mL syntelation vials were used to prepare each polymer
sample. After the monomer and initiator were added to the
vial, the vial was flushed with nitrogen to remove the
oxygen in the vial. Each vial was then stoppered with

cotton and heated in an oil bath at 140°C with constant

mixing for five hours. Once the samples were cool, 10mL of
toluene was added to each sample. This dissolved both the
polymer formed and the unreacted monomer. The polymer was
then precipitated in methanol by drOp wise addition. The

solid polymer was then filtered using a Bfichner funnel and
dried overnight in the oven. After drying the polymer was

dissolved in 10mL of toluene and precipitated, filtered and

62

dried a second time using the same methods to ensure the

removal of unreacted monomer.

3.2.3 Materials

The low saturate soybean oil was obtained from Zeeland Farm

Services, Zeeland Michigan, and the allyl alcohol was I
purchased from Fisher Scientific. All other materials used E
were obtained from reliable sources. Prior to usage the E4
styrene and the 2,5-Bis(tert-butylperoxy)-2,5-

dimethylhexane was stored in the refridgerator to prevent

any autopolymerization (styrene) and degradation

(initiator). The styrene was rotovapped under vacuum to

remove the inhibitor (4-tert-butylcatechol) prior to mixing

with the allyl ester monomer.

3.2.4 Characterization

The polymer product was characterized using Gel Permeation
Chromatography (GPC), Thermogravimetric Analysis (TGA),
Differential Scanning Caliometry (DSC) and Nuclear Magnetic
Resonance (H-NMR). GPC samples were prepared by dissolving
a 20mg sample into tetrahydrofuran. IOOuL of each sample was
injected into the column. The GPC was equipped with Waters
icocratic pumps, a Waters 717 autosampler and a Waters 2414

refractive index. Waters breeze software was used to

63

collect and analyze the data. TGA was performed using a TA
Instruments TGA Q500 in a Nitrogen atmosphere. The samples
were heated in a platinum pan to 500°C from room temperature
at a rate of 10°C/min, until the sample was completely
degraded. A TA Instruments DCS 02000 with auto sampler was
used for obtaining the DSC spectra. The samples were
prepared using a standard aluminum pan; each sample was

cooled to -103C where it was allowed to equilibrate. The

Penn—fl

samples were then heated to 130°C at a rate of 10°C/min in a
nitrogen atmosphere. H-NMR was performed using a Varian

Inova-300 operating at 300.103 MHz.

3.2.5 Results

The molecular weight of the polymers formed were found to
be relatively low and is dependent on the monomer ratio.
Both the number average molecular weight (Mn) and the
weight average molecular weight (Mw) are proportional to
the amount of styrene monomer. The Mn (Figure 26)
increases linearly with increasing styrene concentration in
the monomer mixture. The Mw also increases but has a much
faster rate of increase. This difference in rate gives a

broad molecular weight distribution.

64

 

 

 

 

 

 

9000 ; r500
80003 .450
7000{ 140°

1 ~350
6000: i

f r300
50001

i 3 :250 E

4000:

: -200
30005

: L150
2000 3 ~100
10003 >50 i

0 ‘ 1 T r . T . o
60 65 70 75 80 85 90 95
Styrene Content [Mole %]

 

 

 

Figure 26: Molecular Weight as a Function of Monomer Feed

The broad molecular weight distribution could be an effect
of chain transfer to the internal double bond of the allyl
ester. This chain transfer will lead to termination of the

chain growth and a broad distribution would result.

The TGA (Figure 27) confirms that both the styrene and the
allyl ester are found in the polymer. This is seen in the
two degradation peeks, the first at approximately 190°C and
the second at approximately 400°C. These two peaks would

correlate to the allyl ester and styrene respectively (TGA

traces for samples 2-4 can be seen in Appendix 3).

65

k1

 

..4

 

 

r

LAILJLAAJ
'uvva r

O
0"

Weight %
“r

.75

O
O
ID
a 1 a
O

 

O

.50

Derivative Weight % (%/°C)

AAAALAJ
. fiYV'

 

 

. . . . . . . . . . . . . . . . . 0,00
0 100 200 300 400 500
Temperature (°C)

 

Figure 27: TGA of Styrene/Allyl Ester Polymer (Sample 1)

The DSC curve (Figure 28) confirms a random copolymer was
produced. There is only one Tg (glass transition
temperature) shown between 40°C and 60°C. This is
indicative of a random copolymer, a graft or block
c0polymer would show the two individual Tg's for the
homOpolymers that are within the copolymer. Since the T9

of styrene is approximately 366°C (in air)", and is not

seen in the curve, the configuration of the monomers can

only be random.

66

 

 

 

Heat Flow (mW)

   

 

 

 

-20 0 20 40 60 80 100 120 140
Temperature ( C)

'“"Sample 1 ""Sample 2 ""Sample 3 """" Sample 4

Figure 28: DSC Traces of the Four Copolymer Samples

The H—NMR spectra are used to determine the amount of allyl
ester that has been incorporated into the copolymer.

Figure 29 is a simulated H-NMR spectrum (actual spectra can
be found in Appendix 4), along with the structure of the
c0polymer. This simulation was used to determine the sets
of peaks that relate to the two monomers used to produce
the polymer. In this case the proton attached to the
benzene ring in the styrene (at 7.2ppm) and the terminal

methyl group in the ester chain (at .9ppm).

67

 

 

 

Terminal
Styrene Methyl

 

 

 

 

 

Figure 29: Simulated H-NMR and Copolymer Structure

68

The heights of these two peaks correlate to the number of

protons in the sample that will correspond to each of the

structures .

By using the number of hydrogen's found in

each structure (5 for the ring in styrene and 3 in the

methyl group) the total number of each structure and the

ratio between them can be found, and consequently the ratio

of styrene to ester in the copolymer.

The heights of these

two peaks and the resulting ratios are seen in Table 10.

 

Styrene 87.2 ppm

Ester @ 0.9 ppm

 

 

 

 

 

 

. Ratio
Vla1# Peak Height 5H Hzigfit 3H Styrene/Ester
1 2587 517 137 46 100 : 9
2 2006 401 186 62 100 : 15
3 3202 640 580 193 100 : 30
4 3049 610 567 189 100 : 31

 

 

 

 

 

 

 

Table 10: H-NMR Peak Heights of the Copolymers and the

Resulting Monomer Ratios in the Copolymer

When the copolymer composition and the initial monomer feed

are compared (Figure 30) there is an initial increase in

allyl ester in the polymer with increasing allyl ester in

the monomer feed.

that can be incorporated into the copolymer.

69

However, there is a maximum allyl ester

.m‘:]

_r-. ... 1.4
5‘

 

35 1:

 

3o 4: O

25 a.
20 "
15 a.

lot

Copolymer Composition (Mole Ratio Ester)

 

T T

0 10 20 30 40 50 60 70
Peed Composition (Mole Ratio Ester)

o A A A A 4T A L4 L4 L L A L 1 A_A L A L i .L L 1 L A A L A L ' L 1 r _1'

 

 

 

Figure 30: Composition of Allyl Ester in the Monomer Feed

and the Resulting Copolymer

This maximum of 30% allyl ester is most likely due to the
long chains of the ester. These chains would interfere
with the ester homopolymerizing, and therefore a need for
styrene monomers to separate the esters when they are
polymerized. This is in agreement with Gan et al. the
allyl ester of palm oil did not homopolymerized to any

appreciable extent.

70

CHAPTER 4

CONCLUSIONS

4.1 Review of Werk and Results

Allyl Esters from soybean oil were produced using two
different methods, transesterification of the triglycerides
and transesterification of the methyl ester that was
produced from the triglyceride. Both of these methods
produced the desired product (as proven by GC, FTIR and H-
NMR), however not to the same extent. The conversion of
the soybean oil was significantly higher than the methyl
ester, and although it may be possible to achieve similar
conversion the process would not be more efficient than the
production from soybean oil.

The kinetics of the transesterificaton of soybean oil was
also investigated. The equilibrium constants were
calculated for various allyl alcohol/soybean oil/potassium
hydroxide ratios. The reactions using the same reactant
concentrations but different potassium hydroxide
concentrations produced different equilibrium conversions.
The allyl esters were also copolymerized via free radical
polymerization with styrene. The polymers produced were

found to have increasing molecular weight with increasing

71

styrene concentration. By using TGA and DSC, the polymers
were found to have both monomers integrated into the
polymer matrix and a random copolymerization was achieved.
The maximum ratio of styrene to ester found in the
00polymers was 100:30. This is likely the maximum amount of
ester that can be integrated in the polymer due to the bulk

of the ester chains.

4.2 Future Werk

There has been a general push in society to produce
biobased materials in all areas of industry. It would be
useful to explore any uses for the copolymers that were
produced. One likely use for the polymer is a fuel
additive for biodiesel to reduce the cloud point, pour
point or the cold filter plug point. These polymers long
chains that can interrupt the formation of crystals and
would be able to incorporate into the biodiesel because
they contain the same type of molecules, just like the
alpha olefin polymers can incorporate into petroleum
disesl. Copolymerizing the materials with other vinyl
monomers may also produce useful biobased materials that

can be used in industry.

72

 

Appendix 1: Theoretical Iodine Value Calculation

The soybean oil in our lab contains the following weight

percent of each component (as a FAME)

 

 

 

 

 

 

Weight Name Structure Molecular weight
% (g/mol)
4.41 Palmitic 16:0 270.46
3.23 Stearic 18:0 298.56
21.90 Oleic 18:1 296.50
61.59 ILinoleic 18:2 294.48
8.87 Linolenic 18:3 292.46

 

 

 

 

 

 

Table 11: Composition of Soybean Oil Used in Experiments

The average molecular weight of a FAME

(.0441 .. 270.46 i) + (.0323 * 298.56 -g—) + (.2190 * 296.56 i) +
mol mol

 

 

 

 

mol
(.6159 * 294.48 —g—) + (.0887 * 292.46-g— - 293.81—9—
mol mol mol
Average C=C per mole
: :: = = C
.2190"=lC C+.6159"'2C C-i-.0887*3C C=1.72C
Mole Mole Mole Mole

To produce the allyl ester there is an addition of the
”allyl” (41.089/mol) and a ”subtraction" of the methyl

(15.04g/mo1).

293.81i— + 41.08-3— - 15.04—9- = 319.851—

mol mol mol .mol

73

In the allyl “addition” there is an addition of 1 double
bond per mole

C - C
mol

2.72

 

To produce the methyl ester from the soybean oil the
glycerol backbone (41.08 g/mol) is ”subtracted" and the
methyl (15.04 g/mol) is added, one for each fatty acid in
the triglyceride. To work backwards from the FAME there
are 3 FAMEs per triglyceride and 3 methyl's need to be

removed and one glycerol backbone needs to be added.

3 * 293.81i + (3 * 15.04)—g— — 41.08—9—1 . 877.39i

mol mol mo mol

Since there are three FAMEs per triglyceride, there are
three times the double bonds per mole.

C - C
mol

C - C
mol

 

 

(3*1.72 ) =5.16

Iodine values are calculated on a cg of iodine basis and
each mol of iodine reacts with a mole of C=C, the following
are the theoretical iodine values for each ester and the

starting soybean oil reactant.

 

 

 

The Fame
19* mol *1.72C -C* molIz *254g12 *100cg =148.69
293.819 mol molC = C 1770112 g

74

The allyl ester

mol * 2.72C - C * mol 12 * 254912 * 100cg = 216.00
319.85g mol molC = C mol 12 g

 

 

lg*

The soybean oil

mol * 5.16C - C * mol 12 * 254912 * 100cg

——-—— = 149.38
877.399 mol molC = C 1110112 9

 

 

lg*

75

Appendix 2: Equilibrium Constant Calculation Method

The equilibrium constant is calculated using the general
kinetics equation; the concentration of the products
divided by the concentration of the reactants, each
concentration is raised to the power of its stoichiometric

ratio (equation 1).

[GlycerolIAllyl Ester]3
[Allyl Alcohol]3[Soybean 0:7]

 

(1)

The initial masses of materials are the variables S

(Soybean oil), and A (Allyl Alcohol).
The moles of initial materials (SM and A“, equations 2 and

3) were calculated using the molecular masses for soybean
oil (876 g/mole) and allyl alcohol (58 g/mole)

A

=— 3
58 ( )

S
S - —- 2 A
M 876 ( ) M

The volume of the initial materials (Sv and Av, equations 4

and 5) were calculated using the density of soybean oil
(.92 g/mL) and allyl alcohol (.854 g/mL)

S A
SV=— (4) AV‘-8—54_-

.92 (5)

76

The total volume of materials was calculated using equation
6

TV =Sv+Av (6)
Next, the concentration of the initial materials in mol/L

was calculated using equations 7 and 8

S 1 A 1
s -—* 7 =—*
C TV 1000 ( ) AC TV 1000

 

 

(3)

Using the GC data; where Aazis the percent allyl alcohol in

the sample, EEC is the percent allyl ester in the sample, IGC

is the percent internal standard in the sample, and I is
the grams of internal standard in the GC sample the grams

of allyl alcohol (An) and allyl ester (E6) in the GC sample

was calculated (equations 9 and 10).

 

*
(9) EG-_ (10)

1% (equation 11) represents the amount of allyl alcohol and

allyl ester in the original GC sample. The amount of
soybean in the original GC sample is calculated using the
initial material placed in the GC vial (M) and the amount
of ester and alcohol calculated (equation 12).

TG=AG+EG (11) SG=M-TG (12)

77

The masses that were placed in the GC vial were then used

to calculate the percentages of soybean oil (Sp)! allyl

alcohol (AP) and allyl ester (Ep) in the original product

(equations 13, 14 and 15).

A,,=—i—*100 (13) EP=LHOO (15)S,,=——S—G——*100
(To +36) (To +SG) (TG +SG)

(16)
However to calculate the equilibrium constant the amount of
glycerol in the product also needs to be calculated. This
creates a circular argument since the total mass of the end
product depends on the amount of glycerol produced but the
amount of glycerol produced is dependant on the amount of

reactants used (in this case the amount of allyl alcohol

used, Aug. Using a computer, the circular argument seen

using equations 17 through 21 was solved.

A,*T
100

s,*T
100

 

 

Am.- (17) sPG- (18)

E,*T
100

Am * 92

958 (20) T=S+A—GPG (21)

EPG '

 

(19) Gm:

These equations produce the mass of allyl alcohol (Aug,
soybean oil (SP6), allyl ester (Em) and glycerol (GPG, this

is calculated using the mass of allyl alcohol, the
molecular weight of glycerol, 9Zg/mole and the molecular

weight of total ester used, 9589/mole) after the reaction

78

as well as the total mass of the material after the
reaction less the mass of glycerol (T).
From the masses calculated the volumes of each component in

the product was calculated, using the densities of each in
g/mL (Spv is soybean oil, APV is allyl alcohol, EP" is the
allyl ester and Gm,is the glycerol), along with the total

volume, Tm,(equations 22-26)

 

S A E
SW -—9”; (22) AW '75:: (23) EN -—8;GS (24)
(3
Gpv-lngl (25) TPVESPV+APV+EPV+GPV (26)

The moles of Product were calculated next, equations 27-30,

using the molecular weight of each component in g/mole (SPM
is soybean oil, Am,is allyl alcohol, Em,is the allyl ester

and Gulis the glycerol)

 

 

S A
S - PG 27 A -——”£ 28
PM 876 ( ) P” 58 ( )
E G
E - PG 19 G -49 30
P” 319.33 ( ) P” 92 ( )

Next the concentrations of each component in the product
were calculated in mol/L (equations 31-34) using the moles

and volumes calculated previously.

 

 

 

 

 

s 1 A
S - P” *— (31) A -—’1"—* (32)
PC 7,, 1000 ”C T”, 1000
E 1 G
E - ”'*—— (33) G - ”3* (34)
PC 7",, 1000 PC 7,, 1000

79

Finally the equilibrium constant was calculated using the
general kinetics equation was calculated (equation 35) as

well as the percent conversion (equation 36).

 

- [GlycerolIAllyl Ester]3 K a GPC * E ,3,C ( 3 5)
[Allyl Alcohol]3[Soybean Oil] Age * 5pc
C M * 100 ( 3 6 )
SM

80

Appendix 3: TGA Traces of the Copolymer Samples

1.0

In

0
h

 

 

 

“ 1.00

 

 

vvvvvvvvvvvvvv U I I I I 1 I I I I I I I I I’ y I I I I I I I I I I I I I I I v I r I

50 100 150 200 250 300 350 400 450
Temperature (°C)

Figure 31: TGA Trace for Copolymer Sample 2

81

Derivative Weight % (%lC)

Weight %

O
O
0’.

o
o
h

 

 

 

rrYV‘VTY

l I
IYfoVrTYYj'

 

 

IIIITI I I 'v v TVfil‘ II 'I III 'I I II'II I I If‘I‘I’TVII 'Vv'1'1

50 100 150 200 250 300 350 400 450 500
Temperature (°C)

Figure 32: TGA Trace for Copolymer Sample 3

82

.00

.75

.50

.25

.00

.75

.50

.25

.00

Derivative Weight 8 (%/C)

 

 

 

 

 

 

50 100 150 200 250 300 350 400 450 500
Temperature ( C)

Figure 33: TGA Trace for C0polymer Sample 4

83

1.50

"1.00

0.75

Derivative Weight % (t/C)

Appendix 4: H-NMR Spectra of the Copolymer Samples

H mHmEmm Hmfihaomoo How Esuuommm mzzumuwm musmwm

 

 

 

 

ON.“ 3.52 3&2 damn :32 $2 3.3 3:83 8.3%
59“ H n m e m u h
11111115113111.4133 . . 1):. ..1!.1I1)\ -1. .a 1.1!. 11!} 5... 1}}! \1 11111

 

84

 

N mamfimm Hmfihaomoo Esupowmm mzzlm «mm musmflm

 

 

 

 

2.88
3....me . 8.3
m3 $.me 33 3mm 3 3: ~33
r 111. j ill .IljflLlJ.
and H v m m u a
1 A I! 1 1/...) ..J [1111111 1.1111 1 1.1 1111;,11ll11111 .. 111 11111 ..1 \111 1,111 11111111
3 ..:_
f... , 1 11 1 .. . .
1 ., . _ j a“
is _, m .__.
. ..., .A 7 3 .
r . W ., .
., A , _

 

 

 

 

85

m mamEMm Hmehaomou Esupommm MSZIE ”mm musmfim

@3on
$.Hwom 932 . 3......
2.82 3.2 we»... omHKH Hm HSH mm.mm

.l.’|l 1"]
. ,

NHéN omdwm

 

1'1: Ill .1l11f11 J.» J

and H n n e m u H.

 

 

11 L 11 L L a a _ L1
{'1‘} g
ill. 1.! . . u\ 1! '1’ ..lllfll " ll":’ll iulthI-Pl 11 ..Il Nul‘gf11} » 1 .‘i” {11!}! .‘a‘ilosll
‘4' all 1’ \I. ... ., C... -I, .1 5‘ ., |\\|\.
.: H. ... \ i
ll 1 _ ‘4
I i
r‘ u. . i
1 v . _
. . .1 :7
7 i
. , _
_

 

 

86

v mamewm umfihaomou Esuuommm mzznmunm musmflh

 

 

 

$.de $.38
23 . Hmemmm . we:
3 mm 3.8: 3.3 mH 3 SEN OHHRH _ meme
.1 1 111 _ _ , 1 HLI. 1 1.1 .1111 11 1.1111 1r
sen H a n w m m h
I p21,... 1 .. )1. .. W \ Z
r < , i.
,9
H 11 1. .3.
.2

 

87

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