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Lecture 6

Renewable Materials from Fats

BSE 4514: Industrial Processing


Lecture 6
Fats C18:0=stearic
Common Fatty Acids
Chemical Names and Descriptions of some Common Fatty Acids (FAs)

Common Name C double bonds Scientific Name Sources


Butyric acid 4 0 butanoic acid butterfat
Caproic Acid 6 0 hexanoic acid butterfat
Caprylic Acid 8 0 octanoic acid coconut oil
Capric Acid 10 0 decanoic acid coconut oil
Lauric Acid 12 0 dodecanoic acid coconut oil
Myristic Acid 14 0 tetradecanoic acid palm kernel oil
Palmitic Acid 16 0 hexadecanoic acid palm oil
Palmitoleic Acid 16 1 9-hexadecenoic acid animal fats
Stearic Acid 18 0 octadecanoic acid animal fats
Oleic Acid 18 1 9-octadecenoic acid olive oil
Ricinoleic acid 18 1 12-hydroxy-9-octadecenoic acid castor oil
Vaccenic Acid 18 1 11-octadecenoic acid butterfat
Linoleic Acid 18 2 9,12-octadecadienoic acid grape seed oil
Alpha-Linolenic Acid
(ALA) 18 3 9,12,15-octadecatrienoic acid flaxseed (linseed)
oil
Gamma-Linolenic Acid
(GLA) 18 3 6,9,12-octadecatrienoic acid borage oil
Arachidic Acid 20 0 eicosanoic acid peanut oil,fish oil
Gadoleic Acid 20 1 9-eicosenoic acid fish oil
Arachidonic Acid (AA) 20 4 5,8,11,14-eicosatetraenoic acid liver fats
EPA 20 5 5,8,11,14,17-eicosapentaenoic acid fish oil
Behenic acid 22 0 docosanoic acid rapeseed oil
Erucic acid 22 1 13-docosenoic acid rapeseed oil
DHA 22 6 4,7,10,13,16,19-docosahexaenoic
Lecture 6

Fats: Triglycerides (TGs)


Triglycerides are common fats found in plants as liquids (oils)
and animals as solids (tallow) and sometimes oils.
C18:1 oleic
These molecules are
C18:1 oleic similar to HCs!
C16:0 palmitic
Olive oil
Triglycerides are formed from the esterification of a fatty acid with
glycerol (acid + alcohol = ester).
3 FAs joined at a glycerol juncture
O
=

CH3(CH2)7CH=CH(CH2)7C-OH HO CH2
O
HO CH
=

+ = Olive oil + 3H2O


CH3(CH2)7CH=CH(CH2)7C-OH
O HO CH2
=

CH3(CH2)14C-OH
Lecture 6

Fats: Saturated vs. Unsaturated


saturated FA: only CH2, no C=C;
packs into crystals efficiently,
Tm>room T; solid fat at room T;
bad fat

unsaturated FA: some CH2, some C=C; does


not efficiently pack into crystals, Tm<room T;
liquid at room T; good fat

Molecules have Tm depending on unsaturation


Lecture 6

Plant Oils

these are the big ones in US; soy is most important for
renewable materials ~22% of total plant oil market
animal fats are of secondary importance b/c of larger distribution of FAs
and higher FFA/TG ratio
from Bio-Based Polymers and Composites, Wool and Sun, Elsevier, 2005
Lecture 6

Structure of Soybean Oil

~11% palmitic C16:1

~23% oleic C18:1

~53% linoleic C18:2

~8% linolenic C18:3


Lecture 6

Products from Plant Oils


Epoxies (EPO)
Cross-linked polyesters (CPE)
Polyurethanes (PUR)

You have most likely heard of these materials. Plant oils


are functionalized then those functional groups are
cross-linked to make a thermosetting or network
polymer. The functionality is either epoxy, polyester, or
polyurethane.
Lecture 6

Network Polymers
So far, we have talked about thermoplastic polymers. These are polymers
that have inter-molecular interactions in the form of non-covalent bond
interactions such as friction (entanglements), hydrogen-bonding,
crystallinity, etc. Plasticized starch, PLA, and PHA are technically
thermoplastic (even though for native starch, and even cellulose, there
are so many of these non-covalent interactions that they act like covalent
bonds when summed up): they have a glass transition temperature (Tg)
and a melting temperature for crystals (Tm). The structure can be re-
processed over and over again simply by putting enough energy into the
polymer to overcome most of the inter-molecular interactions and
forming a new shape (the process is reversible, usually through
temperature by melting crystals and re-forming them upon cooling).
These polymers can be recycled and re-used.

Cross-linked or thermosetting polymers only have inter-molecular


interactions in the form of covalent bonds. The polyisoprene from HW #2
is an example. Typical thermosetting polymers are tire rubber and most
adhesives and glues. If you put energy into the system and destroy the
covalent interactions, the material cannot be recycled and re-used b/c
you have irreversibly damaged the material.
Lecture 6

Thermoplastic Polymers
entanglement=friction
xtal
-
+
energy
ionic bond or
salt bridge hydrogen bond

entanglement=friction
Lecture 6

Thermosetting or Network Polymers

covalent bonds

energy

if the energy is high enough to break the inter-molecular covalent bonds,


then it will also break the intra-molecular covalent bonds!
Lecture 6

Functionality
Functionality, f, means specific chemical sites in a molecule that are
amenable to chemical reaction
f

f 2
f
f
Mf

f
f Network
f
keep reacting functional groups, f, until we form a network of high
properties
RT
E Network has a Tg but no Tm
Mf
Lecture 6

Places to functionalize on TGs


Introduce polymerizable groups onto TG using standard synthetic techniques.

most
likely

C=C is most reactive in oxidation reactions (rancid oil, drying oils for paints,
so functionalizing stabilizes it)
Lecture 6

Soybean Oil (SO) Functionality


Not only is E a
function of f (# and
distance) but distance
f is from chain end
(how much of chain is
pendant)

pendant groups (does not support


and may plasticize)
what is f? main chain (supports )
what is a saturated FA?
Lecture 6

Epoxies
Epoxidized soybean oil (ESO) can be purchased commercially. It is currently
used as a plasticizer in PVC (an alternative to carcinogenic dioctyl phthalate
or DOP). Usually low Mw or oligomeric.

Petroleum-based epoxies are based on bisphenol-A and have terminal epoxy


groups that can react with amines, polycarboxylic acids, or anhydrides or self-
polymerize to ethers with a suitable catalyst. All routes easily form networks.
Lecture 6

Epoxies
Epoxidized vegetable (soybean) oils have internal epoxy groups (not on chain
ends) that are much less reactive and cannot be cross-linked the same as
petroleum-derived epoxies.

oxidation rxn
Lecture 6

Epoxies
~90% conversion of C=C or ~4.1-4.6 epoxies/TG

Once you have ESO, you can react to form a


network just like petroleum-based epoxies. Not
easy to use NH2 so usually want to use an acid
catalyst, anhydride, or Lewis acid (electrophile or
e- acceptor such as metal chloride, etc.) to
polymerize. A great catalyst is citric acid b/c it is
a fermentation product or naturally-occurring so
bio-based! This usually gives a rubbery material
with low E and Tg.

Phthalic (acid) anhydride gives a glassy or


rubbery material depending on molar ratio of
epoxy to PA. Contains aromatic rings so high E
is possible. You first have to convert epoxy group v. standard epoxy chemistry!
to OH and then react to form an ester.

from Polymer Science and Technology, J.R. Fried, 1995


Lecture 6

Epoxies

b~9%

curing=network formation; higher T=faster cure (usually 140oC); reacted


under the same conditions, Tg can as a function of anhydride reactant: PA
(65oC), hexahydrophthalic (49oC), maleic (35oC), and dodecylsuccinic (31oC)

from Natural Fibers, Plastics and Composites, ed. Wallenberger and Weston, 2004
Lecture 6

Epoxies
The biggest markets for epoxies are in composites where the fiber is usually
glass or carbon but can now include cellulosic. The properties of these
composites can be quite high when you imagine the property of the fiber
(from previous lecture) and the properties of ESO networks as shown in
previous slide.
for 50:50composite=polymerpolymer+fiberfiber
=0.5(30 MPa)+(0.5)(350 MPa)
=190 MPa

There are about 3.4 x 109 lbs of long fiber-reinforced thermosetting composites
sold in the U.S. each year; the resin is usually ca. 30% of the material so ~1.1 x
109 lbs of network polymer is needed meaning that you could sell over a billion
pounds of soybean oil based renewable material per year just to this market!

Other markets: elastomers, adhesives, foams, coatings: all networks!


Lecture 6

Polyurethanes (PUR) from Polyols


Easy processing and low price; $3 billion market U.S.; $9 billion market globally

polyol (bio-based) + isocyanate (not bio-based) = PUR


again, relying on synthetic chemistry; can be partial replacement right now
Dow and Cargill make commercially

Preparing polyols from soybean oil (SO):

1) hydrolysis of ester bonds


2) functionalize C=C
Ford soy-based PUR foam for seat backs and
cushions in 2008 Mustang (5% soy-based
polyol in PUR); looking to replace 40% and
could save $26 million/year and soy-based
polyols have 1/4 the environmental impact of
petroleum-based PUR.
Lecture 6

Polyols from ESO


1) Hydrolysis of ester bonds: does not maintain TG (so difficult to form
network without multifunctional reactants or highly unsaturated FA)
Lecture 6

Polyols from ESO


2) Form polyol and react with isocyanate: traditional PUR chemistry
Start from epoxidized soybean oil (ESO): brings out a subtlety in SO
functionalization: that several materials can be formed from ESO and ESO
is what is sold commercially by chemical companies.
Step 1: form polyol

Yields different polyols w/ different structures


so different properties and the resulting PURs hi OH
will be different low
, props=f(X) so want to optimize reactants
so you have a nice pouring system to fill a
mold and a strong material when xlinked
Lecture 6

Polyols from ESO


Reaction products have (viscosity) that depends on:
a) H-bond, i.e., -OH content
b) xtals, i.e., can saturated chain portions of TG pack into xtals?

J. Polym. Sci. Pt. A, 38, 3900-3910 (2000).


Lecture 6

Polyols from ESO

J. Polym. Sci. Pt. A, 38, 3900-3910 (2000).


Lecture 6

Polyols from ESO

OH forms

CH-CH disappears
SO: Mw~872 g/mol
ESO: Mw~947 g/mol
soy polyol: Mw~1000-1300 g/mol = monomer for PUR

J. Polym. Sci. Pt. A, 38, 3900-3910 (2000).


Lecture 6

Polyurethanes from ESO-based polyols


Step 2: react ESO-based polyol w/ isocyanate

=pendant group

+ diisocyanate

=
-O-C-NH-
carbamate
PUR

J. Polym. Sci. Pt. B, 42, 809-819 (2004)


Lecture 6

Polyurethanes from ESO-based polyols

What do you notice about MDI?

Polymer Science and Technology, J.R. Fried, 1995


Lecture 6

Polyurethanes from ESO-based polyols

J. Polym. Sci. Pt. B, 42, 809-819 (2004)


Lecture 6

Effect of different vegetable oil

Elongation at Break (%)


Tensile Strength (MPa)

J. Polym. Sci. Pt. B, 42, 809-819 (2004)


Natural Fibers, Plastics and Composites, ed. Wallenberger and Weston, 2004
Lecture 6

Effect of different vegetable oil

Different oils have different unsaturations so different functionality!


What does linseed oil have?

Bio-Based Polymers and Composites, Wool and Sun, 2005


Lecture 6

Polyurethanes
- Have high strength if xlink density is high
- Good solvent resistance
- High abrasion resistance
- High resistance to O2 and O3
- But can be attacked by microbes or biodegraded!
- 85% foams and 15% elastomers

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