CH3(CH2)7CH=CH(CH2)7C-OH HO CH2
O
HO CH
=
CH3(CH2)14C-OH
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
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.
Thermoplastic Polymers
entanglement=friction
xtal
-
+
energy
ionic bond or
salt bridge hydrogen bond
entanglement=friction
Lecture 6
covalent bonds
energy
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
most
likely
C=C is most reactive in oxidation reactions (rancid oil, drying oils for paints,
so functionalizing stabilizes it)
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.
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
Epoxies
b~9%
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!
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
=pendant group
+ diisocyanate
=
-O-C-NH-
carbamate
PUR
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