Special Report

Polyurethanes from vegetable oils

IntroductIon olyurethanes are versatile plastics, which occupy an important position in the global market of high performance synthetic polymers. Since, urethane group is a structural combination of ester and amide, its properties lie between these groups. Polyurethane, a class of polymers prepared by reacting a dihydroxyl monomer with a diisocyanate monomer (Fig 1), are widely used in high resiliency flexible foam seating, bedding, rigid foam insulation panels, microcellular foam seals, gaskets, durable elastomeric wheels, tires, footwear, gel pads, print rollers, automotive suspension bushings, electrical potting compounds, high performance adhesives, surface coatings (paint, varnish), sealants, fibers, seals, gaskets, carpet underlay, hard plastic instrument bezels, structural parts, flexible plastics as straps and bands. By selecting suitable monomers or combination of components, the end properties of these polymers can be tuned from coating, soft material, elastomer, foam, to hard plastics.

OMPRAKASH S. YEMUL BHASKAR S. DAWANE & RAHUL V. PINJARI School of Chemical Sciences Swami Ramanand Teerth Marathwada University Nanded 431606 Maharashtra Corresponding author: omyemul@gmail.com stock used by the chemical industry and it is expected to increase up to 25% by 2020. Oils and fats constitute the most important renewable raw materials for the chemical industry, followed by carbohydrates and other renewable such as proteins and protein surfactants. The potential for polyols derived from vegetable oils to replace petrochemical-based polyols began garnering attention beginning around 2004, partly due to the rising costs of petrochemical feedstocks and partially due to an enhanced public desire for environmentally-friendly green products. In addition, they have the potential to cut carbon emissions and reduce CO2 quantities in the atmosphere: since the CO2 released during degradation can be reabsorbed by crops grown this tends to carbon neutral (Fig. 2). Cargill estimates that its shift from petroleum to vegetable oil based polyols has reduced CO2 emission and burning fuel by 36% and 61%, respectively. Vegetable oil as source of raw material The plant oils available in large quantities from various oilseeds are one of the cheapest, most abundant, and annually renewable natural resource. The versatile chemistry applied to triglycerides, a component of oil, (Fig. 3) have led to variety of polymeric structures from linear, processible polymers to
203

The conventional polyurethanes are prepared from petroleum based polyols, which are polluting, non-biodegradable, and emit more CO2 during production. Developing polyols that are environment-friendly, biodegradable, and non-polluting have greatly attracted both academic and industrial scientists. One of the options is from readily renewable resources as raw materials. Renewable raw materials make up an approximate 10-12% of the feed-

hO Polyol

Oh

OCn diisocyanate catalyst

nCO

O O O C

h n

h n

O C n

Polyurethane Fig. 1: Synthesis of polyurethanes by reacting polyol and diisocyanate Chemical Weekly May 17, 2011

Special Report
crosslinked systems applicable as resins and coatings etc. The synthesis of monomers as well as polymers from plant fats or oils has already found industrial applications and being used increasingly; recent developments in this field offer promising new opportunities. Today, high-performance bio-based nylons, polyesters and thermoplastic elastomers are commercially used in a variety of applications. In most cases, these products also provide a cost savings compared to the respective petroleumbased polymers.
Vegetable oil

Plant (Photosynthesis)

Biodegradable plastics

Polymerization

The first plant oil used in manufacture of polyurethanes is Castor oil (Fig. 4), which contains triglyceride structure with rincinoleic acid possessing hydroxyl group and unsaturation as a major component of the oil. Castor oil triglyceride is directly used as polyol in the manufacture of rigid one-shot polyurethane foam. The secondary hydroxyl groups have less reactivity than primary hydroxyl groups in petroleum based polyols (Fig. 5). The foam produced from castor oil has poor compressive strength. Other vegetable oils such as soya bean oil, peanut oil, and canola oil are unsaturated fatty acids without any hydroxyl groups. Such unsaturations are utilized for further chemistry. The comparative polyol structures from petroleum and vegetable oil have been presented in (Fig. 5). Treatment of these vegetable oils with peroxy acids gives epoxides which then react with nucleophiles (like methanol) to give hydroxyl groups (Fig. 6(a) in a single step process. Although epoxidation of double bonds is an easy process, it produces secondary hydroxyl group (again less reactive) with additional dandling chains, which consequently affects the mechanical properties of resultant polyurethane. Several other processes

204

Chemical Weekly May 17, 2011

Special Report
o ho R o C R o C o R o n Petroleum based polyester polyol h

ho

o o o o o

o oh

oh

Latral chains

Latral chains

Vegetable oil based polyol Fig. 5: comparative structures of petroleum based polyester polyol and vegetable oil based polyol o

In another attempt the double bond was reacted with alcohols in presence of mercury catalyst producing primary hydroxyl based honey bee polyol (Fig. 7(a)); the catalyst toxicity however poses threat to environment. Ozonolysis (Fig. 7 (b)), a special case of oxidation, is a direct, more powerful and fairly controlled process for cutting double bonds. Treatment of the vegetable oils with ozone cleaves the double bond, and esters or alcohols can be made, depending on the conditions used to process the ozonolysis product. The process utilizes ozone, which is available cheaply. The resultant polyol has primary hydroxyl group and possess

(a)

o o o o o o

(b)

o o o o o

Peroxy acid

Alcoholysis
o o o oR o oR o oR o

CO

h2

Catalyst

o o o o

oh oh

oh

oh

oh

oh

Fig. 6: (a) Alcoholysis treatment for triglycerides producing polyol; (b) Hydroformylation process for producing polyol

such as hydroformylation and oxidation of the C-C double bond are used to introduce hydroxyl groups onto the carbon chain of the fatty acids. In the former method the double bond is treated with carbon monoxide and hydrogen in the presence of a metal catalyst to add a -ChO (formyl) groups to the chain (hydroformylation reacChemical Weekly May 17, 2011

tion) followed by its hydrogenation to yield desired (primary) hydroxyl groups (Fig. 6 (b)). Despite production of primary hydroxyl group using hydroformylation, the feasibility of the process and contamination of costly metal catalyst (cobalt, ruthenium complex) in polyol hampers commercialization.

reactivity and properties close to polyol from petroleum source. Solution cast thin films of polyurethanes have been developed in the laboratory from methyl oleate (Soybean oil based fatty acid) as presented in Fig. 8. It is a clear, transparent thin film, which has very good optical clarity.
205

Special Report
(a)
o o o o o o

(b)

o o o o o

Catalyst

hO

Oh

Ozone
o o o

hO

Oh
o o o o o o oh oh

o o o o

oh

oh o o

o oh o

oh

Fig. 7: (a) Honey bee polyol; (b) ozonolysis of vegetable oil producing polyol

2.

3.

4.

5.
Fig. 8: Illustration of the film transparency segmented polyurethane film

Companies manufacturing natural oil polyols are Ford Motor Company, Dow Chemicals (Renuva), huntsman (JEFFADD), Envirofoam Chemicals Ltd., U.K. Cargill (BiOhTM), MCPU
206

Polymer Engineering and Shivathene Linopack Ltd. reFerenceS 1. Polyurethanes from Vegetable Oils

Zoran S. Petrovic Polymer Reviews, 2008, 48(1) 109-155. Polymers from Renewable Resources: A Perspective, Charlotte K. Williams; Marc A. hillmyer Polymer Reviews, 2008, 48(1) 1- 10. Polymers from plants to develop biodegradable plastics, Udo Conrad, Trends in Plant Science, 2005, 10(11), 511-512. Vegetable oils in production of polymers and plastics, Suresh S. narine and Xiaohua Baileys Industrial Oil and Fat Products, Sixth Edition, Volume 6, Page 279 (2008), Ed Fereidoon Shahidi. novel Thermoplastic Polyurethane Elastomers Based on Methyl-12-hydroxy Stearate, Omprakash S. Yemul and Zoran S. Petrovi Contemporary Science of Polymeric Materials, Chapter 2, 2010, pp 29-39, ACS Symposium Series, Volume 1061.
Chemical Weekly May 17, 2011