Umeet al.

, IJSID, 2013, 3 (1), 86-92

ISSN:2249-5347

IJSID

International Journal of Science Innovations and Discoveries

Research Article

An International peer Review Journal for Science

Available online through www.ijsidonline.info

MEDIUM ALKYD RESINS Umeobika U.C., Onuegbu T.U., Iloamaeke M.I., Ekwueme I.J

SYNTHESIS AND EVALUATION OF PERFORMANCE CHARACTERISTICS OF RUBBER SEED OIL-MODIFIED SHORT AND

Department of Pure and Industrial Chemistry, Faculty of Physical Science, Nnamdi Azikiwe University, Awka, Anambra State, Nigeria

Received: 14-01-2013 Accepted: 10-02-2013

*Corresponding Author

ABSTRACT resins of varying oil length (35%) for short alkyd and 50% for medium alkyd (oil modified Rubber Seed Oil (RSO) was employed in the production of two samples of alkyd

polyester) using the monoglyceride method. The rubber seed oil and its alkyd resins were

all characterized and evaluated by standard methods, for their physico-chemical properties, Drying schedule and chemical resistance. RSO had an iodine value of RSO gave alkyd resins whose coating properties are comparable to those of commercial 139.59gI2/100g, viscosity of 4.905 St, Free fatty acid of 13.87mgKOH/g and light brown in colour. These results showed that RSO is qualified to be used in production of alkyd resin.

Address: Name: Umeobika Place: Anambra State, Nigeria E-mail: dagombe@yahoo.com

alkyds, as its air-film dried within a few hours and showed good chemical resistance in various solvent media such as water, brine and water. The iodine value of the short and

medium alkyds were 30.90 gI2/100g and 42.50 gI2/100g respectively which showed that in the production. The obtained resins were also characterized by Fourier Transform H stretch for aromatic benzene and C-O stretch for aromatic ester respectively.

the level of unsaturation of the alkyd resins increased with the proportion of the RSO used INTRODUCTION

Infrared Spectrophotometer (FTIR) and results showed absorptions at regions 1957cm -1

and 2644cm-1 for short and medium alkyds respectively which showed the presence of C-

INTRODUCTION Keyword: Rubber seed oil, Oil length, Alkyd resin, Alcoholysis, Chemical resistance

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Umeet al., IJSID, 2013, 3 (1), 86-92 are large expanse of land of rubber plantation scattered around the length and breadth of the southern part of the country, The oil which is obtained from the seed of rubber tree is presently not exploited industrially in Nigeria where there INTRODUCTION

irrespective of its reported potentials such as alkyd synthesis, epoxydation of oil, production of metal soap, biodiesel etc., (Okiemen and Ebhoaye, 1992, Ikhuoria et al., 2002). These rubber estates are capable of providing about 13,000 ton of rubber modified polyesters (Stevens, 1999). This study gears in establishing the effect of oil length in the drying time of the oil modified alkyd resins. largely due to their unique properties such as film hardness, durability, gloss and gloss retention, resistance to abrasion etc. impacted on them through modification with drying oil (Aigbodion et al., 2001). 2000, Kildiran et al., 1996 and Majumder, 1999). Alkyd resins are by far the most important class of coating resins. It is estimated that alkyd resins contribute about

seed oil annually (Nwakwo et al., 1986). The oil is unsaturated and comprise mainly of oleic, linoleic and linolenic acids. The

function of oils and fats in alkyd is to provide the site for free radicals cross linking, which is the mechanism of drying of oil70% of the conventional binders used in surface coatings (Bajpai, 2000). The popularity of alkyd resins as vehicle for coating is

modified with a monobasic fatty acids or drying oil with suitable catalyst at controlled temperature (Aigbodion et al., 2000). The oils that are mostly employed for alkyd resin synthesis are linseed, soybean, castor and tall oils (Ogunyi and Njikang, drugs, food etc. However, drying oils are available locally, which have remained untapped. These include rubber oil, soybean oil, walnut oil and tobacco oil (Adefarati, 1986). These drying oils owe their value as raw materials for decorative and impervious and abrasion resistance films. The advantages claimed in surface coating applications include excellent odour and heat bleach ability, good drying properties and more uniform polymer structure (Kirk and Othmer, 1947). MATERIALS AND METHODS Sample Collection and Preparation These oils are largely imported to Nigeria for the formulation of coatings for metal cans used in packing of beverages,

Alkyd resin is defined as the product of polycondensation reaction between a polybasic acid and polyhydric alcohol

protective coatings to their ability to polymerize or dry after they have been applied to surface to form tough, adherent,

were air dried in the oven at 500C for 72 hours and shelled to obtain the kernels which were then blended to obtain rubber seed meal. Rubber seed oil (RSO) was then extracted from the meal with n-hexane using a soxhlet apparatus. Alkyd Preparation according to the monoglyceride method as described by Ikhuoria and Aigbodion, 2005, 2006. In a typical experiment, the RSO Rubber seed oil modified short alkyd (35% oil length) and medium alkyd(50% oil length) alkyd resins were prepared

Rubber seeds were collected from the Rubber Research Institute of Nigeria, Iyanomon, Benin city. The rubber seeds

was reacted with glycerol at a temperature range of 230-2500C in a three necked flask, fitted with motorized stirrer, nitrogen gas inlet, a dean and stark trap carrying a water condenser. Alcoholysis was complete when one part of the reaction mixture 1800C and then phthalic anhydride and xylene was introduced to the flask. Then the reaction temperature was raised to below 10. International Journal of Science Innovations and Discoveries, Volume 3, Issue 1, January-February 2013

dissolved in three parts of anhydrous methanol and formed a clear solution. The reaction temperature was cooled to about

between 230-2500C and then monitored to completion by determination of the acid value periodically, until it dropped to

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Umeet al., IJSID, 2013, 3 (1), 86-92 Characterization of the Samples 1639-90, (1994), ASTM D 1541-60, (1979) and ASTM D 1962-67, (1979). Performance Characteristics of Alkyd Films The physico-chemical properties of RSO and its resins were determined using ASTM standard methods (ASTM D The performance characteristics of the films were determined in terms of drying schedule and chemical resistance.

Films of RSO alkyd were prepared by applying thin spread the resin on clear glass panel and dried at room temperature. The drying process was monitored in terms of the time of set-to- touch, surface-dry and dry-through. resistance of the films to different solvent media (water, brine, NaOH, HCl) was determined. RESULTS AND DISCUSSION seed oil, which is recommended standard in the production of alkyd resin.

The chemical resistance was determined using ASTM (D 1308-67) standard test method at room temperature. The The physico-chemical properties of the rubber seed oil was presented in Table 1. The colour of RSO was light brown.

It had a specific gravity of 0.89 which indicated that the oil is less dense than water. This value is quite comparable to the linRSO in form of a drying oil. This is a very important requirement in alkyd synthesis as the surface formulated with the resin dry, hard solid film (Sullivan, 1976). may want to be put to use immediately after coating. Iodine value is also another vital parameter employed in ascertaining the suitability of oil for alkyd synthesis. It shows the level of unsaturation of the oil. The result is indicative of the fact that RSO is quite suitable in alkyd synthesis and its level of unsaturation will accommodate the cross-linking reactions for alkyds to form bearing seed (Cocks and Rede, 1966). The saponification value of RSO was 68.30mgKOH/g. The saponification value reveals the average molecular weight of fatty acids of triglycerides present in RS. Properties Acid value (mgKOH/g) Viscosity (Stokes) Specific gravity Colour Table 1: Physico-chemical Properties of Rubber Seed Oil (RSO) Light brown 167.30 139.59 4.905 0.89 13.87 RSO The acid value of RSO was 13.87mgKOH/g, as it was used to measure the level of deterioration of oil. Sometimes high The iodine value was 139.59 gI2/100g, which when based on the drying oil classification (MacDonald et al., 1994) puts

acid value of oil could be due to hydrolytic reaction during processing of the oil or as a result of enzymatic action in the oil

Saponification value (mgKOH/g) Iodine value (gI2/100g)

colour of the alkyd could be attributed to the colour of RSO and also to high temperatures of reaction, oxidation and catalyst (McDonald et al., 1994). This alkyd can be utilized in the production of pigmented coatings where very bright colour is not a major requirement.

The physico-chemical properties of short and medium oil modified resin were presented in Table 2. The darkening

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the cause of the reaction and the resistance of alkyd flow, which was brought about by intermolecular friction arising from increase in molecular size. of the alkyds could be attributed to the dimerization and polymerization reactions at the reactive double bonds of the oil of RSO used in the production as it was observed that the iodine value of the medium alkyd was higher than that of short The alkyds were essentially polyesters. Table 2: Physico-chemical Properties of Short and Medium RSO modified Alkyd Resins Short Dark brown 6.20 392.70 30.90 23.00 Medium Dark brown 8.40 342.10 42.50 12.30 342.10mgKOH/g for short and medium alkyds respectively as compared to that RSO. This was due to polymerization reaction. Properties Colour Acid value (mgKOH/g) Saponification value (mgKOH/g) Viscosity (Stokes) The iodine values of the alkyds were observed to have decreased considerably to 30.90mgKOH/g and 42.50mgKOH/g

The viscosity of the alkyds was much higher than the RSO. This was due to the formation of 3-dimensional structure in

Umeet al., IJSID, 2013, 3 (1), 86-92

for short and medium alkyds respectively as compared to that of RSO (139.59mgKOH/g). The decrease in level of unsaturation alkyd. The saponification values of the alkyds were observed to have increased greatly considerably to 392.70mgKOH/g and

during alkyds synthesis (Momodu, 2011). The result also showed that the level of unsaturation increased with the proportion

resistance to acid, brine, water but poor resistance to alkali. The poor alkali resistance of alkyds may be explained on the basis that they consist essentially of ester groups, which are known to be susceptible to hydrolysis by alkali (Momodu, 2011). Acid (0.1NH2SO4) Alkali (0.1NKOH) Solvent Media Table 3: Chemical Resistance to Rubber Seed Oil modified Alkyd Films Short 1 1 1 2 Medium 1 1 1 2

The chemical resistance of the alkyds prepared by RSO was shown in Table 3. Films of these samples showed excellent

Iodine value (gI2/100g)

set to touch after 52 minutes and 42 minutes respectively, surface dry after 2 hours and 2 hours for short and medium alkyd be used as binder in surface coating formulation as it showed comparable coating properties to other reported oil modified alkyd.

respectively and completely dried after 10 hours for both alkyds. Based on this result, it can be inferred that RSO alkyd could

The drying schedule of RSO alkyd film was shown in Table 4. It was observed that the short and medium alkyds were

Brine (5%w/wNaC l) Water (Cold)

1= film not removed, 2=film removed

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alkyd dried more by process of auto oxidation than evaporation while the short alkyd was vice versa. The process of auto oxidation had been recognized to the related to the amount of double bonds present in the oil as measured by iodine value.

Table 4 showed that medium alkyd exhibited a faster drying rate than the short alkyd. This was because the medium

Umeet al., IJSID, 2013, 3 (1), 86-92

RSO wave no.(cm-1) 463 915 1165 1418 3458

Table 5: FTIR Absorption Band of RSO, Short and Medium Alkyd Resins Short (cm-1) 419 740 1286 1490 1957 2614 3409 Medium (cm-1) 577 743 1143 1455 1957 2644 3434

Figure 1: FTIR of RSO

C-H deformation for alkyl and aryl groups C-O stretch for esters, ethers and alcohol C=C double bond stretch for alkenes and aromatics C-H stretch for aromatic benzene C-O bond stretch for aromatic ester Free O-H stretch

Functional group (broad description) C-H deformation for methyl groups

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Figure 2: FT-IR of Short Alkyd Resin

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Umeet al., IJSID, 2013, 3 (1), 86-92

medium alkyds as shown in figures 1, 2 and 3 respectively depicts the characteristic listed in Table 5. The absorption band in for esters, ethers and alcohol respectively. Furthermore, in short and medium alkyds, there were absorptions at regions1957cm-1 and 2644cm-1 which showed the presence of C-H stretch and C=O stretch for aromatic benzene and aromatic ester which was as a result of reactions of phthalic anhydride and glycerol. CONCLUSION alkyd resin as indicated by physico-chemical and infra-red analysis. The alkyd films were highly resistant to acid, brine, water. resistance and relatively longer drying time. It is our wish that further studies be carried out to improve those properties. REFERENCES Rubber seed oil was used in the preparation of alkyd resin. RSO seems to be more promising in the production of

the regions 1165cm-1, 1418cm-1 and 1744cm-1 in RSO which showed the presence of C-O stretch, C=C stretch and C-H stretch

The Fourier Transform Infra-Red Spectra (FTIR) analysis was presented in Table 5. The spectral of RSO, short and

Figure 3: FT-IR of Medium Alkyd Resin

1. 2. 3.

Therefore, they can be useful in formulation of non-polluting coatings. However, it has its short comings such as poor chemical

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Industrial Utilization of Natural Rubber (Hevea brasiliensis) seed, latex and wood, Rubber Research Institue of Nigeria. 27Aigbodion, A.I. and Spillai, C.K., (2000): Preparation, Analysis and Application of Rubber Seed Oil and its Derivatives in International Journal of Science Innovations and Discoveries, Volume 3, Issue 1, January-February 2013

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4. 5. 6. 7. 8. 9.

ASTM D 1639-90, (1994): Standard Method for Acid Value of Organic Materials. In: Annual Book of American Society for Testing and Material Standards. 6: 260-261. of American Society for Testing and Material Standards. 29: 259-61. for Testing and Material Standards. 29: 186-189.

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ASTM D 1962-1967, (1979): Test for Saponification Value of drying oils, fats and polymerized fatty acids. In: Animal Book Bajpai, M. And Seth S., (2000): Use of Unconventional Oils in Surface Coating: Blends of alkyd resin with epoxy esters. Pigment and Resins Technology. 29(2): 82-87. Cocks, L.V and Rede, C.V., (1966): Laboratory Handbook for Oil and Fat Analysis, London Academy Press, London. 305-309. Based Alkyd Resins. J. Appl. Polym. Sc. 101: 3073-3075. fumarized rubber seed oil. Progress in Org. Coatings, 52:238-240. 36.

ASTM D 1541-60, (1979), Test for Iodine Value of drying oils and their derivatives. In: Annual Book of American Society

10. Ikhuoria, E.U, Aigbodion, A.I and Okieimen, F.E., (2005). Preparation and Characterization of water reducible alkyds with 11. Kildiran, G., Yucek, S.O. and Turkay, S., (1996): In-situ alcoholysis of soyabean oil. J. Amer. Oil Chem.Soc. 73(2): 252-8. Paint India. 60:57-65.

Ikhuoria, E.U. and Aigbodion, A.L., (2006). Determination of Solution of Viscosity Characterization of Rubber Seed Oil

12. MacDonald, P., Edward, R.A. and Greenhalg, J.F.D., (1994): Animal Nutrition, 4 th Edition, Longman Publishers. 22-28, 3213. Majumder, S., Kumar, D., Nirvan, Y.P.S., (1999): Acrylate grafted dehydrated castor oil alkyd. A binder for exterior paints. 14. Momodu, V.M., Omorogbe, S.O, Ikhuoria, E.U., and Aigbodion, A.I. (2011): Synthesis and Evaluation of Performance 15. Nwakwo, B.A., Aigbekaen, E.O. and Sugay, G.A., (1986): Estimates of Natural Seed Production in Nigeria. In: Enabor EE (ed.) Industrial Utilization of Natural Rubber Seed, Latex and Wood. Rubber Research Institute of Nigeria, Benin City, 78. 80. 139-144. Characteristics of Walnut (Tetracarpidium conophorum) Seed Oil-Modified Alkyd Resin. Researcher; 3(7): 63-66.

16. Ogunyi, D.S. and Njikang, G.N., (2000): Preparation and evaluation of alkyd resin from Castor Oil. Pak J. Sc. Res. 43(6): 37817. Okieimen .E F., Bakare, O.I and Okieimen, C,O., (2002): Studies on the epoxidation of rubber seed oil. Ind. Crops Prod. 15: 18. Okieimen .E F. and Ebhoaye, J.E., (1992): Studies in the thermal degradation of polyvinyl chloride in the presence of metal 19. Stevens, M.P., (1999). Polymer Chemistry: An Introduction. In: Polyester. 3 rd ed. Oxford University Press, 335-358. soaps of rubber seed oil. Eur. Polym. J. 28(1): 1423-1425.

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