Synthesis and Characterization of Alumina filled Polyesteramide Derived from Jatropha curcas Seed oil

The Jatropha curcas seed oil converted to N,N-bis (2-hydroxy ethyl) fatty amide (JCHEFA) by reacting with diethanol amine. JCHEFA reacted with phthalic acid to obtained Jatropha curcas polyesteramide (JCPEA). The JCPEA treated with aluminium hydroxide to synthesized alumina filled polyesteramide (JCAPEA). The synthesized JCHEFA, JCPEA and JCAPEA have been characterized by the measurement of physic-chemical properties like specific gravity, refractive index, acid value, iodine value, soponification value. The synthesized intermediates and the final resin were also characterized by FT-IR, 1HNMR spectroscopic analyses.


INTRODUCTION
Polyesteramide resins are amide modified alkyds which contain both amide (-CONH-) and ester (-COOC-) linkages and known for the improve performances over traditional alkyds [1][2][3] .Incorporation of aluminium in the polymeric resin further improves the performances notably in terms adhesion, hardness and the water vapor resistance ability 4 .
Use of renewable raw materials in the chemical industries attracted the attention of academia and scientist as it reduces the dependence on non-renewable resources such as Jatropha curcas is medium sized tree largely cultivated in rural areas.It grows rapidly in hardy to dry weather conditions.Jatropha curcas tree yielded non edible seeds which contain about 48 % oil.The seed oil-a triglyceride which contain appropriate percentage of unsaturated fatty acids 15 .
Keeping these facts in mind and abundant availability of the Jatropha curcas seed oil in present work we have make an effort to utilize this seed oil in making alumina filled polyesteramide.

Materials
The seeds of Jatropha curcas were collected from the local areas of Shahjahanpur district.The oil was extracted from the dried and crushed seeds through the soxhlet apparatus using petroleum ether as a solvent (60-80 o ).The fatty acid composition and the results of the physico-chemical characterizations are summarized in the Table 1.Phthallic acid, diethyl ether, methanol were used of analytical grade (Merk-India).Diethanol amine of analytical grade procured from the s.d.Fine chemicals India and was distilled under reduced pressure before use.

Synthesis of Jatropha curcas N,N-bis (2-hydroxy ethyl) fatty amide (JCHEFA)
Diethanol amine 0.03 mol was taken in four necked round bottom flask fitted with an electrical stirrer, thermometer, dropping funnel and condenser.The reaction mixture was heated at 180±5 o C. The Jatropha curcas oil (0.1 mol) was added drop wise into the reaction mixture over a period of one hour.The progress of the reaction was monitored by TLC.After the completion of the reaction the product was dissolve in diethyl ether and washed with dilute aqueous sodium chloride solution.The ethereal solution filtered and evaporated in rotatory vacuum evaporator to obtained JCHEFA.

Synthesis of Jatropha curcas Polyesteramide (JCPEA)
JCHEFA and phthalic acid in equal molar ratio and xylene as a solvent were placed in four necked round bottom flask fitted with a Dean-stark trap thermometer and mechanical stirrer.Reaction mixture was heated up to 200±5 o C. The progress of reaction was monitored by taking the acid value 12 at regular intervals.After the completion of reaction the product was taken out from the reaction flask and excess of xylene was removed under reduce pressure to obtain JCPEA.

Synthesis of Alumina filled Polyesteramide (JCAEA)
Polyesteramide of Jatropha curcas seed oil (0.01 mole) dissolved in xylene was placed in four necked round bottom flask fitted with Deanstark trap, thermometer and mechanical stirrer.The aluminium hydroxide, Al(OH) 3 0.004 mole added to the reaction mixture.The content heated up to the 140 o C. The progress of reaction was monitored by the taking acid values at regular intervals.After completion of reaction the product was taken out from the reaction flask and excess of xylene was removed under reduce pressure to obtain JCAPEA.

Test methods
Physico chemical characterizations of JCHEFA, JCPEA and JCAPEA were performed as per standard laboratory methods 12 .The structural elucidation was carried out by FT-IR, 1 HNMR spectroscopic techniques.The FT-IR spectra of these materials were taken on Perkin Elmer 1750 FT-IR spectrometer (Perkin Elmer Citus instruments Norwalk CT) using NaCl cell. 1 HNMR spectra of the resins were recorded on Jeol GSX 300 MHz FX-1000 spectrometer using deuterated chloroform and DMSO as a solvent and tetra methyl silane as an internal standard.

RESULTS AND DISCUSSION
Figure 1 show the scheme for the preparation of JCHEFA, JCPEA and JCAPEA.Significant increase in the hydroxyl value indicates the conversion of triglyceride (oil) into diol (JCHEFA).The JCHEFA reacted with phthalic acid to obtained polyesteramide through the condensation polymerization.The progressive decrease in acid values indicates the conversion of carboxylic group to ester linkage with reaction of hydroxyl group of JCHEFA.The same was confirmed by the collection of water in Dean-Stark trap.Polyesteramide contain both carboxylic and hydroxyl groups at the terminals.The carboxyl terminal of JCPEA coupled with the  The IR spectrum of JCHEFA shows the strong band at 3440 cm -1 a characteristic band for the primary alcoholic group.In addition to this band carbonyl of amide appears at 1640 cm -1 indicate the formation of amide linkage.The band for the aliphatic chain CH 2 appears at 2840-2920 cm -1 for symmetric and asymmetric stretching respectively.
The 1 HNMR spectrum of JCHEFA shows the peak at =3.6 ppm for the CH 2 attached to the nitrogen of amide, CH 2 attached to hydroxyl group appears at 4.4 ppm.The multiplet peak for proton of double bonded carbons appears at 5.2-5.6 ppm.In addition to these peaks terminal methyl group appears at 0.90 ppm and aliphatic chain CH 2 appears as multiplet at 1.2-1.50ppm.
The IR spectrum of JCPEA shows band at 1746 cm -1 for the carbonyl of ester in addition to band at 1642 cm -1 of the amide confirm the formation of ester linkage as repeating unit.The other characteristic bands like strong band at 3410 cm -1 appears for alcoholic group, symmetric and asymmetric bands for the chain CH 2 appears at 2862 cm -1 and 2940 cm -1 respectively; whereas the characteristic band for the disubstituted benzene ring appears at 770 cm -1 .
The IR spectrum of JCAPEA shows the band at 1760 cm -1 for the carbonyl of ester and 1664cm -1 for carbonyl of amide.The band for -OH group appears at 3520 cm -1 ; whereas bands for the -CH 2 -symmetric and asymmetric stretching appears at 2866 cm -1 and 2946 cm -1 respectively.It has been found that absorption bands for the carbonyl of ester and amides both shifted mark ably in higher frequency region on incorporation of alumina.Furthermore band for the -OH group appears in higher frequency region and also more spreads.
The 1 HNMR spectrum of JCAPEA show the sharp peak of chain -CH 2 -adjacent to carbonyl of ester at 2.1 ppm, multiplet peak for the -CH=CHappears at = 5.31-5.37ppm, aromatic proton appears at =7.6-8.2 ppm, broad peak for chain -CH 2 -appears at = 1.20-1.32ppm, terminal -CH 3 appears at =0.93 ppm.It has been found that peak for the aromatic proton shifted towards down field due the presence of alumina in polymer backbone 16 .

CONCLUSION
Jatropha curcus seed oil a renewable and abundantly available raw material utilized successfully in the synthesis of Polyesteramide and alumina filled polyesteramie resins.Utilization of renewable resources in chemical industries reduces the pressure on consumption of non renewable resources like petroleum.The synthesized resins were characterized by taking the physical and chemical properties and by spectroscopic studies.