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Full Paper

Summary: Biobased epoxy materials were prepared from diglycidyl ether of bisphenol A (DGEBA) and epoxidized castor oil (ECO) initiated by a latent thermal catalyst. The physicochemical and mechanical interfacial properties of the DGEBA/ECO blends were investigated. As a result, the thermal stability of the cured epoxy blends showed a maximum value in the presence of 10 wt.-% ECO content, which was attributed to the excellent network structure in the DGEBA/ ECO blends. The storage modulus and glass transition temperature of the blends were lower than those of neat epoxy resins. The mechanical interfacial properties of the cured specimens were signicantly increased with increasing the ECO content. This could be interpreted in terms of the addition of larger soft segments of ECO into the epoxy resins and thus reducing the crosslinking density of the epoxy network, which results in increasing toughness in the blends.

KIC values of the DGEBA/ECO blends as a function of ECO content.

Effect of Biodegradable Epoxidized Castor Oil on Physicochemical and Mechanical Properties of Epoxy Resins
Soo-Jin Park,* Fan-Long Jin, Jae-Rock Lee
Advanced Materials Division, Korea Research Institute of Chemical Technology, P.O. Box 107, Yusong, Daejeon 305-600, South Korea Fax: (82) 42-861-4151; E-mail: psjin@krict.re.kr

Received: May 25, 2004; Revised: July 15, 2004; Accepted: July 15, 2004; DOI: 10.1002/macp.200400214 Keywords: biodegradable; cationic polymerization; crosslinking; mechanical properties; thermal properties

Introduction
Recently, replacement of petroleum-derived raw materials with vegetable oil-based polymeric materials has become important from the social and environmental viewpoints.[1,2] Vegetable oils are complex multi-component mixtures of different triacylglycerols, that is, esters of glycerol and fatty acids.[3] Vegetable oils containing unsaturated fatty acids can be valuable in chemical industry because they can be used in polymerizations to make biobased polymers.[46] Among them, castor oil represents a promising raw material based on its low-cost, low toxicity, and its availability as a renewable agricultural resource. Castor oil is used commercially in large amounts, and its major constitution, ricinoleic acid (12-hydroxy-cis-9-octadecenoic acid), is a
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hydroxyl fatty acid.[5] There have been many studies on the synthesis and characterization of a wide variety of polymers based on vegetable oil. Patel et al. and Zlatanic et al. reported interpenetrating polymer network from castor oilbased polyurethanes with poly(methyl methacrylate) and 4,40 -diphenylmethane diisocyanate and polyols based on vegetable oils.[7,8] Hu and co-workers also examined polyurethaneurea/vinyl polymer hybrid aqueous dispersions based on renewable material.[9] Diamond et al. studied modeling the polymerization behavior of vegetable oil derived macromonomers in solution by computer simulation.[10] Srivastava and co-workers showed gel point prediction of metal-lled castor oil based polyurethanes system.[11] Thames et al. examined cationic ultraviolet curable coatings from castor oil glycidyl ether and epoxy
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DOI: 10.1002/macp.200400214

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resins.[12] And, Gultekin and co-workers reported styrenation of castor oil and linseed oil by macromer method.[13] Recently, Park et al. studied synthesis and thermal properties of epoxidized vegetable oil initiated by a thermal latent catalyst.[14] Latent catalysts are inert under normal conditions, such as ambient temperature and room light, but they show activity with external stimulation, such as heating or photoirradiation. The use of latent catalysts increases the storage stability and handling of thermosetting resins.[15] Therefore, latent catalysts are important in the eld of thermosetting resins, such as epoxy resins and multi-functional vinyl ethers.[16] The use of liquid rubbers, such as carboxyl-terminated butadiene acrylonitrile (CTBN) and amine-terminated butadiene acrylonitrile (ATBN), as impact modiers to increase the toughness of the epoxy resins, can lead to a reduction of nal thermal and mechanical properties.[17] Thus, it is more interesting that the introduction of biobased epoxidized castor oil into the epoxy network leads to an improvement in the toughness of the epoxy resins without degrading the thermal properties and elastic modulus. In this work, novel biobased epoxy blends were prepared from diglycidyl ether of bisphenol A (DGEBA) and epoxidized castor oil (ECO) initiated by N-benzylpyrazinium hexauoroantimonate (BPH) as a latent thermal catalyst, and the effect of the ECO contents on the physicochemical and mechanical interfacial properties of the DGEBA/ECO blends was studied by using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), an universal test machine (UTM), and scanning electron microscopy (SEM).

Figure 1.

Chemical structures of DGEBA, ECO, and BPH.

ed to react at 55 8C for 7 h. After the reaction was complete, the crude product was ltered and washed with a saturated solution of NaCO3 and distilled water, and then dried with anhydrous sodium sulfate. Finally, the toluene was removed by distillation under a vacuum oven at 80 8C for 2 h (yield, 84%). FT-IR (KBr): 3 009 cm1 (C C), 822, 833 cm1 (epoxide group). 1 H NMR (CDCI3): d 5.3 (2H, C C), 2.93.1 (2H, epoxide group). 13 C NMR (CDCI3): d 129.7130.2 (C C), 54.0, 54.3 (epoxide group). Sample Preparation DGEBA and ECO were mixed to obtain the biobased blends at a weight ratio of 100:0 to 60:40. DGEBA and ECO were mixed in an oil bath at 80 8C for 30 min and then 1 wt.-% of the latent thermal catalyst (BPH) was added to the mixture. The mixture was completely mixed by a mechanical stirrer and degassed in a vacuum oven to eliminate air bubbles before measuring. The preparation of the specimens for physicochemical and mechanical tests was as follows: bubble-free mixtures were poured into the mold and cured at 120 8C for 1 h, at 160 8C for 2 h, and nally postcured at 200 8C for 1 h in a convection oven. Characterization and Measurements The curing of the DGEBA/ECO blends was performed at a heating rate of 10 8C min1 under the nitrogen gas with a dynamic differential scanning calorimeter (Perkin Elmer, DSC6). The temperature dependence of the loss fact (tan d) for the blends was obtained from their dynamic mechanical properties using a dynamic mechanical analyzer (RDS-II, Rhemetrics Co.) in a three-point bending mode. The measurements were performed at a frequency of 1 Hz and the temperature ranged from ambient temperature to 250 8C at a heating rate of 5 8C min1. The specimen dimensions were 3 mm 12 mm 35 mm. Thermogravimetric analyses were carried out with a duPont TGA-2950 analyzer to measure the weight loss of the cured
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Experimental Part
Materials Epoxy resins used in this study were DGEBA supplied by Kukdo Chem. of Korea (YD-128), which had an epoxide equivalent weight of 185190 g equiv.1 and a density of about 1.16 g cm3 at 25 8C. ECO was synthesized by reaction of castor oil with glacial acetic acid and hydrogen peroxide using Amberite IR-120 as a catalyst.[14] BPH, which was used as a thermal cationic latent catalyst, was synthesized by a known procedure.[18] The chemical structures of the DGEBA, ECO, and BPH are shown in Figure 1. Synthesis of Epoxidized Castor Oil Castor oil (91.8 g, 0.14 mol), glacial acetic acid (21.0 g, 0.35 mol), Amberlite (23 g), and toluene (40 g) were charged into in a round, four-necked 500 mL ask equipped with a mechanical stirrer, thermometer sensor, and reux condenser. The mixture was heated to a constant temperature of 55 8C. Then, 30% H2O2 (56.7 g, 0.5 mol) was added slowly and allowMacromol. Chem. Phys. 2004, 205, 20482054 www.mcp-journal.de

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S.-J. Park, F.-L. Jin, J.-R. Lee

DGEBA/ECO blends from 30 to 850 8C at a heating rate of 10 8C min1 in a nitrogen atmosphere. The fracture toughness parameter, critical stress intensity factor (KIC), of the DGEBA/ECO blends were measured using a single-edge-notched (SEN) test in a three-point exural test, which was conducted according to the ASTM E-399 using an universal test machine (Instron Model 1125 mechanical tester) at a cross-head speed of 2 mm min1. The exural properties of the blends were surveyed with an Instron Model 1125 mechanical tester according to ASTM D-790. All mechanical property values were obtained by averaging of ve experimental values. To investigate the phase morphology of the specimens, the fractured surfaces after KIC test were observed by means of a scanning electron microscope (SEM, JEOL JXA 840A).

Table 1. Peak maximum temperature and cure activation energies (Et) of the DGEBA/ECO blends as a function of ECO content. DGEBA:ECO Tp 8C Ea kJ mol
1

100:0 205 78

90:10 206 110

80:20 205 107

70:30 201 97

60:40 196 94

Results and Discussion

Physicochemical Properties
To investigate the curing behavior of the DGEBA/ECO blends, the thermal latent properties, peak maximum temperature, and cure activation energy were investigated by using dynamic DSC. Figure 2 shows the dynamic DSC scan curves for the blends initiated by BPH at a heating rate of 10 8C min1 and the results are given in Table 1. The Tp shows a maximum value at 10 wt.-% ECO and decreases with increasing the above this content. This result shows that the blends with 10 wt.-% ECO content forms good network structures at relative high temperature. The fractional conversion as a function of temperature for the DGEBA/ECO blends is shown in Figure 3. Both the polymerization of neat epoxy resins and the blends initiated by BPH do not proceed below 140 and 100 8C, respectively. But, both of the polymerizations are performed rapidly above these temperatures. BPH is, therefore, an excellent thermally latent initiator in the absence of co-

initiators. The polymerization of the blends is initiated at low temperature, which can be attributed to the polymerization of ECO at relative low temperature.[14] The polymerization range of the blends is larger than that of the neat epoxy resins, which is due to the feature of internal epoxy groups in the trifunctional ECO.[19] The cure activation energy (Ea) of the blends were determined by DSC scans at different heating rates, based on FlynnWallOzawas equation, as follows [Equation (1)]:[20]   AEa Ea ln q ln 1 ln ga 5:33 1:052 R RTP Ea is the cure activation energy, q the heating rate, A the Arrhenius frequency factor, Tp the peak maximum temperature, g(a) the function form of a, and R the gas constant. Table 1 shows the Ea determined by Equation (1) as a function of ECO content. The Ea shows a maximum value at 10 wt.-% ECO and decreases with increasing the above this content. From these results, it is expected that the addition of 10 wt.-% ECO to DGEBA can lead to an excellent network structure in the DGEBA/ECO blends.[21] The thermal degradation behavior of the DGEBA/ECO blends was studied with TGA at a heating rate of 10 8C min1 in a nitrogen atmosphere and the TGA thermograms are shown in Figure 4. As observed, the decomposition

Figure 2. blends.

Dynamic DSC thermograms of the DGEBA/ECO

Figure 3. Conversion of the DGEBA/ECO blends as a function of temperature.

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Figure 4.

TGA thermograms of the DGEBA/ECO blends.

curve behavior of the blends is largely similar to those of neat epoxy resins. Thermal stability factors, including initial decomposed temperature (IDT; 5% weight loss) and temperatures of maximum rate of degradation (Tmax) of the blends, can be determined from the TGA thermograms.[22,23] The results of the IDT and Tmax of the blends are listed in Table 2. It can be seen that the decomposition of the blends commences near at 358 8C and rapidly continues until 433 8C. From these results, it can be conrmed that the biobased blends containing 40 wt.-% ECO still show excellent thermal stabilities. And, the IDT and Tmax of the blends show maximum values at 10 wt.-% ECO, which can be attributed to the excellent network structure in the DGEBA/ECO blends.[21]

Figure 5. tan d (a) and storage modulus (b) of the DGEBA/ECO blends as a function of temperature.

Dynamic Mechanical Analysis

To evaluate the effect of the ECO content on glass transition temperature and crosslinking density of cured epoxy resins, the storage modulus and loss factor (tan d) measurement were conducted by DMA in a wide temperature range 0 to 250 8C at a heating rate of 5 8C min1. Figure 5 shows the temperature dependence of the tan d and storage modulus of cured DGEBA/ECO specimens. From the DMA spectra, the blends show a single relaxation and locate at a lower temperature than that of neat epoxy resins with increasing
Table 2. Thermal stabilities of the cured DGEBA/ECO blends. 100:0 378 431 90:10 384 438 80:20 371 437 70:30 360 435 60:40 358 433

the ECO content. It conrms that the ECO is partially miscible with the epoxy resins.[24] The glass transition temperature (Tg) value was recorded as the maximum value of the tan d curve. The crosslinking density (r) of cured specimens was calculated from the equilibrium storage modulus in the rubber region over the a-relaxation temperature according to the rubber elasticity theory [Equation (2)].[25]  0 r G fRT 2 Tg is the a-relaxation temperature, G0 the storage modulus at Tg 30 8C, f the front factor, R the gas constant, and T the absolute temperature at Tg 30 8C. The obtained Tg, G0 , and r are summarized in Table 3. The Tg and r of the DGEBA/ECO blends are systematically decreased with increasing the ECO content. This is caused by the addition of larger soft segments of ECO into the epoxy resins and decrease the rigidity of the epoxy network,
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DGEBA:ECO IDT 8C Tmax 8C

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S.-J. Park, F.-L. Jin, J.-R. Lee

Table 3. Dynamic mechanical analysis of the cured DGEBA/ ECO blends. DGEBA:ECO Tg 8C 100:0 90:0 80:20 70:30 60:40
a) b)

Storage modulus (GPa) Glassy regiona) 1.27 1.19 1.22 1.15 1.15

Rubbery 103 mol cm3 regionb) 0.102 0.077 0.065 0.051 0.041 4.61 3.68 3.18 2.54 2.13

197 169 158 150 131

Storage modulus at 30 8C. Storage modulus at Tg 30 8C.

leading to an increase the motion of segments of the macromolecules in the blends.[21] The loss factor intensities of the blends gradually increase with increasing the ECO content. And, Tg and G0 of the blends are 131 8C and 1.15 GPa at 40 wt.-% ECO, respectively. Therefore, the biobased epoxy blends are still maintaining relative higher Tg and G0 .

Figure 6. KIC values of the DGEBA/ECO blends as a function of ECO content.

Eb

L3 DP 4bd3 Dm

Mechanical and Mechanical Interfacial Properties

The mechanical and mechanical interfacial properties for the DGEBA/ECO blends were determined, in terms of the fracture toughness, exural strength (sf), and elastic modulus in exure (Eb). Fracture toughness of cured specimens was measured by three-point bending tests for the critical stress intensity factor (KIC), as follows [Equation (3)]:[26] KIC PL Y b d 3=2 3

P is the rupture force, L the span length between the supports, a the depth of notch, b the specimen width, d the specimen thickness, and Y the geometrical factor. Figure 6 shows the obtained KIC values of the DGEBA/ ECO blends for different content of ECO up to 40 wt.-%. As observed, the neat epoxy resins have high crosslinking density and brittleness, with a KIC value of 1.7 MPa m1/2. The toughness is signicantly increased with increasing the ECO content and shows a maximum value of 3.5 MPa m1/2 at 30 wt.-% ECO content. The addition of larger soft segments of ECO into the epoxy resins leads to an increase of the exible properties of the network structure, which is probably due to the reduced crosslinking density in the blends.[21,27] The exural strength (sf) and elastic modulus (Eb) in exure values of the blends were obtained with the threepoint bending tests and were calculated as follows [Equation (4) and (5)].[26] sf 3PL 2bd2 4

P is the applied load, L the span length, b the specimen width, d the specimen thickness, DP the change in force in the linear portion of the load-deection curve, and Dm the change in deection corresponding to DP. Figure 7 shows the result of exural strength (sf) values of the blends as a function of ECO content. The sf values of the blends indicate that exural strength increases from 87.6 to 117.1 MPa with increasing ECO content of 30 wt.%. This result means that the addition of larger soft segments of ECO into the epoxy resins increases the ductility, resulting in increasing the exural strengths of the blends.[21,27] The elastic modulus (Eb) in exure values of the blends are shown in Figure 8. The Eb values are constant,

Figure 7. sf values of the DGEBA/ECO blends as a function of ECO content.

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Figure 8. Eb values of the DGEBA/ECO blends as a function of ECO content.

although the ECO content is increased. From the results of the mechanical and mechanical interfacial properties, it is conrmed that the addition of ECO into the epoxy resins leads to the increase in fracture toughness and exural strength without decreasing the elastic modulus in the blends. SEM was used to examine the morphology on fractured surfaces of the specimens after KIC tests. In Figure 9(a), the SEM micrograph of the neat epoxy resins shows regulative cracks in the fracture surface, indicating a brittle fracture surface. On the other hand, the micrographs of the blends show tortuous cracks and exhibit many ridges with increasing the ECO content, indicating a reinforced morphology, as shown in Figure 9(b)(e). This is why the DGEBA/ECO blends exhibit higher mechanical and mechanical interfacial properties than those of the neat epoxy resins.

Figure 9. SEM micrographs of the DGEBA/ECO blends after KIC tests: (a) 100:0; (b) 90:10; (c) 80:20; (d) 70:30; (e) 60:40 (magnication of 500).
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Conclusion
In this work, the epoxy blends were newly prepared from commercial DGEBA and biobased ECO initiated by BPH as a latent thermal catalyst, and the effects of ECO content on the cure behavior, thermal stabilities, and mechanical properties of the DGEBA/ECO blends were discussed. The cure activation energy and initial decomposed temperature of the blends showed a maximum value at 10 wt.-% ECO content, which was attributed to the excellent network structures in the DGEBA/ECO blends. The glass transition temperature and storage modulus of the blends were decreased with increasing the ECO content. And, the mechanical and mechanical interfacial properties of the blends were signicantly increased with increasing the ECO content. This could be attributed to the addition of larger soft segments of ECO into the epoxy resins and thus increased the exible properties of the epoxy network, resulting in an improvement in the toughness of the blends.

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