Fully Biobased Composites of an Itaconic Acid Derived Unsaturated

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Fully Bio-based Composites of an Itaconic Acid Derived Unsaturated Polyester Reinforced with Cotton Fabrics Zenghui Dai, Zewen Yang, Zhiwei Chen, Zhongxiang Zhao, Yongjian Lou, Yanyan Zhang, Tianxing Liu, Feiya Fu, Yaqin Fu, and XiangDong Liu ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.8b03539 • Publication Date (Web): 26 Sep 2018 Downloaded from http://pubs.acs.org on September 30, 2018

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ACS Sustainable Chemistry & Engineering


Fully Bio-based Composites of an Itaconic Acid Derived Unsaturated Polyester Reinforced with Cotton Fabrics

ZengHui Dai1, ZeWen Yang1, ZhiWei Chen1, ZhongXiang Zhao1, YongJian Lou1, YanYan Zhang1, TianXing Liu2, FeiYa Fu1, YaQin Fu1, XiangDong Liu1*

1

College of Materials and Textile, Zhejiang Sci-Tech University, No. 928 Second

Street, Xiasha Higher Education Zone, Hangzhou 310018, People’s Republic of China. 2

Hangzhou Foreign Languages School, No. 299 Liuhe Road, Hangzhou 310023,

People’s Republic of China. Correspondence to: Xiang Dong, Liu, (E-mail: [email protected]).

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ACS Paragon Plus Environment ACS Paragon Plus Environment

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ACS Sustainable Chemistry & Engineering Abstract: In this study, a fully bio-based composite reinforced by cotton fabrics was successfully fabricated by copolymerizing a bio-derived unsaturated polyester (PEOI) with a green diluent, dimethyl itaconate (DI). The PEOI prepolymer was synthesized from itaconic acid (IA), oxalic acid (OA) and ethylene glycol (EG) via a simple polycondensation process and was characterized by Fourier transform infrared spectroscopy

(FTIR),

nuclear

magnetic

resonance

(NMR),

and

viscosity

measurements. Subsequently, the prepolymer was dissolved in DI to prepare a polymerizable unsaturated polyester resin (UPE) with low viscosity, excellent reactivity for free radical polymerization, and good compatibility with cotton fibers. After being reinforced by cotton fabrics, the resulting composites showed satisfactory material performance, including a strong tensile strength at break approximately 34 MPa, a glass transition temperature (Tg) of approximately 108 °C, and thermal decomposition temperatures (Td5%) ranging from 224 to 276 °C. These green composites derived from renewable resources are hopeful candidates for replacing petroleum-based UPE resins, and the family of IA derivatives may play promising roles in fabricating fully bio-based composites.

KEYWORDS: Dimethyl itaconate, Green composites, Itaconic acid, Unsaturated polyester resins, Cotton fabric

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INTRODUCTION Scientists are becoming more aware of the importance of a sustainable and highly eco-friendly environment. Much effort has been directed toward the fabrication of bio-based renewable polymers from naturally derived chemicals.[1-5] Successful bio-based thermoplastics include polylactic acid (PLA), polyhydroxyalkanoates (PHA), furan resins, and polybutylene succinate (PBS), which have been commercialized over many years.[6-10] The synthesis of bio-based thermosetting resins has also attracted increasing attention. Several kinds of bio-based thermosets, e.g., epoxy, polybenzoxazine, unsaturated polyester resins (UPEs), and phenolic resins (PF), have been increasingly reported during the last decade.[11-20] Because of the advantages of low cost, simplicity of the curing process, and good combination of weatherability and mechanical properties, UPE-based composite products have been widely applied in the construction, transportation, and marine industries.[21-24] Currently, commercially available UPEs are mainly synthesized from petrochemical products.[25] For a long time, researchers have found it difficult to obtain suitable bio-based monomers and diluents with an active unsaturated double-bond structure for crosslinking via radical polymerization.[26, 27] However, this difficulty may have been addressed because biotechnology has enabled the development of several fermented products suitable for preparing UPEs.[28-32] The most widely used and outstanding UPE is itaconic acid (IA),[3,

28, 33-36]

which is

composed of two carboxylic acid functionalities and an α, β-unsaturated double bond.[37-39] The structural features of IA simply allow it and its derivatives such as 3



ACS Sustainable Chemistry & Engineering dimethylitaconate (DI) for the applications of bio-based UPEs. In fact, a few articles published over the past few months have reported the feasibility of producing bio-based UPEs using existing UPE manufacturing processes.[40, 41] Combining materials into composites is an effective way to improve strength and other properties of the material. Recently, fully green composite materials composed of natural fibers and bio-based polymers have gained increasing interest in both academia and industry.[42-46] Although some special performances of green composites are inferior to those of the high-tech composites that are reinforced by artificial fibers such as aramid and carbon, green composites have advantages such as low cost, eco-friendliness, and biodegradability and can be potentially used for packing, automobile, and construction. The intent of this work is to explore fully bio-based composites with satisfactory mechanical performance and acceptable cost. We have already observed the chemical properties and availabilities of IA and its derivatives and are thus interested to develop a new composite system based on IA. Here, we report a successful combination: the reinforcement of cotton fabric, the active diluent of DI, and the bio-UPE, which is synthesized from IA, oxalic acid (OA), and ethylene glycol (EG). It has been reported that EG can be obtained from cellulose in a catalyzed conversion.[47,

48]

The simplest dicarboxylic acid, OA, can also be

synthesized from starch, cellulose, or glucose.[49-53] The UPE we designed is miscible with 30 wt % DI, therefore, a series of UPE mixtures with low viscosity and longterm storage stability are prepared using a simple process. After being reinforced by cotton fabrics, the resulting composites show excellent tensile strength, dynamic mechanical 4


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ACS Sustainable Chemistry & Engineering performances, and thermal stabilities.

EXPERIMENTAL SECTION Materials. Itaconic acid (IA), oxalic acid (OA), p-toluenesulfonic acid (PTS), tert-butyl peroxybenzoate (TBPT), hydroquinone (HQ), and styrene were purchased from Shanghai Aladdin Reagent Co., Ltd (Shanghai, China). Ethylene glycol (EG) and N,N-dimethylformamide (DMF) were purchased from Hangzhou Gaojing Fine Chemical Co., Ltd (Hangzhou, China). Dimethyl itaconate (DI) was obtained from TCI chemical industrial reagent (Shanghai, China). All chemicals were of analytical grade and were used directly without further purification. Cotton fabrics (CO, thickness 0.23 mm, square meter quality 104 g/m2) were obtained from Shaoxing Qidong Textile Co., Ltd (Zhejiang, China),. Characterization. 1H-NMR spectra were recorded on a Bruker Ascend 400 spectrometer (Bruker Corp., Switzerland). FTIR spectra were obtained on a Nicolet 5700 FTIR plus spectrometer (Nicolet Corp., USA) from 400 to 4000 cm−1 with 4 cm-1 resolution. Viscosity was measured by Physical MCR 301 rotational rheometer (Anton Paar Trading Co., Ltd., China). DSC tests were performed on a DSC-Q2000 (TA Instruments Corp., USA) at a heating rate of 10 ºC/min in a nitrogen flow (35 mL/min). Stress-stain data were obtained from a universal material testing machine (HESON HS300C, Shanghai Hesheng Instrument Technology Co., Ltd., China). The sample dimension was 50 x 10 x 1 mm and the stretching rete was 40 mm/min. Dynamic mechanical analyses (DMA) were performed on a DMA-1 analyser 5



ACS Sustainable Chemistry & Engineering (Mettler-Toledo Corp., Switzer-land) using a controlled single cantilever bending mode (1 Hz, 15 mm amplitude) at a heating rate of 3 ºC/min from 25 ºC to 180 ºC. The samples were of 10.0 mm width and approximate 1.0 mm thickness. TGA (Mettler-Toledo corp., Switzer-land) technology was used to analyze thermal decomposition products of the cured resins. The TGA test has a heating rate of 10 ºC/min from 30 to 800 ºC, and the helium flow for TGA tests is 40 mL/min. To analyze the degree of the cross-linking reaction of the DI-UPEs, Soxhlet extraction method was used. The cured sample was precisely weighed, extracted with DMF reflux for 48 h in a Soxhlet extractor, dried at 60 ºC for 24 h and weighted. To evaluate water absorptivity of the resins, a cured resin (m3) was immersed in deionized water (10.0 mL), and weighed again (m4) after 24 hours at room temperature, the ratio of the sample weight gain value (m4-m3) to the sample weight (m3) is the water absorptivity. The interfacial bonding effect between fibers and resin in the composites was analyzed by scanning electron microscopy (SEM) (SU8010, Hitachi Corp., Japan). The sample was broken in liquid nitrogen and the fracture surface morphology was studied after gold coating (40 s, 10 mA). Fatigue properties were examined by a fatigue test machine (DSW-3200, Sichuan Dexiang Kechuang Instrument Co., Ltd., China). Gel permeation chromatograms (GPC) (GPC500, Agilent Technologies Inc., USA) technology was used to measure the molecular weight of the prepolymer. Synthesis of the unsaturated polyester prepolymer (PEOI). To a mixture of EG (15.8 g, 255 mmol), IA, and OA (molar ratios were listed in Table 1), PTS catalyst 6


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ACS Sustainable Chemistry & Engineering (0.48 g, 2.50 mmol) and HQ inhibitor (0.55 g, 5.00 mmol) were further mixed. With nitrogen gas protection, the mixture was heated to 160 ºC at an atmosphere for 2 h and at a reduced pressure of 0.08 MPa for next 5 h to obtain the pale yellow mixture, the resulting pale yellow mixture was washed with a large amount of distilled water (90 °C) to remove residual monomers and a polymerization inhibitor from the mixture. The obtained viscous liquid was dried in a vacuum oven at 80 °C until its weight became constant. The prepolymers were named as PEOI30, PEOI50, PEOI70, PEOI90 and PEI, according to the mass fraction of IA in the acids. Preparation of the bio-based composites. To a UPE mixture containing of a PEOI (3.50 g) and DI (1.3 mL, 9.48 mmol), TBPB initiator (0.05 g, 0.27 mmol) was further mixed. To evaluate cross-lining behavior of the liquid mixtures, gel content test was carried out using Soxhlet extraction method. After heated the mixtures at 110 ºC for 3 h, the resulting solid resin (5 g) was extracted using DMF for 48 h, and the residual resin was weighted. To prepare composite, the resulting mixture was applied onto cotton fabrics (80 mm x 60 mm) using an immersion method to control the weight ratio of resin/fabric to 6:4. Four pieces of the wet fabrics were heated at 110 ºC under a pressure of 15 MPa for 3 h to obtain the UPCom plate having a thickness of 0.65 mm. It was further cut to a rectangular shape (length: 10 mm; width: 60 mm) for next tests.

RESULTS and DISCUSSION Synthesis and characterization of UPEs. As shown in Scheme 1, the PEOI 7



ACS Sustainable Chemistry & Engineering prepolymers were synthesized via the condensation reactions of EG with IA and OA in the presence of the PTS catalyst. The average molecular weights of the PEOI prepolymers were measured by the gel permeation chromatograms (GPC) method, and the results are shown in Table 1. As expected, the polymer molecular weight distribution index of the prepolymers centers at 2.0, and the Mw values range from 800 to 1450. Figure 1 shows the FTIR spectra of PEOI30, PEOI50, PEOI70, PEOI90 and PEI. The broad absorption peak at 3521 cm-1 can be attributed to the stretching vibration of -OH, and the peak at 2939 cm-1 is assignable to the -CH2- units in the polymer chain. Meanwhile, the peaks at 1728 cm-1 is attributable to the stretching vibration of the ester group C=O, and the peak at 1638 cm-1 is attributed to stretching vibration of C=C structures. It was also found that the absorption of these double bond peaks increases with the increase in IA molar content. 1

H-NMR spectra are given to further confirm the chemical structures. As shown

in Figure 2, almost all of the peaks match well with those of the protons of the PEOIs. However, the peaks that appeared at approximately 2.3 ppm could not be assigned to the IA structure in the prepolymer chain. Thus, we further analyzed the 13C NMR spectra of PEOI70 and PEI100. As shown in Figure S1, the peaks at 118 ppm and 14 ppm suggest that some IA structures had isomerized to mesaconate at high temperature. By comparing the peaks of H1, H2, and H9 in Figure 2, it can be confirmed that the great majority of IA moieties remained in the polymer chains.

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In the present work, DI was used as an active diluent to replace St, the most commonly used petrochemical diluent. The UPEs were prepared by mixing DI with the PEOI prepolymers (Table 1), which were synthesized from IA, OA and EG via a melt polycondensation method. The viscoelastic behaviors of the UPEs and the mixture of EG, OA, and IA are shown in Figure 3(1). The viscosity values of the UPEs decrease slowly with increasing shear rate, which is a typical characteristic of a polymer solution. In the case of the mixture, because the small-molecular-weight compounds have no macromolecular chain entanglement,[54] their viscosities are significantly lower than those of the UPEs, and no shear-thinning behavior was observed.

The viscosity of UPEs is an important factor in the preparation of fiber-reinforced composites. In particular, for liquid molding techniques, the viscosity at room temperature should be below 1000 mPa·s to ensure good processability.[55, 56] Figure 3(2) shows the relationships between the viscosity of the UPEs and temperature. The UPE resins are yellow and transparent, and no precipitation is observed after being stored at room temperature for 6 months. The viscosity values of the UPEs decrease exponentially with increasing temperature and become steady at above 110 ºC. The UPEs have a very small viscosity value at approximately 15 mPa·s. Such low 9



ACS Sustainable Chemistry & Engineering viscosity is beneficial for the infiltration of the UPE and DI molecules and is thus suitable for the molding process to produce reinforced composites. Generally, commercially available UPE products containing 40 wt% St have a low viscosity of approximately 375 mPa·s at room temperature.[57] As shown in Table 2, the viscosities of the UPEs prepared in the present work range from 341 to 654 mPa·s, indicating that the process performance of the UPEs is comparable to that of commercially available UPE products that use St as the active diluent.[58] However, when DI is replaced by St and AESO, the bio-based UPEs show higher viscosity values of 897 mPa·s and 17.5 Pa·s, respectively. These results suggest that DI is a more suitable active diluent for bio-based PEOI prepolymers than St or AESO. To evaluate the polymerization activity of the bio-based UPEs more accurately, a nonisothermal curing process of the DI/PEOI70 system was carried out on a DSC device, and the temperature of the exothermic peak was compared with those for other UPE mixtures (Table 2). These temperatures were found to be 103 ºC, 98 ºC, and 136 ºC, for the radical copolymerization of DI/PEOI70, St/PEOI70 and AESO/PEOI70, respectively. The exothermic peaks are usually used as an index for evaluating the activity of UPEs during crosslinking polymerization. In general, a lower peak temperature means a higher reactivity of the C=C double bond in the UPE systems.[59] The curing temperatures of the bio-based and St-based UPEs are similar to each other but are lower than those of AESO-based UPEs, further illustrating the potential of bio-based UPEs. Table 2 also summarizes the gel content data for evaluating the degree of crosslinking. The gel contents ranged from 93.3% to 98.3%, suggesting that the 10


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ACS Sustainable Chemistry & Engineering bio-based UPEs are almost fully crosslinked. On the other hand, the low swelling capacity (＜2.6 wt %) of the cured UPEs (measured by immersing 5 g of the test sample in a 50 mL graduated cylinder containing 20 mL of distilled water, followed by remeasuring the liquid volume after 24 h and weighing the test sample) implies that the UPEs have a very high crosslinking density. The tensile properties analysis of fiber composite.

Figure 4 shows the tensile strength and the elongation of cotton fabric-reinforced composites. The breaking tensile strength of UPCom70 is 34.1 MPa, which is higher than that of UPCom100 (32.8 MPa) or of the cotton fabric itself (about 16.8 MPa). The tensile strength at break of the composites increases with increasing proportion of IA to OA from 30:70 to 70:30 but decreases with further increase in IA content. Although increasing IA units in the prepolymer chains generally leads to a higher crosslinked network, the increased viscosity of the UPE resins may result in poorer wettability on the fiber surface, thus affecting the binding at the interface between the fabric and the cured resin. Other reasons might include the isomerization to mesaconate

structure

as

described

above,

and

some

reactions

occurred

intramolecularly. If the itaconic acid units exceed a concentration level, the itaconic acid units may react with adjacent ones to form noneffective crosslinking structures. A similar behavior also happened to the St-UPE70 resin, which is composed of 30% St 11



ACS Sustainable Chemistry & Engineering and 70% PEOI70. When the St-UPE70 resin is used to prepare the UPComs composite, the tensile strength is 36.3 MPa, and the elongation at break is 13.4%. These values are comparable to those of UPCom70, the composite made from DI-diluted UPE resin, indicating that DI is as good an active diluent as St. Dynamic mechanical properties of the composites. The glass transition temperatures (Tg) of the UPComs can be obtained from the DMA curves (Figure 3(3)). In general, the Tg of a thermosetting resin primarily depends on the chemical structure of the monomer and the crosslinking density of the network.[60, 61] In the case of the UPComs, the crosslinking density is mainly controlled by the molar ratio of the two binary acids, OA and IA, in the polymerization step of producing the PEOI prepolymers. As shown in Table 3, the Tg values range from 64.5 to 108.2 ºC and have the highest values at the optimum condition for preparing UPCom70. Because the strong intermolecular polarity of the polyesters limits the movement of the polymer chains, commercially available UPE resins generally have high Tg values.[62] However, bio-based UPE resins have rarely been reported to have Tg values of up to 100 ºC because their molecular structures lack a benzene ring structure. For example, Dai et al. reported that UPE resins synthesized from AESO and IA have Tg values ranging from 32 to 78 ºC.[37] Sadler et al. developed an isosorbide-based UPE with a Tg lower than 76 ºC.[63] Rorrer et al. synthesized a maleic UPE with 40 wt% St as the active diluent and observed that its composite of glass fibers have a Tg of approximately 90 ºC.[64] In contrast, the bio-based UPE prepared in the present work has a high Tg of over 100 ºC (approximately 110 ºC) even in the absence of St, suggesting that the 12


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ACS Sustainable Chemistry & Engineering UPE systems can produce a highly crosslinked network structure. We next calculate the crosslinking density of the UPCom composites using the elastic theory of rubber.[37]: ve = E'⁄(3RT)

(1)

where T is the absolute temperature at Tg, E' is the storage modulus at Tg, R is the gas constant, and ve is the crosslinking density. As shown in Table 3, the results of ve are in good agreement with the gel content data, suggesting that crosslinking density is related to the viscosity of the UPEs. Thermal stability analysis of curing resin.

Figure 5 shows the thermal degradation curves of the UPCom composites under a nitrogen atmosphere. As shown by the important thermal degradation parameters Td5% and R600 in Table 3, all the composites have good heat resistance (Td5% > 230.8 ºC). The lowest Td5% and R600 values are obtained for UPCom30, which can be attributed to the lowest double-bond density among the UPEs. The highest carbon residue rate of R600 is obtained for the UPCom100 composite because it has the lowest elemental oxygen content. Such thermal stability results are more acceptable than those of the AESO/St-based resins previously reported.[37] The bonding effect of the polymeric matrix on the cotton fibers.

13




For fiber-reinforced composites, the bonding effect at the interface between the fibers and the polymeric matrix is an important factor of their mechanical properties. To further analyze the interfacial bonding effect at the interface between cotton fiber and UPE resin, the fracture morphology of the five composites after tensile testing were subjected to SEM observation. As shown in Figure 6a, the tensile fracture morphology of the UPCom30 composite has a weak effect on interface bonding as deep gaps exist on the fracture surface, which are believed to have resulted from fibers being pulled out of the polymeric matrix. The result is assignable to the low crosslinking density of the UPE30 network and is in good agreement with the poor tensile properties of the UPCom30 composite. Other UPCom composites, including UPCom50 and UPCom100 (Fig. 6b-e), exhibit good binding fracture without voids in the fiber root, suggesting that the UPE resins are compatible with cotton fibers.

Fatigue resistance is an important index to estimate the lifetime of composite materials. As shown in Figure 7, the UPComs exhibit excellent mechanical properties even after ten thousand times of the bending process. All UPComs maintained above 85 % tensile strength by comparing with their starting samples. To further evaluate the bonding effect at the interface between the fibers and the 14


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ACS Sustainable Chemistry & Engineering polymeric matrix, the interlaminar shear strength (ILSS) test was carried out on the bio-based composites. The bonding model (detailed in Supporting Information page S4) was used and the results are shown in Figure S3. The ILSS of the composites range from 3.83 to 5.25 MPa, but the pure resin samples from 1.5 MPa to 2.3 MPa. In addition, thermo-oxidative aging test was carried out on the composites to mimic their lifetime being exposed to air. After exposed the samples at 90 °C for 14 days, all composites still have strong material properties (Figure S4), which all maintained at least above 90 % to the starting samples. These results suggest that the unsaturated polyester and cotton fabric are well bonded.

CONCLUSION The fully bio-based UPEs containing IA units and their composites reinforced with cotton fabrics were successfully prepared. It was found that DI is very suitable as an active diluent for the IA-derived unsaturated polyesters because it endows them with a very low viscosity and good compatibility with cotton fibers. After being reinforced with cotton fabrics, the resulting fully biobased UPE composites achieve satisfactory mechanical and thermodynamic properties due to the strong binding effect at the interface between the fiber surface and UPEs and the high crosslinking density as a result of the free radical polymerization. Compared with other previously reported biobased UPEs and commercial St-based UPEs, the composites in this work can potentially replace petroleum-based UPEs in various application areas, such as construction, transportation, and marine industries. 15




ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website. Mw values of the unsaturated polyester prepolymers, viscosities of the UPEs, and mechanical, thermal, and thermodynamic properties of the UPCom composites.

AUTHOR INFORMATION Corresponding Author Liu Xiangdong, Tel: +86-571-86843785, E-mail: [email protected]. Notes The authors declare no competing ﬁnancial interest.

ACKNOWLEDGEMENTS This work was financially supported by the Natural Science Foundation of China (51573167) and Public Welfare Technology Application Research Project of Zhejiang Province (2017C31035 and 2017C33154).

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Scheme 1.

Synthesis of PEOI and their crosslinking products.

28


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ACS Sustainable Chemistry & Engineering Table 1. The Weight-average molecular weight of PEOI

a

PEOI

EG/OA/IA (mol)

Mwa (g/mol)

PDIb

PEOI30

1.04/0.7/0.3

824

1.91

PEOI50

1.04/0.5/0.5

1089

2.14

PEOI70

1.04/0.3/0.7

1448

2.21

PEOI90

1.04/0.1/0.9

1420

2.06

PEI

1.04/0/1.0

1443

2.14

Weight-average molecular weight of PEOI is measured by gel permeation chromatography (Figure S2). bPDI

is the molecular weight distribution of the PEOI.

29



Page 30 of 39

ACS Sustainable Chemistry & Engineering Table 2. Viscosity, curing temperature, gel content, and water absorption of the UPEs and their cured samples, respectively.

Gel content

Viscosity 25 ºC

Tmaxa

Qb

(wt %)

(mPa·s)

(ºC)

(wt %)

UPE30

93.3

341

-

1.8

UPE50

98.3

401

-

2.6

UPE70

97.9

427

103

1.1

UPE90

94.1

572

-

2.1

UPE100

95.9

654

-

1.6

St-PEOI70

95.2

897

97.7

1.9

AESO-PEOI70

97.3

17500

136

2.3

UPEs

a

Tmax is the peak temperature of the curing process; bQ is the water absorption of the cured resin.

30


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ACS Sustainable Chemistry & Engineering Table 3. Mechanical and thermal properties of the UPCom composites E′b Composites

Tga

(ºC)

vec/103 (mol -3

(MPa)

m )

Td5%d (oC) R600e (%) Ts f (MPa)

UPCom30

64.5

2062

1.28

230.8

8.56

22.3

UPCom50

106.0

3032

1.15

224.8

13.17

29.6

UPCom70

108.2

3319

1.23

276.5

12.45

34.1

UPCom90

101.7

2844

1.12

270.8

11.47

32.8

UPCom100

95.4

2663

1.12

263.0

16.72

31.4

AESO-PEOI70

78

2053

1.05

248.3

17.92

39.1

St-PEOI70

90

2508

1.18

266.4

13.5

36.3

a

TBPB (2 wt % of total weight) used as initiator, Ts f is the tensile properties of the composite

31




Figure 1.

The FTIR spectra of PEOI30, PEOI50, PEOI70, PEOI90, and PEI.

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Figure 2.

The 1HNMR spectra of PEOI30, PEOI50, PEOI70, PEOI90, and PEI.

33




Figure 3

(1) The viscosity behavior of the UPEs and the mixture of EG, OA, and

IA (105:30:70); (2) The relationship of the viscosity of the UPEs vis temperature; Storage modulus E′ (3) and loss factor Tan (δ) (4) of the UPCom30, UPCom50, UPCom70, UPCom90, and UPCom100.

34


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Figure 4. Tensile strength and elongation at break of the composites.

35




Figure 5.

TGA curves of the UPCom30, UPCom50, UPCom70, UPCom90, and

UPCom100.

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Figure 6.

The fracture surface of composites (a) UPCom30, (b) UPCom50, (c)

UPCom70, (d) UPCom90, and (e) UPCom100; (f) Photo of the composite.

37




Figure 7.

Antifatigue properties of the composites.

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ACS Sustainable Chemistry & Engineering TOC Graphic Page For Table of Contents Use Only

Green composite was fabricated using unsaturated polyester synthesized from itaconic acid, reactive diluent of dimethyl itaconate, and cotton fabric.

39


Fully Biobased Composites of an Itaconic Acid Derived Unsaturated

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