A Low-Dielectric Polymer Derived from a Biorenewable Phenol

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A Low Dielectric Polymer Derived from a Bio-renewable Phenol (Eugenol) XingRong Chen, Linxuan Fang, Xiaoyao Chen, Junfeng Zhou, Jiajia Wang, Jing Sun, and Qiang Fang ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.8b03594 • Publication Date (Web): 27 Aug 2018 Downloaded from http://pubs.acs.org on August 27, 2018

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ACS Sustainable Chemistry & Engineering

A Low Dielectric Polymer Derived from a Biorenewable Phenol (Eugenol) Xingrong Chen, Linxuan Fang, Xiaoyao Chen, Junfeng Zhou, Jiajia Wang, Jing Sun* and Qiang Fang*

Key Laboratory of Synthetic and Self-Assembly Chemistry for Organic Functional Molecules, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, PR China.

* E-mail: [email protected], [email protected]

KEYWORDS: Biomass; Eugenol; Organosiloxane; Benzocyclobutene; High-Performance Polymer.

ABSTRACT: A novel dielectric polysiloxane with low dielectric constants (< 2.77) at frequencies ranging from 0.1 to 30.0 MHz was synthesized. The monomer was prepared from renewable eugenol using an extremely low amount of B(C6F5)3 catalyst. After thermal curing, the polysiloxane displayed high thermostability with an onset degradation and glass transition temperature of 400 and 201 °C, respectively. The coefficient of thermal expansion (CTE) was 64 ppm/°C, and it displayed a low water uptake (< 0.15 %) when immersed in deionized water at room temperature for 144 h. These properties are comparable to other highperformance synthetic polymers, thus eugenol could be considered as a sustainable feedstock to prepare the high performance polymers.

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INTRODUCTION

With the rapid consumption of fossil oil, considerable research efforts have been devoted to the conversion of bio-based compounds to high-performance materials, because the renewability and remarkable abundance of these compounds could significantly reduce the demand for fossil oil resources.[1] In particular, these bio-based molecules[2] with special chemical structure which is difficult to synthesize through a simple procedure have been paid much attention.[3] Furthermore, of various bio-based compounds, those containing aryl skeletons also have aroused the interest of both academia and industry. Because they can be converted to high-performance polymers, which could possess high thermostability and low water uptake, as well as good dielectric properties.[4-8] Among the aryl bio-based molecules, a phenol, which named as eugenol has attracted much research interest recently.[9] This phenol can be extracted abundantly from clove, and the bifunctional nature of eugenol implies that it could be used as a feedstock for the synthesis of polymers.[10-11] However, there were a few high performance polymers derived from eugenol reported. Some research has paid much attention to transform the eugenol to cyanate esters,[12-15] which are difficult to be synthesized and have low storage stability. Hence, developing a facile method to effectively prepare high performance materials from eugenol is still necessary. More recently, we have reported a new high-performance polysiloxane[16], which can be easily synthesized from a commercial tetraethoxysilane (TEOS) through the PiersRubinsztajn reaction.[17-18] Such an interesting reaction inspires us to utilize it for the conversion of eugenol. Moreover, considering the high reactivity and great properties of the


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benzocyclobutene (BCB) resins[19], we choosed a BCB-based organosilane[20] as a reactant. Catalyzed by an extremely low amount of B(C6F5)3 (0.5 mol %), eugenol was successfully converted to a functional organosiloxane, which can be easily transformed to a cross-linked polymer after treating at high temperature. This material showed good thermostability and low dielectric constant, as well as low water uptake. To the best of our knowledge, this is the first example for the conversion of eugenol to a high-performance polymer under such a mild reaction condition. Because of the good properties of the eugenol-based organosiloxane, this contribution would offer a new method to prepare bio-based high-performance polymer with the potential application in the microelectronic industry. Here, we report the details.

EXPERIMENTAL SECTION

Materials. 4-Bromobenzocyclobutene was purchased from Chemtarget Technologies Co., China. Eugenol was purchased from Sigma Aldrich. Tris(pentafluorophenyl)borane [B(C6F5)3] was purchased from Alfa and used as received. Chlorodimethylsilane was purchased from Beijing HWRK Chem Co., China. Tetrahydrofuran (THF) was purchased from Sinopharm Chemical Reagent Co., China, and purified by distillation under reduced pressure over CaH2 before use. Other solvents and reagents were used as received. Instruments. 1H NMR and 13C NMR and 29Si NMR spectra were recorded on a JEOL ecz400 or Agilent 500/54/ASP instrument using TMS as an internal standard and CDCl3 as a solvent. Elemental analysis (EA) was carried out on Elementar vario EL III. Mass spectrometry (MS) was performed on an Agilent Technologies 5973N at room temperature. FT-IR spectra were detected on a Thermo Scientific Nicolet spectrometer with KBr pellets. Differential Scanning


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Calorimetry (DSC) was performed using a TA Instrument of DSC Q200 at a heating rate of 10 °C min−1 under nitrogen flow with a flowing rate of 50 mL min−1. Thermo-gravimetric analysis (TGA) was performed on a NETZSCH TG 209 apparatus under a nitrogen atmosphere and air, respectively, at a heating rate of 10 °C min−1 and a protective flowing rate of 10 mL min−1, a purge flowing rate of 50 mL min−1. Dynamic mechanical analysis (DMA) was performed in air on the DMA Q800 V7.5 Build 127 instrument with a heating rate of 3 °C min-1 in air for three times with the rectangular samples in a size of 5 cm × 1 cm ×0.2 cm. Thermomechanical analysis (TMA) was performed in N2 on the TMA Q400 V7.1 Build 89 instrument with a heating rate of 3 °C min-1 in N2 with a flowing rate of 50 mL min−1 for three times. The surface roughness of polymer films was measured by atom force microscopy (AFM) using the AC (tapping) mode on an environment control scanning probe microscope (Nanonavi Esweep) in a 5 µm × 5 µm area at room temperature. Static contact angle was investigated by JC2000C of Shanghai Zhongchen Equipment Ltd., China, at room temperature. The nano-scratch tests were performed by a UNHT/NST (CSM Company) system on a silicon wafer at room temperature. Dielectric constant and dissipation factor of polymer cylinders with a radius of 1 cm and thickness of 2 mm were measured by the standard capacitance method with Agilent 4294A precision impedance analyzer in a range of frequencies from 0.1 to 30 MHz for three times.

Synthesis of the BCB-SiH. To a stirring mixture of magnesium turnings (7.2 g, 0.261 mol), chlorodimethylsilane (37.84 g, 0.4 mol) and THF (200 mL) at room temperature was added dropwise 4-bromobenzocyclobutene (36.6 g, 0.2 mol) in N2. After addition of 4bromobenzocyclobutene, the mixture was allowed to stir overnight at room temperature and


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then quenched with water (100 mL). The organic phase was extracted with ethyl acetate (200 mL) and concentrated under reduced pressure. The residue was purified by distillation (61 °C, 4 mmHg) in vacuum. Pure BCB-SiH was obtained as a colorless liquid in a yield of 90%. 1H NMR and

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C NMR spectra of BCB-SiH can be seen in Figure S1 and Figure S2 of

Supporting Information, respectively. 1H NMR (400 MHz, CDCl3, ppm) δ 7.50 (d, J = 7.2 Hz, 1H), 7.34 (s, 1H), 7.16 (d, J = 4.9 Hz, 1H), 4.62 ~ 4.46 (m, 1H), 3.29 (s, 4H), 0.48 ~ 0.38 (m, 6H).

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C NMR (101 MHz, CDCl3, ppm) δ 147.29, 145.66, 135.43, 132.28, 127.70, 122.01,

29.83, -3.54.

Synthesis of the BCB-Si-E. To a stirring mixture of eugenol (4.10 g, 25 mmol), B(C6F5)3 (64 mg, 0.5 mol %) and cyclohexane (10 mL) was added BCB-SiH (8.10 g, 50 mmol) via a syringe at room temperature. After addition of BCB-SiH, the mixture was allowed to stir for additional 30 min. The formed product was purified on SiO2 gel through a short column chromatography using hexane as the eluent. Pure BCB-Si-E was obtained as a colorless liquid with a yield of 86%. 1H NMR (400 MHz, CDCl3 ppm) δ 7.48 (dd, J = 7.3, 3.1 Hz, 2H), 7.33 (s, 2H), 7.06 (d, J = 7.7 Hz, 2H), 6.66 (d, J = 8.1 Hz, 1H), 6.58 (s, 1H), 6.54 (d, J = 8.1 Hz, 1H), 5.84 (ddt, t, J = 14.3, 10.5, 6.7 Hz, 1H), 4.96 (m, 2H), 3.18 (s, 10H), 0.45 (d, J = 5.2 Hz, 12H). 13C NMR (101 MHz, CDCl3, ppm) δ 147.90, 146.10, 145.58, 145.54, 144.57, 137.67, 135.78, 135.69, 133.29, 131.89, 127.31, 121.97, 121.94, 121.55, 121.30, 120.46, 115.33, 77.37, 77.05, 76.73, 39.41, 29.96, 29.90, -0.79, -0.82.

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Si NMR (79 MHz, CDCl3, ppm)

δ 9.48, 9.35. HRMS-ESI (m/z): Calcd for C29H34O2Si2 [M]+ 470.21; Found 470.2093. Anal. Calcd for C29H34O2Si2: C, 73.99; H, 7.28; Found: C, 73.96; H, 7.15.


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Preparation of cured BCB-Si-E for the measurement of DMA and TMA. BCB-Si-E (about 1.5 g) was added to a flat bottom glass tube filled with N2, and the tube was heated to 180 °C and kept at the temperature for 2 h. The tube was then maintained at 200 °C for 2 h, 230 °C for 2 h, 250 °C for 2 h, 280 °C for 1 h and 300 °C for 0.5 h, respectively. Thus a fully cured sample was prepared.

Preparation of the BCB-Si-E film for the measurement of surface morphology and static water contact angle. A solution of BCB-Si-E (1.0 g) in mesitylene (15 mL) was allowed to stir at 190 °C for 12 h in a sealed tube under N2. After the pre-polymerization was completed, the tube was cooled to room temperature. The obtained pre-polymer solution of BCB-Si-E was spin-coated on the surface of a silicon wafer. The wafer was then heated at 250 °C for 1 h to prepare a cured BCB-Si-E film. Measurement of water uptake. By using an analogous procedure previously reported,[21] the water uptake of cured BCB-Si-E was measured at room temperature. Fully cured sample was placed into 20 mL of deionized water in a round-bottom flask for an appropriate time. The final results were estimated by the data from 3 samples.

RESULTS AND DISCUSSION

Synthesis and characterization of the monomer. The procedure for the conversion of eugenol to a functional monomer BCB-Si-E was shown in Scheme 1. As depicted in Scheme 1, BCB-Si-E was prepared in a high yield by using extremely low amount of B(C6F5)3 (0.5 mol %) as the catalyst. Because of the reaction of BCB-Si-H with eugenol can produce H2 and CH4, the degree of the reaction can be easily monitored through observing the production


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of bubbles. Ceasing of the bubbles imply that the reaction has completed.

Scheme 1. Synthesis and thermo-crosslinking reaction of BCB-Si-E.

The chemical structure of BCB-Si-E was confirmed by NMR spectra, elemental analysis and HR-MS. Figure 1 depicts 1H NMR,

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C NMR and

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Si-NMR spectra of BCB-Si-E. As

shown in the 1H NMR spectra (Figure 1a), the peaks at about 3.2 ppm (H9, H9, H10' and H10') are attributed to the protons at the four-membered-ring of BCB-Si-E. The characteristic peaks reflecting the protons at CH3-Si are observed at about 0.5 ppm (H7 and H7'). For the allylic groups, these proton signals appear at about 3.2 ppm (H3), 5.0 ppm (H1) and 5.8 ppm (H2), respectively. As can be seen from Figure 1b, the characteristic peaks of 39.4 ppm and 29.9 ppm are attributed to C3 and C14, C14’, C15, C15’ of BCB-Si-E, respectively. The

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Si-NMR

spectrum of BCB-Si-E (Figure 1c) depicts that there are two types of silicon atoms in the monomer at the peaks of 9.48 ppm and 9.35 ppm, respectively, which could be attributed to the differently substituent positions on eugenol. Thus, all signals of the NMR spectra are consistent with the proposed structure of BCB-Si-E.


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Figure 1. 1H-NMR (a), 13C-NMR (b) and 29Si-NMR (c) spectra of BCB-Si-E.

Thermo-crosslinking reaction. At high temperature, the four-member ring of the BCB unit has a tendency to form a highly reactive o-quinodimethane[22-23] intermediate through a thermal ringopening reaction. Such a reactive intermediate can react with itself to produce a dimer or with some dienophiles to form the Diels-Alder adducts[24-25] via the[4+2] or [4+4] cycloaddition reactions. In our previous work[26], we have demonstrated that BCB and allyl group can undergo a [2+4] cycloaddition reaction to form a 6-membered-ring unit at heating. In this work, the thermocrosslinking reaction of BCB-Si-E was monitored by differential scanning calorimetry (DSC) from room temperature to 350 °C, and the results are shown in Figure. 2. As depicted in Figure 2, the first scan (red line) shows a curing onset temperature of about 174 °C and a maximum exothermic peak temperature of 259 °C. This thermo-crosslinking behavior of BCB-Si-E is similar to that of


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the BCB-based polymers or monomers.[4] The second scan (blue line) exhibits a clear Tg of 121 °C. No obvious exothermic peak is observed, indicating the completion of the thermo-crosslinking reaction.

Figure 2. DSC traces of BCB-Si-E at a heating rate of 10 °C min−1 in N2.

The degree of thermo-crosslinking reaction of BCB-Si-E was detected by FT-IR spectroscopy, and the results are depicted in Figure 3. As shown in Figure 3, the characteristic peak of the terminal C=C bond[27] at 1638 cm-1 disappears after thermal curing. Moreover, the peak at 1050 cm-1 attributed to the CH2 vibration[20] of the four-member ring at BCB group also disappears. These results demonstrate that the thermo-crosslinking reaction of BCB-Si-E has completed. According to the DSC curves, the cured BCB-Si-E was prepared by gradient heating (the detail procedure was depicted in experimental section). The completely cured samples were obtained to study their properties.


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Figure 3. FT-IR spectra of BCB-Si-E before and after curing.

Thermostability. The thermostability of cured BCB-Si-E was investigated by thermos-gravimetric analysis (TGA). As shown in Figure 4, cured BCB-Si-E displays a 5 % weight loss temperature (T5d) of about 400 °C and a maximum weight loss peak temperature of 481 °C in N2, respectively (TGA curve in air can be seen in Figure S3 of Supporting Information). These data are better than these of the polycarbonates and cyanate esters,[28] which derived from the renewable softwood lignin with T5d of 346 °C and 375 °C, respectively. It is noted that the residual mass is about 1.87% in N2 above 550 °C.


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Figure 4. TGA curves of cured BCB-Si-E in N2 with a heating rate of 10 °C min−1.

The glass transition temperature (Tg) of BCB-Si-E was measured by DMA, and the results are shown in Figure 5. As can be seen from Figure 5, cured BCB-Si-E possesses high storage modulus of 5.9 GPa at room temperature, which is higher than these of commercial epoxy resins[29] (DER331 and DEN431). Moreover, the Tg (201 °C) of cured BCB-Si-E can also be obviously observed from Figure 5, which is higher than that of bio-based epoxy resin [30] and cyanate esters[9] that prepared from eugenol and rosin. The high thermostability and modulus of the polymer is attributed to the highly cross-linked and rigid structures with aryl units formed in the cured product.

Figure 5. DMA curves of cured BCB-Si-E at a heating rate of 3 °C min−1. Here, E’ is storage modulus and E’’ is loss modulus, respectively.

Dimensional stability is an important parameter to estimate the properties of materials. In our case, the dimensional stability of cured BCB-Si-E was detected by static thermal mechanical analysis (TMA). As shown in Figure 6, cured BCB-Si-E maintains a coefficient of thermal expansion (CTE) of 64 ppm /°C from room temperature to 172°C. Such a low CTE ACS Paragon Plus Environment

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is comparable to that of eugenol-based epoxy resin.[31]

Figure 6. TMA curve of cured BCB-Si-E at a heating rate of 3 °C min−1.

Surface morphology and mechanical properties of the film. The film uniformity is also an important feature for the low dielectric materials[19], which could significantly influence the dielectric properties. Thus, the morphology of the film surface was investigated by AFM and the results can be seen from Figure 7. The BCB-Si-E film on a silicon wafer was prepared by using a spin-coating procedure at room temperature. The film exhibits an average roughness of 0.4 nm and a peak-to-valley roughness of 4.8 nm in an area of 5 µm × 5 µm. Such a smooth surface of the film implies that the BCB-Si-E possesses good film-forming ability

[16]

. The above results

demonstrated that the current material could have potential applications in the microelectronics industry.

The nanoscratch tests were performed to investigate the adhesion of the film on a silicon wafer and the results can be seen in Figure S4. The film exhibits a good bonding strength with an average value of 0.64 GPa (detailed data are shown in Figure S5). The good film-forming ability and high


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bonding strength to the silicon wafer suggest that this polymer can be potentially applied as a highperformance coating material.

Figure 7. AFM image of a cured BCB-Si-E film on a silicon wafer (5 µm × 5 µm): (left) planar graph; (right) 3D image (45°).

Dielectric constant and dissipation. The dielectric constant (Dk) and dissipation (Df) of cured BCB-Si-E were investigated by the standard capacity method, and the results are depicted in Figure 8. As shown in Figure 8, cured BCB-Si-E exhibits an average Dk of 2.77 with a Df of below 7 × 10-3 in the range of frequencies from 0.1 to 30 MHz. These data are comparable to those of BCB resins (about 2.8)[32] and polybenzoxazine resins (2.81).[33] Furthermore, the Dk of cured BCB-Si-E is lowered than that of other sustainable feedstockbased material, for example, anethole-based BCB resin (near 2.9).[5] Such a low dielectric constant and dissipation factor exhibit that the polymer can be used as a encapsulation resin for integrated circuit (IC) dies, or the laminated matrix resin for the production of printed circuit boards.


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Figure 8. Dielectric constants (Dk) and dielectric loss (Df) of cured BCB-Si-E

Hydrophobicity. Considering that the Si-O bonds in the polymer might be hydrolyzed under humidity, the hydrophobicity of cured BCB-Si-E was investigated by measuring its static water contact angle and uptake of water. As shown in Figure S6 of Supporting Information, the BCB-SiE film on a silicon wafer exhibits a static water contact angle of about 98°. Table 1 summarizes water uptake of cured BCB-Si-E. As shown in Table 1, the cured sample displays a low water uptake (< 0.15 %), when immersing it in water for 144 h. This low water uptake is better than that of a commercial bisphenol A-type epoxy resin (near 1.25%). [34] These results demonstrate that the polymer possesses good hydrophobicity. Thanks to the high hydrophobicity, the polymer displays low water uptake, which is significant for the polymer to maintain stability in a humid condition. The great hydrophobicity of this polymer could be attributed to the highly crosslinked structures, which can greatly decrease the water uptake of the polymer and prevent the sensitive bonds from hydrolysis[35].


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Table 1. Water uptake of cured BCB-Si-E at room temperature.

CONCLUSIONS

In summary, we have successfully prepared a novel low k polymer based on a renewable phenol (eugenol) by using an extremely facile method. After cured at high temperature, the cross-linked polymer exhibited low dielectric constant, good thermostability, high storage modulus and low water uptake. These good overall properties enable this material to be potentially applied in microelectronic industry, such as encapsulation resins for integrated circuit (IC) dies, or the laminated matrix resin for the production of printed circuit boards. This work developed a facile method for the conversion of eugenol to a high-performance polymer under a mild condition, which could significantly expand the research for conversion of sustainable feedstocks to highperformance materials.

ASSOCIATED CONTENT

Supporting Information

The Supporting Information is available free of charge on the ACS Publications website at http://pubs.acs.org at DOI: 1

H NMR and 13C NMR spectra of BCB-SiH, and additional figures as mentioned in the text.

AUTHOR INFORMATION


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Corresponding Author

* E-mail: [email protected], [email protected]

Notes

The authors declare no competing financial interest.

ACKNOWLEDGMENTS

This work was implemented under the financial support from Ministry of Science and Technology of China (2015CB931900), the National Natural Science Foundation of China (No. 21574146, 21504103, 21774140 and 21774142), the Science and Technology Commission of Shanghai Municipality (16JC1403800), the Strategic Priority Research Program of the Chinese Academy of Sciences (Grant XDB 20020000).

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For Table of Contents Use Only

Toc Graphic

Synopsis：：

A high-performance polymer with low dielectric constant and low water uptake based on a renewable allylphenol (eugenol) is reported.


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A Low-Dielectric Polymer Derived from a Biorenewable Phenol

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