Synthesis of condensed polynuclear aromatic resin from furfural extract oil of reduced-pressure route II

Petroleum Science, Oct 2013

As an industrial byproduct of oil refining, furfural extract oil from reduced-pressure route II with high aromatic content was used to prepare heat-resistant condensed polynuclear aromatic (COPNA) resin for the first time. The basic properties of furfural extract oil and the resultant COPNA resin were characterized by infrared spectroscopy (FT-IR), nuclear magnetic resonance spectroscopy (1H-NMR), thermogravimetric analysis (TGA) and elemental analysis (EA). The result showed that heat treated furfural extract oil was successfully used for the synthesis of heat-resistant COPNA resin. The average structural parameters of raw materials and prepared resin were calculated by the improved Brown-Ladner method, and the averaged molecular structure of the resin was obtained. The reaction mechanism for the synthesis of COPNA resin was suggested as an acid-catalyzed positive ion type polymerization.

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Synthesis of condensed polynuclear aromatic resin from furfural extract oil of reduced-pressure route II

Synthesis of condensed polynuclear aromatic resin from furfural extract oil of reduced-pressure route II Wu Mingbo Jiang Wei Wang Yuwei Li Shibin Zheng Jingtang with high aromatic content was used to prepare heat-resistant condensed polynuclear aromatic (COPNA) method, and the averaged molecular structure of the resin was obtained. The reaction mechanism for the synthesis of COPNA resin was suggested as an acid-catalyzed positive ion type polymerization. Furfural extract oil; reduced-pressure route; COPNA resin; synthesis; reaction mechanism - (1H-NMR), thermogravimetric analysis (TGA) and elemental analysis (EA). The result showed that heat treated furfural extract oil was successfully used for the synthesis of heat-resistant COPNA resin. The average 1 Introduction The synthesis of COPNA resin was firstly reported by with good lubricity, mechanical properties and mouldability, this resin has attracted considerable attention for its potential al, 2010a; 2010b; Tanemura et al, 2011; 2012; Zhao et al, (Nakajima et al, 1995; Nawa, 1996; Nawa and Ohkita, 1997). Recently, a number of similar raw materials including coal derived and petroleum based mixtures have been successfully used to prepare COPNA resin (Guo et al, 2002; Li et al, oil from reduced-pressure route , commonly used as fuel oil for boilers or for the manufacture of synthetic rubber, is a byproduct of oil refining. With a high aromatic content, narrow molecular weight distribution and low content of heavy metals, furfural extract oil is theoretically considered as an ideal candidate raw material to prepare COPNA resin. route its volatile components. Then, COPNA resin was eventually synthesized through the reaction of the thermally condensed oil and the cross-linking agent (1, 4-benzenedimethanol, PXG), which was catalyzed by p-toluene sulfonic acid (PTS). The resultant resin as well as the raw materials were characterized by elemental analysis (EA), infrared spectroscopy (1H-NMR) and thermogravimetric analysis (TGA). 2 Experimental 2.1 Raw materials Furfural extract oil from reduced-pressure route China. PXG (AR) and PTS (AR) were both purchased from was obtained from Tianjin Chemical Reagent Company, China. Quinoline was purchased from Tingxin Chemical Reagent Company, China. 2.2 Heat treatment of furfural extract oil from reduced-pressure route II Furfural extract oil from vacuum second side-cut was added into a reaction kettle equipped with a thermometer and mechanical stirrer. The reaction kettle was heated to 420 °C for 3 h. A small amount of the light fraction of furfural extract oil was found to have evaporated after heat treatment and the thermally condensed oil was obtained. 2.3 Preparations of COPNA resin The thermally condensed oil, PXG and PTS (with a weight ratios of 75:20:5) were fully mixed in a reactor, and then the mixture was stirred and heated in a nitrogen flow o min and kept for 1 h, then heated to 150 oC and held until a the viscosity of this system increased gradually, indicating that the degree of polymerization increased gradually during the reaction. 2.4 Characterization The prepared COPNA resins and the raw materials were For TGA measurements, about 10 mg sample was placed gravimetric analyzer, and heated from room temperature to 900 oC at a heating rate of 10 o The scan frequency of each spectrum was 15 s-1 with a -1. 1H - N M R s p e c t r o m e t e r w a s used to characterize the state of different hydrogen in prepared COPNA resins and the raw materials. The solvent used was chloroform, the internal standard label was trimethylphenylsilane, the sweep length was 10,000 Hz, and the resonance frequency was 500 MHz. element analyzer. The structural data of the obtained COPNA formula (Wu et al, 2012a; 2012b). 3 Results and discussion 3.1 Properties of furfural extract oil and thermally condensed oil The basic properties of furfural extract oil and its thermally condensed oil are given in Table 1. We can see that the average molecular weight of furfural extract oil was 273, Notes: M, average molecular weight; CR, carbon residue ratio; condensed oil were both higher than those of furfural extract oil. These results showed that polymerization reactions took place during the process of heat treatment. Table 2 shows the elemental analysis of furfural extract oil and thermally condensed oil. After the thermal condensation of furfural extract oil, the total content of other elements was from 1.10 to 1.16, and the fA The results indicated that some ingredients in furfural extract oil can be removed by heat treatment and condensation in this process. 3.2 Properties of COPNA resin 3.2.1 Basic properties of COPNA resin Table 3 shows the basic properties of the obtained COPNA resin. Tables 1 and 3 indicate that the residual 1412 32.6 5.6 17.9 12.4 110 6.1 0.4 1.5 2.9 1.22 addition, the average molecular weights in Tables 1 and 3 showed that the average degree of polymerization was around 3. 3.2.2 FT-IR analysis condensed oil and COPNA resin are shown in Fig. 1. Peaks at 3,420-3,550 cm-1 in Fig. 1 were attributed to N-H stretching vibration and O-H stretching vibration. Peaks at 3,046 cm-1 and 1,602 cm-1 were attributed to aromatic C-H and C=C stretching vibrations. The peak at 1,455 cm-1 was from C-H bending vibration. These peaks clearly revealed the existence 3432 3046 2923 2854 3430 3046 2854 2920 3445 3045 1600 1440 of the elements C, H, N and O, as well as the corresponding chemical bonds they formed. The peaks at 750 cm-1 cm-1 -1 were possibly generated by the out-ofplane bending vibrations of 2, 3, 4-aromatic C-H. These substitution reaction. -1 attributed to the C-H stretching vibration in –CH – were weakened in Fig. 1(b). The peaks between 900 cm-1 2and 650 cm-1 -1 -1 -1) attributed to out-of-plane bending vibration of C-H in aromatics were weaker than those of Fig. 1(a). These changes indicated that condensation of furfural extract oil occurred during heat treatment. cm-1 were stronger than those of Fig. 1(b), indicating the occurrence of the cross-linking reactions between PXG and thermally condensed oil. The peaks in Fig. 1(c) at 1,600 cm-1 attributed to C=C stretching vibration and the peaks between 900 cm-1 and 650 cm-1 belonged to out-of-plane bending vibration of C-H in aromatics were much stronger than those of Fig. 1(b), indicating that the cross-linking reactions changed the types of aromatic substitution. 3.2.3 1H-NMR analysis The 1H-NMR spectra of furfural extract oil, thermally condensed oil and COPNA resin are shown in Fig. 2. The absorption resonance of hydrogen in aromatic rings. Fig. 2 2 aromatic rings, respectively. hydrogen in weight). HA refers to the weight ratio of aromatic H in aromatic rings. Similarly, H and H refer to the weight 3 hydrogen in the A increased from oil, while there was a distinct decrease in the content of H . This was because -H was mostly located on side-chains, and the decrease in -H demonstrated side-chain cleavage and an increase in polymerization degree, which was in accordance content of H after synthetic reaction, indicating that the aromatics connected with –CH2– of PXG. 3.3 Mechanism of COPNA resin synthesis 1H-NMR, elemental analysis and average molecular weight analysis of furfural extract oil, thermally condensed oil and COPNA resin, the average structural parameters, including CT, HT, fA, HAU A T, RA, RN, and CR method. The obtained average structure parameters are shown in Table 5, in which the S, O and N levels were negligible. The reaction mechanism and averaged molecular structure of COPNA resin are as follows: H2÷C H2÷C H÷ H÷ CH2OH C÷H2 3.4 Heat resistance analysis The thermal decomposition behavior of furfural extract oil, thermally condensed oil, and COPNA resin are shown in even at 50 oC, while the degradation onset temperature of thermally condensed oil was above 200 oC, demonstrating that most light fractions were removed during thermal condensation. Compared with the weight loss of thermally condensed oil, the weight loss of COPNA resin was almost unchanged in the initial stage, and its loss rate was relatively slow after 250 oC in comparison with those of furfural extract oil and thermally condensed oil. When the temperature was raised to 500 oC, the weight left of COPNA resin still condensed oil. 4 Conclusions With short side chains, lower steric hindrance, high aromatic content and purity, furfural extract oil from reducedpressure route is selected as raw material for the preparation c Fig. 3 TGA curves of furfural extract oil (a), thermally condensed oil (b) and COPNA resin (c) of COPNA resin. After heat treatment, the polymerization degree has increased and side-chain cleavage occurred and the content of heavy aromatics has increased remarkably. COPNA resin has been successfully prepared from thermally condensed oil with PXG as a cross-linking agent and PTS condensation and polymerization mechanisms, the average molecular structures of raw material and COPNA resin are 1H-NMR, element analysis and average molecular weight analysis. The degree of polymerization is found to be around 3. The resulting COPNA resin with high heat resistance is a potential binder in carbon material preparation. Nomenclatures A Total average carbon number Total average hydrogen number Ratio of aromatic carbon number to total carbon number Average condensation degree of average molecular Total average rings Average aromatic rings Average naphthenic rings Average carbon number on the rings Acknowledgements 20 aromatic resins from aromatics-enriched feedstocks . Carbon Techniques . 2002 . 119 ( 02 ): 10 - 14 (in Chinese) Kusakabe K, Gohgi S and Morooka S. Carbon molecular sieving membranes derived from condensed polynuclear aromatic (COPNA) Engineering . 2010 . 26 ( 5 ): 54 - 56 (in Chinese) properties of condensed poly-nuclear aromatics resin using coal tar 136(4 ): 13 - 17 (in Chinese) Lin Q L , Zheng R G and Tian P H. Preparation and characterization of 29(5 ): 537 -543 Lin Q L , Zheng M Z , Qin T , et al. Preparation of solid carbon spheres poly-condensate of fused polynuclear aromatics (COPNA) resin . 1996 . 61 ( 10 ): 1737 -1746 Nawa K and Ohkita M. Reliability of the laminate from advanced synthesis of heat-resistant resin from ethylene tar . Applied Mechanics and Materials . 2012 . 217 - 219 : 1159 -1165 Tanemura K , Suzuki T , Nishida Y , et al. Synthesis of the sulfonated condensed polynuclear aromatic (S-COPNA) resins as strong protonic acids . Tetrahedron . 2011 . 67 ( 6 ): 1314 -1319 Tanemura K , Suzuki T , Nishida Y , et al. Synthesis of the strongly acidic sulfonated condensed polynuclear aromatic (S-COPNA) resins using condensed poly-nuclear aromatic resin using tiroxane as crossinglinking agent . New Carbon Materials. 2012a . 27 ( 6 ): 469 - 475


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Mingbo Wu, Wei Jiang, Yuwei Wang, Shibin Li, Jingtang Zheng. Synthesis of condensed polynuclear aromatic resin from furfural extract oil of reduced-pressure route II, Petroleum Science, 2013, 584-588, DOI: 10.1007/s12182-013-0310-5