Fast pyrolysis of pine wood was carried out to yield a liquid bio-oil mixture that was separated into organic and aqueous phases. The organic phase (ORG-bio-oil) was characterized by gas chromatography–mass spectroscopy, 31P-nuclear magnetic resonance spectroscopy, and Fourier transform infrared (FTIR) spectroscopy. It was further used as a raw material for producing a mixture of biphenolic compounds (ORG-biphenol). ORG-bio-oil, ORG-biphenol, and bisphenol-A were reacted with cyanogen bromide to yield cyanate ester monomers. Cyanate esters were characterized using FTIR spectroscopy and were thermally cross-linked to develop thermoset materials. Thermomechanical properties of cross-linked cyanate esters were assessed using dynamic mechanical analysis and compared with those of cross-linked bisphenol-A-based cyanate ester. ORG-biphenol cyanate ester was observed to have a superior glass transition temperature (350–380°C) as compared to bisphenol-A cyanate ester (190–220°C). Cyanate esters derived from bio-oil have the potential to be a sustainable alternative to the bisphenol-A-derived analog.
WangGFuGGaoTL, et al.Preparation and characterization of novel film adhesives based on cyanate ester resin for bonding advanced radome. Int J Adhes Adhes2016; 68: 80–86. DOI: 10.1016/j.ijadhadh.2016.02.004.
5.
InamdarACherukattuJAnandA, et al.Thermoplastic-toughened high-temperature cyanate esters and their application in advanced composites. Ind Eng Chem Res2018; 57: 4479–4504. DOI: 10.1021/acs.iecr.7b05202.
6.
ToldyASzlancsikASzolnokiB. Reactive flame retardancy of cyanate ester/epoxy resin blends and their carbon fibre reinforced composites. Polym Degrad Stabil2016; 128: 29–38. DOI: 10.1016/j.polymdegradstab.2016.02.015.
7.
ZhanGZZhaoLHuS, et al.A novel biobased resin-epoxidized soybean oil modified cyanate ester. Polym Eng Sci2008; 48: 1322–1328. DOI: 10.1002/pen.21096.
8.
LeiYXXuMZJiangML, et al.Curing behaviors of cyanate ester/epoxy copolymers and their dielectric properties. High Perform Polym2017; 29: 1175–1184. DOI: 10.1177/0954008316672291.
9.
ZegaouiAWangARDayoAQ, et al.Effects of gamma irradiation on the mechanical and thermal properties of cyanate ester/benzoxazine resin. Radiat Phys Chem2017; 141: 110–117. DOI: 10.1016/j.radphyschem.2017.06.010.
10.
KumarKSSNairCPRNinanKN. Investigations on the cure chemistry and polymer properties of benzoxazine-cyanate ester blends. Eur Polym J2009; 45: 494–502. DOI: 10.1016/j.eurpolymj.2008.11.001.
11.
WangYQWuGLKouKC, et al.Mechanical, thermal conductive and dielectrical properties of organic montmorillonite reinforced benzoxazine/cyanate ester copolymer for electronic packaging. J Mater Sci Mater El2016; 27: 8279–8287. DOI: 10.1007/s10854-016-4834-5.
12.
OhashiSKilbaneJHeylT, et al.Synthesis and characterization of cyanate ester functional benzoxazine and its polymer. Macromolecules2015; 48: 8412–8417. DOI: 10.1021/acs.macromol.5b02285.
13.
WanLZhangXWuGL, et al.Thermal conductivity and dielectric properties of bismaleimide/cyanate ester copolymer. High Voltage2017; 2: 167–171. DOI: 10.1049/hve.2017.0056.
14.
HamertonI. High-performance thermoset-thermoset polymer blends: a review of the chemistry of cyanate ester-bismaleimide blends. High Perform Polym1996; 8: 83–95. DOI: 10.1088/0954-0083/8/1/006.
15.
IredaleRJWardCHamertonI. Modern advances in bismaleimide resin technology: a 21st century perspective on the chemistry of addition polyimides. Prog Polym Sci2017; 69: 1–21. DOI: 10.1016/j.progpolymsci.2016.12.002.
16.
BartonJMHamertonIJonesJR. A study of the thermal and dynamic mechanical-properties of functionalized aryl cyanate esters and their polymers. Polym Int1993; 31: 95–106. DOI: 10.1002/pi.4990310114.
17.
ChaplinAHamertonIHowlinBJ, et al.Development of novel functionalized aryl cyanate ester oligomers. 1. Synthesis and thermal characterization of the monomers. Macromolecules1994; 27: 4927–4935. DOI: 10.1021/ma00096a013.
18.
NgFFCoutureGPhilippeC, et al.Bio-based aromatic epoxy monomers for thermoset materials. Molecules2017; 22: 48. DOI: 10.3390/molecules22010149.
19.
HernandezEDBassettAWSadlerJM, et al.Synthesis and characterization of bio-based epoxy resins derived from vanillyl alcohol. ACS Sustainable Chem Eng2016; 4: 4328–4339. DOI: 10.1021/acssuschemeng.6b00835.
20.
TritaASOverLCPolliniJ, et al.Synthesis of potential bisphenol A substitutes by isomerising metathesis of renewable raw materials. Green Chem2017; 19: 3051–3060. DOI: 10.1039/c7gc00553a.
21.
KoelewijnSFCooremanCRendersT, et al.Promising bulk production of a potentially benign bisphenol A replacement from a hardwood lignin platform. Green Chem2018; 20: 1050–1058. DOI: 10.1039/c7gc02989 f.
22.
LlevotAGrauECarlottiS, et al.From lignin-derived aromatic compounds to novel biobased polymers. Macromol Rapid Comm2016; 37: 9–28. DOI: 10.1002/marc.201500474.
23.
RaquezJMDelegliseMLacrampeMF, et al.Thermosetting (bio)materials derived from renewable resources: a critical review. Prog Polym Sci2010; 35: 487–509. DOI: 10.1016/j.progpolymsci.2010.01.001.
24.
JiangYDingDCZhaoS, et al.Renewable thermoset polymers based on lignin and carbohydrate derived monomers. Green Chem2018; 20: 1131–1138. DOI: 10.1039/c7gc03552 g.
25.
ZhaoSHuangXNWheltonAJ, et al.Formaldehyde-free method for incorporating lignin into epoxy thermosets. ACS Sustainable Chem2018; 6: 10628–10636. DOI: 10.1021/acssuschemeng.8b01962.
26.
FacheMBoutevinBCaillolS. Epoxy thermosets from model mixtures of the lignin-to-vanillin process. Green Chem2016; 18: 712–725. DOI: 10.1039/c5gc01070e.
27.
StanzioneJFGiangiulioPASadlerJM, et al.Lignin-based bio-oil mimic as biobased resin for composite applications. ACS Sustainable Chem2013; 1: 419–426. DOI: 10.1021/sc3001492.
28.
StanzioneJFSadlerJMLa ScalaJJ, et al.Lignin model compounds as bio-based reactive diluents for liquid molding resins. ChemSusChem2012; 5: 1291–1297. DOI: 10.1002/cssc.201100687.
29.
CambreaLRDavisMCGarrisonMD, et al.Processable cyanate ester resin from cis resveratrol. J Polym Sci Pol Chem2017; 55: 971–980. DOI: 10.1002/pola.28457.
30.
HarveyBGGuenthnerAJYandekGR, et al.Synthesis and characterization of a renewable cyanate ester/polycarbonate network derived from eugenol. Polymer2014; 55: 5073–5079. DOI: 10.1016/j.polymer.2014.08.034.
31.
HarveyBGGuenthnerAJKoontzTA, et al.Sustainable hydrophobic thermosetting resins and polycarbonates from turpentine. Green Chem2016; 18: 2416–2423. DOI: 10.1039/c5gc02893 k.
32.
KoelewijnSFVan den BoschSRendersT, et al.Sustainable bisphenols from renewable softwood lignin feedstock for polycarbonates and cyanate ester resins. Green Chem2017; 19: 2561–2570. DOI: 10.1039/c7gc00776 k.
33.
HarveyBGGuenthnerAJMeylemansHA, et al.Renewable thermosetting resins and thermoplastics from vanillin. Green Chem2015; 17: 1249–1258. DOI: 10.1039/c4gc01825 g.
34.
MeylemansHAHarveyBGReamsJT, et al.Synthesis, characterization, and cure chemistry of renewable bis(cyanate) esters derived from 2-methoxy-4-methylphenol. Biomacromolecules2013; 14: 771–780. DOI: 10.1021/bm3018438.
35.
DavisMCGuenthnerAJSahagunCM, et al.Polycyanurate networks from dehydroanethole cyclotrimers: synthesis and characterization. Polymer2013; 54: 6902–6909. DOI: 10.1016/j.polymer.2013.10.050.
36.
DavisMCGuenthnerAJGroshensTJ, et al.Polycyanurate networks from anethole dimers: synthesis and characterization. J Polym Sci Pol Chem2012; 50: 4127–4136. DOI: 10.1002/pola.26218.
37.
KammBGerhardtMLeißS. The biorefinery concept – thermochemical production of building blocks and syngas. In: CrockerM (ed) Thermochemical Conversion of Biomass to Liquid Fuels and Chemicals. Cambridge: Royal Society of Chemistry, 2010, pp. 46–62.
38.
BridgwaterAVMeierDRadleinD. An overview of fast pyrolysis of biomass. Org Geochem1999; 30: 1479–1493. DOI: 10.1016/s0146-6380(99)00120-5.
39.
MohanDPittmanCUSteelePH. Pyrolysis of wood/biomass for bio-oil: a critical review. Energ Fuel2006; 20: 848–889. DOI: 10.1021/ef0502397.
40.
BridgwaterAV. Review of fast pyrolysis of biomass and product upgrading. Biomass Bioenerg2012; 38: 68–94. DOI: 10.1016/j.biombioe.2011.01.048.
41.
KanTStrezovVEvansTJ. Lignocellulosic biomass pyrolysis: a review of product properties and effects of pyrolysis parameters. Renew Sust Energ Rev2016; 57: 1126–1140. DOI: 10.1016/j.rser.2015.12.185.
42.
ShenDKJinWHuJ, et al.An overview on fast pyrolysis of the main constituents in lignocellulosic biomass to valued-added chemicals: structures, pathways and interactions. Renew Sust Energ Rev2015; 51: 761–774. DOI: 10.1016/j.rser.2015.06.054.
43.
RahmanMMLiuRHCaiJM. Catalytic fast pyrolysis of biomass over zeolites for high quality bio-oil – a review. Fuel Process Technol2018; 180: 32–46. DOI: 10.1016/j.fuproc.2018.08.002.
44.
MostafazadehAKSolomatnikovaODroguiP, et al.A review of recent research and developments in fast pyrolysis and bio-oil upgrading. Biomass Conversion and Biorefinery2018; 8: 739–773. DOI: 10.1007/s13399-018-0320-z.
45.
WesterhofRJMBrilmanDWFGarcia-PerezM, et al.Stepwise fast pyrolysis of pine wood. Energ Fuel2012; 26: 7263–7273. DOI: 10.1021/ef301319t.
46.
YildizGLathouwersTToramanHE, et al.Catalytic fast pyrolysis of pine wood: effect of successive catalyst regeneration. Energ Fuel2014; 28: 4560–4572. DOI: 10.1021/ef500636c.
47.
WangJXCaoJPZhaoXY, et al.Study on pine sawdust pyrolysis behavior by fast pyrolysis under inert and reductive atmospheres. J Anal Appl Pyrol2017; 125: 279–288. DOI: 10.1016/j.jaap.2017.03.015.
48.
Thangalazhy-GopakumarSAdhikariSRavindranH, et al.Physiochemical properties of bio-oil produced at various temperatures from pine wood using an auger reactor. Bioresource Technol2010; 101: 8389–8395. DOI: 10.1016/j.biortech.2010.05.040.
49.
MullenCABoatengAA. Chemical composition of bio-oils produced by fast pyrolysis of two energy crops. Energ Fuel2008; 22: 2104–2109. DOI: 10.1021/ef700776w.
50.
SerapigliaMJMullenCABoatengAA, et al.Impact of harvest time and cultivar on conversion of switchgrass to bio-oils via fast pyrolysis. Bioenerg Res2017; 10: 388–399. DOI: 10.1007/s12155-016-9812-5.
51.
MullenCABoatengAAGoldbergNM, et al.Bio-oil and bio-char production from corn cobs and stover by fast pyrolysis. Biomass Bioenerg2010; 34: 67–74. DOI: 10.1016/j.biombioe.2009.09.012.
52.
WangJZhongZPDingK, et al.Catalytic fast pyrolysis of bamboo sawdust via a two-step bench scale bubbling fluidized bed/fixed bed reactor: study on synergistic effect of alkali metal oxides and HZSM-5. Energ Convers Manage2018; 176: 287–298. DOI: 10.1016/j.enconman.2018.09.029.
53.
OasmaaAKuoppalaEGustS, et al.Fast pyrolysis of forestry residue. 1. Effect of extractives on phase separation of pyrolysis liquids. Energ Fuel2003; 17: 1–12. DOI: 10.1021/ef020088x.
54.
OasmaaAKuoppalaESolantaustaY. Fast pyrolysis of forestry residue. 2. Physicochemical composition of product liquid. Energ Fuel2003; 17: 433–443. DOI: 10.1021/ef020206 g.
55.
OasmaaASolantaustaYArpiainenV, et al.Fast pyrolysis bio-oils from wood and agricultural residues. Energ Fuel2010; 24: 1380–1388. DOI: 10.1021/ef901107 f.
56.
YanikJKommayerCSaglamM, et al.Fast pyrolysis of agricultural wastes: characterization of pyrolysis products. Fuel Process Technol2007; 88: 942–947. DOI: 10.1016/j.fuproc.2007.05.002.
57.
WangYPZengZHTianXJ, et al.Production of bio-oil from agricultural waste by using a continuous fast microwave pyrolysis system. Bioresource Technol2018; 269: 162–168. DOI: 10.1016/j.biortech.2018.08.067.
58.
WangSRWangKGLiuQ, et al.Comparison of the pyrolysis behavior of lignins from different tree species. Biotechnol Adv2009; 27: 562–567. DOI: 10.1016/j.biotechadv.2009.04.010.
59.
BaiXLKimKHBrownRC, et al.Formation of phenolic oligomers during fast pyrolysis of lignin. Fuel2014; 128: 170–179. DOI: 10.1016/j.fuel.2014.03.013.
60.
ShenDZhaoJXiaoR, et al.Production of aromatic monomers from catalytic pyrolysis of black-liquor lignin. J Anal Appl Pyrol2015; 111: 47–54. DOI: 10.1016/j.jaap.2014.12.013.
61.
FanLLZhangYNLiuSY, et al.Bio-oil from fast pyrolysis of lignin: effects of process and upgrading parameters. Bioresource Technol2017; 241: 1118–1126. DOI: 10.1016/j.biortech.2017.05.129.
62.
StasMKubickaDChudobaJ, et al.Overview of analytical methods used for chemical characterization of pyrolysis bio-oil. Energ Fuel2014; 28: 385–402. DOI: 10.1021/ef402047y.
63.
KanaujiaPKSharmaYKGargMO, et al.Review of analytical strategies in the production and upgrading of bio-oils derived from lignocellulosic biomass. J Anal Appl Pyrol2014; 105: 55–74. DOI: 10.1016/j.jaap.2013.10.004.
64.
MullenCABoatengAA. Characterization of water insoluble solids isolated from various biomass fast pyrolysis oils. J Anal Appl Pyrol2011; 90: 197–203. DOI: 10.1016/j.jaap.2010.12.004.
65.
AnderssonTHyotylainenTRiekkolaML. Analysis of phenols in pyrolysis oils by gel permeation chromatography and multidimensional liquid chromatography. J Chromatogr A2000; 896: 343–349. DOI: 10.1016/s0021-9673(00)00678-6.
66.
MichailofCMKalogiannisKGSfetsasT, et al.Advanced analytical techniques for bio-oil characterization. Wires Energy Environ2016; 5: 614–639. DOI: 10.1002/wene.208.
67.
HaoNBenHXYooCG, et al.Review of NMR characterization of pyrolysis oils. Energ Fuel2016; 30: 6863–6880. DOI: 10.1021/acs.energyfuels.6b01002.
BardeMAdhikariSViaBK, et al.Synthesis and characterization of epoxy resins from fast pyrolysis bio-oil. Green Materials2018; 6: 76–84.
70.
CelikbagYMeadowsSBardeM, et al.Synthesis and characterization of bio-oil-based self-curing epoxy resin. Ind Eng Chem Res2017; 56: 9389–9400. DOI: 10.1021/acs.iecr.7b02123.
71.
SibajaBAdhikariSCelikbagY, et al.Fast pyrolysis bio-oil as precursor of thermosetting epoxy resins. Polym Eng Sci2018; 58: 1296–1307.
72.
MeylemansHAGroshensTJHarveyBG. Synthesis of renewable bisphenols from creosol. ChemSusChem2012; 5: 206–210. DOI: 10.1002/cssc.201100402.
73.
KimPWeaverSNohK, et al.Characteristics of bio-oils produced by an intermediate semipilot scale pyrolysis auger reactor equipped with multistage condensers. Energ Fuel2014; 28: 6966–6973. DOI: 10.1021/ef5016186.
74.
ASTM D4377-00. Standard test method for water in crude oils by potentiometric Karl Fischer titration. ASTM International: West Conshohocken, PA, 2011: 1–7.
75.
ASTM D664-11a. Standard test method for acid number of petroleum products by potentiometric titration. ASTM International: West Conshohocken, PA, 2011: 1–11.
76.
ASTM D1475-13. Standard test method for density of liquid coatings, inks, and related products. ASTM International: West Conshohocken, PA, 2011: 1–4.
77.
BenHXRagauskasAJ. NMR characterization of pyrolysis oils from kraft lignin. Energ Fuel2011; 25: 2322–2332. DOI: 10.1021/ef2001162.
78.
SipilaKKuoppalaEFagernasL, et al.Characterization of biomass-based flash pyrolysis oils. Biomass Bioenerg1998; 14: 103–113. DOI: 10.1016/s0961-9534(97)10024 -1.
79.
KohHCYDaiJTanE, et al.Catalytic effect of 2,2’-diallyl bisphenol A on thermal curing of cyanate esters. J Appl Polym Sci2006; 101: 1775–1786. DOI: 10.1002/app.23533.
80.
KinlochAJTaylorAC. The toughening of cyanate-ester polymers – Part II – chemical modification. J Mater Sci2003; 38: 65–79. DOI: 10.1023/a:1021109731672.
81.
GeorjonOGalyJ. Effects of crosslink density on mechanical properties of high class transition temperature polycyanurate networks. J Appl Polym Sci1997; 65: 2471–2479. DOI: 10.1002/(sici)1097-4628(19970919)65:12<2471:: aid-app18>3.0.co;2-3.
82.
GoertzenWKKesslerMR. Thermal and mechanical evaluation of cyanate ester composites with low-temperature processability. Compos Part A Appl S2007; 38: 779–784. DOI: 10.1016/j.compositesa.2006.09.005.
83.
ZhaoSAbu-OmarMM. Renewable epoxy networks derived from lignin-based monomers: effect of cross-linking density. ACS Sustainable Chem2016; 4: 6082–6089. DOI: 10.1021/acssuschemeng.6b01446.
