Synthesis and physicochemical characterization of polyoxymethylene dimethyl ethers

KANG Mei-rong; SONG He-yuan; JIN Fu-xiang; CHEN Jing

Volume 45 Issue 7

Jul. 2017

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Article Navigation > Journal of Fuel Chemistry and Technology > 2017 > 45(7): 837-845

KANG Mei-rong, SONG He-yuan, JIN Fu-xiang, CHEN Jing. Synthesis and physicochemical characterization of polyoxymethylene dimethyl ethers[J]. Journal of Fuel Chemistry and Technology, 2017, 45(7): 837-845.

Citation:

KANG Mei-rong, SONG He-yuan, JIN Fu-xiang, CHEN Jing. Synthesis and physicochemical characterization of polyoxymethylene dimethyl ethers[J]. Journal of Fuel Chemistry and Technology, 2017, 45(7): 837-845.

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Synthesis and physicochemical characterization of polyoxymethylene dimethyl ethers

KANG Mei-rong¹,
SONG He-yuan^{1, 2},
JIN Fu-xiang^{1, 2},
CHEN Jing^{1
,
,}

1.
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China

Funds:

the National Natural Science Foundation of China 21473225

More Information

Corresponding author: CHEN Jing, Tel/ Fax: +86-931-4968068, E-mail: chenj@licp.cas.cn.
Received Date: 2017-03-30
Rev Recd Date: 2017-05-12

Available Online: 2021-01-23

Publish Date: 2017-07-10

Abstract

Abstract

Polyoxymethylene dimethyl ethers (H₃CO(CH₂O)_nCH₃, PODE_n or DMM_n, n ≥ 2) with unique physical and chemical properties are a potential additive for diesel fuels, which can effectively enhance the combustion efficiency and reduce the emission of pollutants. In this work, a series of pure PODE_n components (n=2-5) were synthesized from methylal and trioxymethylene and obtained with high purity through collaborative separation; their structure and properties were characterized by NMR, FT-IR, Raman, and DFT calculation and a detailed assignment of the expressions in the spectrogram to the various groups was performed. The density and viscosity of PODE_n were measured at 298.15-323.15 K. The results indicate that the density and viscosity of PODE_n decrease gradually with the increase of temperature. Meanwhile, with the increase in the number of -CH₂O-units (n) from 2 to 5, the density, viscosity, flash point, pour point, and the heat of fusion and solidification of PODE_n are all increased. These results are valuable for the practical synthesis and application of PODE_n.
- polyoxymethylene dimethyl ethers,
- synthesis,
- structural characterization,
- physicochemical property

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References(33)

References

[1]	UCHIDA T, KURITA Y, KUBO M. The dipole moments and the strucures of polyoxymethylene dimethyl ethers[J]. J Polym Sci, 1956, 19(92):365-372. doi: 10.1002/pol.1956.120199215
[2]	ARVIDSON M, FAKLEY M E, SPENCER M S. Lithium Halide-Assisted formation of polyoxymethylene dimethyl ethers from dimethoxymethane and formaldehyde[J]. J Mol Catal, 1987, 41(3):391-393. doi: 10.1016/0304-5102(87)80118-9
[3]	VIGIER F, COUTANCEAU C, LÉGERJ M, DUBOIS J L. Polyoxymethylene dimethyl ether (CH₃O(CH₂O)_nCH₃) oxidation on Pt and Pt/Ru supported catalysts[J]. J Power Sources, 2008, 175(1):82-90. doi: 10.1016/j.jpowsour.2007.09.053
[4]	MASAHIRO W, HIROYUKI U, STEVE B, JEAN-LUC D. Fuel cells using an oxy-carbon fuel soluble in aqueous meduim: EP, 1993159A1[P]. 2008-11-19.
[5]	BURGER J, SIEGERT M, STRÖFER E, HASSE H. Poly(oxymethylene) dimethyl ethers as components of tailored diesel fuel:Properties, synthesis and purification concepts[J]. Fuel, 2010, 89(11):3315-3319. doi: 10.1016/j.fuel.2010.05.014
[6]	ZHAO Q, WANG H, QIN ZHF, WU ZH W, WU J B, FAN W B, WANG J G. Synthesis of polyoxymethylene dimethyl ethers from methanol and trioxymethylene with molecular sieves as catalysts[J]. J Fuel Chem Technol, 2011, 39(12):918-923. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract17845.shtml
[7]	WU J B, WU Z W, WANG R Y, SHI R P, QIN Z F, ZHU H Q, DONG M, FAN W B, WANG J G. Recent research progresses in the catalytic synthesis of methyl formate, dimethoxymethane and polyoxymethylene dimethyl ethers from methano[J]. J Fuel Chem Technol, 2015, 43(7):816-828. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18658.shtml
[8]	GAO X C, YANG W M, LIU Z C, GAO H X. Catalytic performance of HZSM-5 molecular sieve for synthesis of polyoxymethylene dimethyl ethers[J]. Chin J Catal, 2012, 33(8):1389-1394. https://www.researchgate.net/publication/275884405_Catalytic_Performance_of_HZSM-5_Molecular_Sieve_for_Synthesis_of_Polyoxy-methylene_Dimethyl_Ethers
[9]	LI H J, SONG H L, ZHAO F, CHEN L W, XIA CH G. Chemical equilibrium controlled synthesis of polyoxymethylene dimethyl ethers over sulfated titania[J]. J Energy Chem, 2015, 24(2):239-244. doi: 10.1016/S2095-4956(15)60307-2
[10]	REN Y, HUANG Z H, MIAO H Y, DI Y G, JIANG D M, ZENG K, LIU B, WANG X B. Combustion and emissions of a DI diesel engine fuelled with diesel-oxygenate blends[J]. Fuel, 2008, 87(12):2691-2697. doi: 10.1016/j.fuel.2008.02.017
[11]	ZHAO Y P, XU Z, CHEN H, FU Y C, SHEN J Y. Mechanism of chain propagation for the synthesis of polyoxymethylene dimethyl ethers[J]. J Energy Chem, 2013, 22(6):833-836. doi: 10.1016/S2095-4956(14)60261-8
[12]	BURGER J, STRÖFER E, HASSE H. Chemical equilibrium and reaction kinetics of the heterogeneously catalyzed formation of poly(oxymethylene) dimethyl ethers from methylal and trioxane[J]. Ind Eng Chem Res, 2012, 51(39):12751-12761. doi: 10.1021/ie301490q
[13]	CHEN J, SONG H Y, XIA C G, KANG M R, JIN R H. System and method for continuously producing polyoxymethylene dialkyl ethers: AU, 2012268915[P]. 2014-05-15.
[14]	CHEN J, SONG H Y, XIA C G, LI Z. Method for synthesizing polyoxymethylene dimethyl ethers catalyzed by an ionic liquid: US, 0288343[P]. 2011-11-24.
[15]	SCOTT A P, RADOM L. Harmonic vibrational frequencies:An evaluation of Hartree-Fock, Moller-Plesset, quadratic configuration interaction, density functional theory, and semiempirical scale factors[J]. J Phys Chem, 1996, 100(41):16502-16513. doi: 10.1021/jp960976r
[16]	PARLAK C. Theoretical and experimental vibrational spectroscopic study of 4-(1-pyrrolidinuyl) piperidine[J]. J Mol Struct, 2010, 966(1):1-7. http://www.sciencedirect.com/science/article/pii/S0022286009007558
[17]	DIKMEN G, ALVER Ö. NMR, FT-IR, Raman and UV-Vis spectroscopic investigation and DFT study of 6-bromo-3-pyridinyl boronic acid[J]. J Mol Struct, 2015, 1099:625-632. doi: 10.1016/j.molstruc.2015.05.063
[18]	ANDERSSON M P, UVDAL P. New scale factors for harmonic vibrational frequencies using the B3LYP density functional method with the triple-ξ basis set 6-311+G(d, p)[J]. J Phys Chem A, 2005, 109(12):2937-2941. doi: 10.1021/jp045733a
[19]	SONG D Y, CHEN J. Densities and viscosities for ionic liquids mixtures containing[eOHmin][BF4], [bmim][BF4] and[bpy][J]. J Chem Thermodyn, 2014, 77:137-143. doi: 10.1016/j.jct.2014.05.016
[20]	MEHRDAD A, NIKNAM Z. Investigation on the interactions of poly(ethylene oxide) and ionic liquid 1-butyl-3-methyl-imidazolium bromide by viscosity and spectroscopy[J]. J Chem Eng Data, 2016, 61(5):1700-1709. doi: 10.1021/acs.jced.5b00428
[21]	LINTON W H, GOODMAN H H. Physical properties of high molecular weight acetal resins[J]. J Appl Polym Sci, 1959, 1(2):179-184. doi: 10.1002/app.1959.070010208
[22]	GUNBAS G, HAFEZI N, SHEPPARD W L, OLMSTEAD M M, STOYANOVA I V, THAM F S, MEYER M P, MASCAL M. Extreme oxatriquinanes and a record C-O bond length[J]. Nat Chem, 2012, 4(12):1018-1023. doi: 10.1038/nchem.1502
[23]	ALLINGER N L, LⅡ J H, SCHAEFER H F. Molecular mechanics (MM4) studies on unusually long carbon-carbon bond distances in hydrocarbons[J]. J Chem Theory Comput, 2016, 12(6):2774-2778. doi: 10.1021/acs.jctc.5b00926
[24]	SHAIKH M S, SHARIFF A M, BUSTAM M A, MURSHID G. Physicochemical properties of aqueous solutions of sodium glycinate in the non-precipitation regime from 298.15 to 343.15K[J]. Chin J Chem Eng, 2015, 23(3):536-540. doi: 10.1016/j.cjche.2013.11.001
[25]	MAZINANI S, SAMSAMI A, JAHANMIRI A. Solubiity (at low partial pressures), density, viscosity, and corrosion rate of carbon dioxide in blend solutions of monoethanolamine (MEA) and sodium glycinate (SG)[J]. J Chem Eng Data, 2011, 56(7):3163-3168. doi: 10.1021/je2002418
[26]	KUMARI A, SANDEEPA K, KUMAR T P, SATYAVATHI B. Solubility, thermodynamic properties, and derived excess properties of benzoic acid in (acetic acid + water) and (acetic acid + toluene) binary mixtures[J]. J Chem Eng Data, 2016, 61(1):67-77. doi: 10.1021/acs.jced.5b00197
[27]	PHOON L Y, HASHIM H, MAT R, MUSTAFFA A A. Flash point prediction of tailor-made green diesel blends containing B5 palm oil biodiesel and alcohol[J]. Fuel, 2016, 175:287-293. doi: 10.1016/j.fuel.2016.02.027
[28]	PRUGH R W. The relationship between flash point and LFL with application to hybrid mixtures[J]. Process Saf Prog, 2008, 27(2):156-163. doi: 10.1002/(ISSN)1547-5913
[29]	PRAK D J L, COWART J S, TRULOVE P C. Density and viscosity from 293.15 to 373.15K, speed of sound and bulk modulus from 293.15 to 343.15 K, surface tension, and flash point of binary mixtures of bicyclohexyl and 1, 2, 3, 4-tetrahydronaphthalene or trans-decahydronaphthalene at 0.1MPa[J]. J Chem Eng Data, 2016, 61(1):650-661. doi: 10.1021/acs.jced.5b00790
[30]	FLETCHER P D I, ROBERTS N A, URQUHART C. Solubility behavior, crystallization kinetics and pour point:A comparison of linear alkane and triacyl glyceride solute/solvent mixtures[J]. J Ind Eng Chem, 2016, 34:382-389. doi: 10.1016/j.jiec.2015.12.012
[31]	GB 19147-2013, Automobile diesel fuels (V)[S].
[32]	BRANDENBURG A, WAPPLER E, KITA J, MOOS R. Miniaturized ceramic DSC device with strain gauge-based mass detection-first steps to realize a fully integrated DSC/TGA device[J]. Sens Actuators A, 2016, 241:145-151. doi: 10.1016/j.sna.2016.02.011
[33]	JIN X, XU X D, ZHANG X S, YIN Y G. Determination of the PCM melting temperature rang using DSC[J]. Thermochim Acta, 2014, 595:17-21. doi: 10.1016/j.tca.2014.09.004