第 45 卷 第 7 期 燃 料 化 学 学 报 Vol．45 No．7

2017 年 7 月 Journal of Fuel Chemistry and Technology Jul． 2017

文章编号： 0253-2409（ 2017） 07-0837-09

Synthe sis and physicoche mical characte rization of

polyoxyme thyle ne dime thyl e the rs
KANG M ei-rong 1 ，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）

Abstract： Polyoxymethylene dimethyl ethers （ H3 CO（ CH2 O） n CH3 ，PODE n or DM M n ，n ≥ 2） w ith unique physical and chemical
properties are a potential additive for diesel fuels，w hich can effectively enhance the combustion efficiency and reduce the emission
of pollutants． In this w ork，a series of pure PODE n components （ n = 2－5） w ere synthesized from methylal and trioxymethylene and
obtained w ith high purity through collaborative separation； their structure and properties w ere characterized by NM Ｒ，FT-IＲ，
Ｒaman，and DFT calculation and a detailed assignment of the expressions in the spectrogram to the various groups w as performed．
The density and viscosity of PODE n w ere measured at 298．15－323．15 K． The results indicate that the density and viscosity of PODE n
decrease gradually w ith the increase of temperature． M eanw hile，w ith the increase in the number of －CH2 O－ 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 ．
Ke y words： polyoxymethylene dimethyl ethers； synthesis； structural characterization； physicochemical property
CLC numbe r： O621．2； TQ519 Docume nt code ： A

Polyoxymethylene dimethyl ethers （ H 3 CO
（ CH 2 O） n CH 3 ，PODE n or DM M n ，n ≥ 2 ） are a
series of polyether compounds w ith the smell of
chloroform． They are similar in structure to methylal
（ viz．，DM M or DM M 1 ） and can be obtained by
inserting oxymethylene groups （ － CH 2 O － ） into the
methylal molecule［1，2］． PODE n are provided w ith
some unique physicochemical properties such as low
toxicity，excellent volatility，low condensation point，
great permeating ability，good solubilizing pow er and
miscibility w ith most organic compounds and w ater；
the solubilities of PODE 2 and PODE 3 in w ater at 20 ℃
are 30% and 28% by mass，respectively［3，4］． PODE n
also exhibit high oxygen content （ 42% － 51%） and
cetane number （ ＞ 63 ） ［5］； as a promising diesel
additive， they can improve the combustibility of
diesel， enhance the efficiency of combustion and
reduce the release of pollutants ［6－9］． To the best of
our know ledge，PODE n w ith n varying from 3 to 8
performed excellently as an oil additive，w ith very
high cetane number （ ≥ 76） ，moderate boiling point，
high flash point，and excellent miscibility w ith diesel
oil． Such outstanding advantages give PODE 3－8 higher
efficiency in combustion and more convenience in
storage and transportation， in comparison w ith
methylal w hich has a low er boiling point［10］．
Especially， the physicochemical properties of
PODE 3－8 matched w ell w ith that of diesel oil and
could be blended directly into diesel w ithout any
change in the engine infrastructure［11］； they have been
considered as a potential diesel additive to further
improve energy efficiency［12］． Furthermore，PODE n
w ith good solubility could also be used as a substitute
for some toxic organic compounds in industry and
have received extensive attention in various
applications．
The catalysts and processes used for the synthesis
of PODE n have been widely studied in the world；
however，the physicochemical properties are rarely
reported so far． It is necessary to accumulate enough
data for chemical research and industrial application． In
this work，therefore，a series of 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． The basic physicochemical properties
including density，viscosity，flash point，pour point
and thermal properties of PODE n monomers （ n = 2 －
5） were then determined．
1 Expe rime ntal
1．1 Synthe sis and se paration of PODE n
PODE n w ere synthesized w ith methylal and

Ｒeceived： 2017-03-30； Ｒevised： 2017-05-12．

*
Corresponding author． Tel / Fax： +86-931-4968068，E-mail： chenj@ licp．cas．cn．
The project w as supported by the National Natural Science Foundation of China （ 21473225） ．
国家自然科学基金（ 21473225） 资助
本文的英文电子版由 Elsevier 出版社在 ScienceDirect 上出版（ http： / / w w w ．sciencedirect．com / science / journal /18725813） ．
 838 燃 料 化 学
trioxymethylene as the raw materials at 413．15 K and
2．0 M Pa in N 2 for 2 h，w ith the functional ionic liquid
as catalyst，as described in the literature［13，14］． After
reaction，PODE n（ n = 1 － 8） w ere produced，as listed
in Figure 1； the ionic liquid w as then separated from
the reaction mixture by centrifugation and the mixed
products of PODE n （ n = 2 to 5 ） w ere isolated by
distillation．
Figure 1 Synthesis of PODE n from
methylal and trioxymethylene
To get the single component of PODE n（ n = 2 to
5） ，a rectifying column w ith 40 theoretical plates w as
used to separate the mixture． The single component
compounds w ere identified by gas chromatography-
mass spectrometry （ GC-M S ） （ Agilent 7890A /
5975C） and quantitatively analyzed by GC （ Agilent
6890 equipped w ith a SE-54 capillary column） ． The
mass fraction purities of the final PODE n samples
proved to be better than 0．999．
1．2 Physicochemical characterization of PODE n
The 1 H NM Ｒ and 13 C NM Ｒ spectra in C 6 D 6
w ere recorded on an Avance TM III-400M Hz NM Ｒ
spectrometer using tetramethylsilane （ TM S ） as an
internal standard at the same time． The FT-IＲ spectra
w ere recorded on a Nexus 870 infrared spectrometer
w ith a resolution of 0．125 cm －1 at room temperature，
using the KBr pellet technique． The Ｒaman spectra
w ere collected at room temperature on an InVia
Ｒaman microscopic spectrometer w ith 1 cm －1
resolution； the excitation source w as a diode laser
operating at 532 nm．
The molecular structure and the FT-IＲ and
Ｒaman spectra of PODE n w ere speculated by density
functional theory （ DFT / B3LY ） w hich can provide
the vibration frequency［15－17］． After the full
optimization of the PODE n molecular geometry，the
theoretical calculation w as then conducted under the
conditions of room temperature and vacuum． The
optimization of structure and energy w as performed at
the level of B3LYP /6-311 +G （ d，p） using Gaussian
09 softw are package； a scaling factor of 0．961 3 w as
used for the calculation of vibration frequency［18］．
The density and viscosity of PODE n （ n = 2，3，
4，5） w ere determined on an Anton Paar Stabinger
SVM 3000 rotational automated viscometer at 293．15 －
323． 15 K w ith an uncertainty of ± 0． 02 K． The
equipment w as calibrated w ith ethanol before each
学 报 第 45 卷
measurement． The average of three measurements w as
reported； the overall accuracies of density and
viscosity measurements at ambient pressure w ere
better than ±5 × 10 －4 g / cm 3 and ±4%，
［19］
respectively ．
The flash points w ere measured using a FP56
5G2 Tag closed-cup apparatus under （ 298 ± 0． 1） K
and atmospheric pressure． The flash tester conformed
to standards of ASTM D93，D1310，D3828，D3278，
and D3941， as specified by the manufacturer． To
ensure an acceptable precision， the dynamic flash
point test method of D3941 w as employed according
to the physicochemical property of PODE n ， from
w hich the deviation w as determined．
The pour points of all samples w ere measured on
a PAC-70X PHASE automatic analyzer that has a
specified accuracy of ± 0． 1 K． The measurement w as
conducted according to ASTM D-5949 and the
uncertainty of the pour point measurement complied
w ith the testing standard．
Differential scanning calorimetry （ DSC ） w as
performed on a DSC200F3 TA instrument． The
accuracy of temperature and enthalpy w as ±0．1 K and
± 0．1%， respectively， as specified by the
manufacturer． The PODE n samples w ere w eighed
inside hermetically sealed Al 2 O 3 crucibles w ith a
pinhole on the lid． The sample pan w as placed in the
calorimeter and subjected to the temperature
programming in nitrogen，viz．，cooling from room
temperature to below the freezing point at 10 K / min，
and then heating to above the melting point at
10 K / min．
2 Ｒe sults and discussion
2．1 Characte rization of PODE n
From the 1 H NM Ｒ （ 400 M Hz，BENZENE-D 6 ）
13
and C NM Ｒ （ 100 M Hz，BENZENE-D 6 ） spectra of
PODE n（ n = 2，3，4，5） ，follow ing information w as
acquired： PODE 2 ，δ 3． 11 （ s，6H） ，4． 37 （ s，4H） ，
55．07，92． 77； PODE 3 ，δ 3． 12 （ s，6H） ，4． 58 （ s，
4H） ，4．78（ s，2H） ，55．14，87．86，93．25； PODE 4 ，
δ 3．11（ s，6H） ，4．57（ s，4H） ，4．78（ s，4H） ，55．16，
88．35，93．28； PODE 5 ，δ3．10（ s，6H） ，4．57（ s，4H） ，
4．80（ s，4H） ，4．83（ s，2H） ，55．26，88．41，88．87，
93．34． No impurity peaks are observed．
The FT-IＲ and Ｒaman spectra of PODE n（ n = 2，
3，4， 5 ） are show n in Figure 2 and Figure 3，
respectively． All PODE n are similar in the
characteristics of spectrogram due to their analogous
molecular structures． In the FT-IＲ and Ｒaman
spectra，the absorption peaks at 2 950 － 2 970 cm －1 are
attributed to asymmetric methyl （ CH 3 － ） stretching
vibrations， w hereas the peaks around 2 900 －
第7期 KANG Mei-rong et al： Synthesis and physicochemical characterization of …… 839

2 960 cm －1 to the asymmetric methylene （ －CH 2 － ）
stretching vibrations． The symmetrical methyl （ CH 3
－ ） and methylene （ － CH 2 － ） stretching vibrations
appear at 2 820 － 2 910 and 2 780 － 2 830 cm －1 ，
respectively［20］． The deformation frequencies of
methyl （ CH 3 － ） and methylene （ － CH 2 － ） are
observed in the range of 1 420 － 1 480 and 1 390 －
1 480 cm －1 ，respectively． There are several C － O
functional groups in the PODE n molecules w ith
different electronic environments； the strong peaks
detected at 940 － 1 230 cm －1 in the FT-IＲ spectra and
910 cm －1 in the Ｒaman spectra are assigned to C － O
stretching vibrations．

Figure 2 FT-IＲ spectra of PODE n

（ a） ： PODE2 ； （ b） ： PODE3 ； （ c） ： PODE4 ； （ d） ： PODE5

The vibration frequency，FT-IＲ intensity and
Ｒaman scattering activity calculated by DFT for
PDOE n are given in Table 1， w ith the detailed
assignment of various radicals． There is often a
deviation betw een the DFT theoretical calculation and
actual measurement，because the simulation w orked
under vacuum conditions，w hereas the measurement
w as conducted under atmospheric conditions． As
given in Table 1，most calculated spectra are in good
agreement w ith the experimental ones． There are also
some shifts in theoretical calculation peaks and each
compound has the same shift rule． In addition，some
of the observed C － O stretches are obviously
distinguished w ith the calculated data， w hile the
observed C － H stretches are in better agreement w ith
the calculated data． The intermolecular and
intramolecular interactions may be used to explain
these phenomena． First， the theoretical calculation
considers only a single isolated molecule and does not
take into account the intermolecular interaction in
liquid environment． Second， since the PODE n
molecule has multiple C － O bonds and tw o methyl
capping ends， w hich locate in different local
environments． The electron environments of C － O are
more complicated than that of C － H and the external
factors may have a greater influence on C －O than that
on C － H，leading to distinguished C － O stretches in
calculation． M oreover，the calculated intensity profile
does not match w ell w ith the experimental spectrum，
w hich may also be ascribed to the impact of the
neighboring molecules on the vibration frequency．
840 燃 料 化 学 学 报 第 45 卷

Figure 3 Ｒaman spectra of PODE n

（ a） ： PODE2 ； （ b） ： PODE3 ； （ c） ： PODE4 ； （ d） ： PODE5

Table 1 Comparison of the e xpe rime ntal and calculate d vibration wave numbe r
and the assignme nt of various radicals in PODE n
Calculated w ave Experimental w ave
PODE n FT-IＲ intensity Ｒaman activity Assignment
number σ / cm －1 number σ / cm －1
PODE2 1 093．1 1 008．0 584．4 υ C－O
1 126．6 1 141．5 214．5 υ C－O
1 208．8 911．0 19．6 υ C－O
1 374．1 124．6 δs CH 3
1 419．9 10．2 δ CH 2
1 429．5 1 450．2 21．9 δ CH 2
1 429．6 18．9 δas CH 3
1 491．2 1 475．2 12．7 δ CH 3
2 779．4 2 834．6 131．0 146．4 υs CH 2
2 791．5 2 903．3 219．2 114．2 υs CH 3
2 859．3 2 910．7 315．2 υs CH 3
2 858．5 2 938．5 80．6 υas CH 2
2 901．2 2 958．7 123．5 υas CH 3
2 901．2 2 955．6 87．2 υas CH 2
3 006．1 2 966．3 111．4 υas CH 3
PODE3 1 091．1 935．0 957．9 υ C－O
1 096．8 973．4 175．6 υ C－O
1 209．7 911．0 30．8 υ C－O
1 368．9 1 390．1 187．6 δs CH 3
1 430．6 1 451．8 18．6 δ CH 2
1 437．0 1 469．0 15．2 δas CH 3
第7期 KANG Mei-rong et al： Synthesis and physicochemical characterization of …… 841

续表 1

Calculated w ave Experimental w ave

PODE n FT-IＲ intensity Ｒaman activity Assignment
number σ / cm －1 number σ / cm －1
1 430．5 1 453．7 22．1 δ CH 2
1 494．0 1 481．8 16．8 δ CH 3
2 790．5 2 781．0 180．9 υs CH 2
2 798．4 2 826．1 176．9 υs CH 3
2 859．5 2 898．7 89．8 υas CH 2
2 783．9 2 824．7 171．9 υs CH 2
2 859．9 2 906．8 321．9 υs CH 3
2 902．4 2 954．6 123．2 υas CH 3
2 902．3 2 954．6 50． 7 υas CH 2
3 007．2 2 997．6 209． 6 υas CH 3
PODE4 1 082．3 960．0 1 457．0 υ C－O
1 123．5 1 107．2 149．2 υ C－O
1 137．7 1 169．7 79．9 υ C－O
1 212．8 911．0 32． 3 υ C－O
1 365．8 1 389．4 244．1 δs CH 3
1 428．2 1 452．6 15．0 δ CH 2
1 430．8 1 469．6 11．8 δas CH 3
1 430．8 1 454．6 13．9 δ CH 2
1 494．2 1 481．0 19．4 δ CH 3
2 768．6 2 827．8 46．4 υs CH 2
2 791．4 2 782．5 196．7 υs CH 2
2 860．4 2 936．5 319．5 υs CH 3
2 801．0 2 826．7 292．4 υs CH 3
2 860．2 2 901．1 108．4 υas CH 2
2 903．1 2 955．7 36．9 υas CH 3
2 903．1 2 936．5 81．8 υas CH 2
3 007．5 2 965．2 105．3 υas CH 3
PODE5 1 074．7 939．6 1870．7 υ C－O
1 124．5 1 109．0 192．2 υ C－O
1 214．2 911．0 26．4 υ C－O
1 364．7 1 484．3 17．0 δ CH 2
1 364．7 1 391．0 300．8 δs CH 3
1 430．1 1 417．0 11．0 δ CH 2
1 431．1 1 470．0 11．7 δas CH 3
1 493．9 1 455．6 20．6 δ CH 3
2 795．4 2 826．5 104．7 υs CH 2
2 795．4 2 784．6 175．9 υs CH 2
2 796．2 107．5
2 797．3 112．4
2 797．3 383．5
2 805．3 101．6
2 805．3 2 827．0 310．8 υs CH 3
2 860．2 2 902．4 125．2 υas CH 2
2 860．4 2 911．7 311．4 υs CH 3
2 903．3 2 945．4 69．7 υas CH 2
2 903．3 2 957．6 59．7 υas CH 3
3 007．7 2 970．0 106．1 υas CH 3
 842 燃 料 化 学 学 报 第 45 卷

2．2 Physicoche mical prope rtie s of PODE n compounds is tighter than that of the corresponding
The density of PODE n at various temperatures is hydrocarbons［22，23］． Figure 4 show s the density curves
summarized in Table 2． Obviously， PODE n have of PODE n （ n = 2 to 5 ） versus temperature． The
higher density than alkanes w ith the same chain density of PODE n decreases almost linearly w ith the
length［21］，w hich is mainly ascribed to that the C － O increase of temperature from 298． 15 to 323． 15 K，
bond （ 0． 143 nm ） is shorter than the C － C bond w hereas increases gradually w ith the increase of chain
（ 0．154 nm） and the molecular skeleton of polyether length （ n） ．
Table 2 De nsity of PODE n unde r diffe re nt te mpe rature s
Density ρ / （ g·cm －3 ）
PODE n
298．15 K 303．15 K 308．15 K 313．15 K 318．15 K 323．15 K
PODE2 0．962 2 0．956 8 0．951 1 0．945 2 0．939 4 0．933 4
PODE3 1．022 0 1．016 8 1．011 6 1．006 3 1．001 0 0．996 0
PODE4 1．067 1 1．062 0 1．056 9 1．051 9 1．046 9 1．041 8
PODE5 1．098 7 1．093 8 1．089 0 1．084 1 1．079 2 1．074 4

Table 3 Viscosity of PODE n unde r diffe re nt te mpe rature s

Viscosity μ / （ mPa·s）
PODE n
298．15 K 303．15 K 308．15 K 313．15 K 318．15 K 323．15 K
PODE2 0．680 9 0．641 2 0．605 5 0．569 1 0．539 5 0．511 2
PODE3 1．133 3 1．054 8 0．978 4 0．916 8 0．861 0 0．811 5
PODE4 1．880 5 1．715 3 1．573 3 1．501 5 1．403 1 1．237 3
PODE5 2．932 9 2．626 7 2．381 0 2．147 5 1．958 3 1．794 6

point is the highest temperature below w hich the flow

Figure 4 Temperature dependence of density for PODE n
■： PODE 2 ； ●： PODE 3 ； ▲： PODE 4 ； ▼： PODE 5
of the sample is not observed w hen the vessel is tilted
from vertical to horizontal［30］． As given in Table 4，
the flash point of PODE n increases gradually w ith the
increase of molecular w eight． As the flash point of
diesel is in general higher than 328．1 K，some low er
than the flash point of PODE n w ith n ＞ 3． The pour
point of PODE n also increases gradually w ith the
increase in the number of －CH 2 O － units （ n = 2 － 5） ；
in general，the pour point of PODE n （ n = 2，3 and
4） is low er than that of the automobile diesel fuels V
of Chinese standard （ 273．1 K ） ． In summary， the
properties of PODE n are strongly related to the chain
length （ n） ．

The viscosity of PODE n （ n = 2 to 5 ） under

different temperatures are given in Table 3 and
Figure 5． Notably，the viscosity of PODE n increases
w ith the grow th of chain length and decreases w ith the
increase of temperature （ from 298．15 to 323．15 K ） ，
similar to their density，w hich may also be explained
by the increase of intermolecular distance and the
decrease of intermolecular attraction w ith the increase
of temperature［24－26］． The flash point and pour point
are important information to characterize the
combustibility of the liquid fuels and convenience in
the storage and transportation． The flash point is the
low est temperature above w hich the vapor-air mixture Figure 5 Temperature dependence of viscosity for PODE n
■： PODE 2 ； ●： PODE 3 ； ▲： PODE 4 ； ▼： PODE 5
can be ignited by a spark［27－29］，w hereas the pour
第7期 KANG Mei-rong et al： Synthesis and physicochemical characterization of …… 843

The DSC technique is pow erful for the 2 to 5． It is know n that the DSC profiles w ere
thermodynamic characterization of materials in a influenced by the heating / cooling rate and the mass of
thermal activated process［32］． The freezing and melting sample［33］． During the cooling process， the onset
profiles are shown in Figure 6 and the transition temperature （ T o ） as the freezing point may
temperature and enthalpy are reported in Table 5． overestimate the real values． The difference betw een
the melting onset temperature and the cooling onset
Table 4 Flash point and pour point of PODE n
temperature becomes smaller w ith the increase of
Sample Flash point T / K Pour point T / K
chain length in PODE n ，w hich is related to the nature
PODE2 289．1 219．1
of sample and the test procedure． PODE n （ n = 2 to 5）
PODE3 293．1 228．1
are volatile organic liquid at room temperature and the
PODE4 350．1 261．1
volatility becomes stronger w ith decrease of chain
a
PODE5 376．1 291．1 length． During the temperature programming，because
b b
Diesel ＞ 328．1 ＜ 273．1 b of its stronger volatility，PODE 2 inside the crucibles
a
： flash point of PODE5 w as measured by TM A 5 automatic suffered from a greater change in the pressure than
closed-cup apparatus according to GB / T 261-2008， as it PODE 3－5 ，although there w as a pinhole on the lid of
exceeded the measuring range of FP56 5G2 Tag closed-cup
crucible． The pressure has an impact on the melting
apparatus； b ： data w ere cited from reference［31］
and cooling onset temperature； the melting point is
Obviously， there are a absorbed latent heat higher w hen measured at higher pressure． As a result，
during the heating process and a released latent heat the difference betw een melting and cooling onset
during the cooling process for PODE n （ n = 2 to 5） ； temperatures becomes small w ith the increase in chain
the absorbed latent heat and released latent heat of length of PODE n ．
PODE n increase gradually w ith the increase of n from

Figure 6 DSC profiles of PODE n

（ a） ： PODE2 ； （ b） ： PODE3 ； （ c） ： PODE4 ； （ d） ： PODE5

M eanw hile，the mass loss of the PODE n samples completely closed system． During the measurement，
also becomes larger w ith the decrease of the samples w ere cooled first and then heated to a
polymerization degree （ smaller n value） in a non － specified temperature． The mass loss of the samples in
 844 燃 料 化 学 学 报 第 45 卷

the heating process w as larger than that in the cooling values of transition enthalpy from the melting
process and the mass loss w ould also be larger at a processes in Table 5 are larger than those obtained
slow er heating / cooling rate． Therefore，the absolute from the cooling processes．
Table 5 The rmal characte ristics of PODE n
Onset temp． Peak temp． Endset temp． Temp． rang Transition enthalpy
Proces PODE n －1
To / K Tp / K Te / K T e －T o / K ΔH / （ J·g ）
M elting PODE2 200．7 206．0 209．4 281．8 74．2
PODE3 228．7 237．7 243．4 287．8 112．4
PODE4 260．4 272．5 278．5 291．3 135．4
PODE5 286．3 300．4 305．9 292．7 182．5
Solidifying PODE2 170．3 169．3 167．1 269．9 -54．7
PODE3 215．9 213．8 208．9 266．1 －95．6
PODE4 246．6 244．6 239．1 265．7 －131．7
PODE5 276．6 271．2 263．6 260．2 －179．5

3 Conclusions The results indicate that the density and viscosity

A series of pure PODE n components （ n = 2 － 5）
w ere synthesized from methylal and trioxymethylene
and obtained w ith high purity through collaborative
separation； their structure and properties w ere
characterized by NM Ｒ，FT-IＲ，Ｒaman，and DFT
calculation． A detailed assignment of expressions in
the spectrogram to the various groups w as also
performed． The density and viscosity of PODE n w ere
measured at 298．15 － 323．15 K．
of PODE n decrease gradually w ith the increase of
temperature． M eanw hile， w ith the increase in the
number of － CH 2 O － 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 w ith the increase in the chain length． All
these results are very important to the practical
synthesis and application of PODE n ．

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聚甲氧基二甲醚的合成及其物理化学性质表征
1 1，
2 1，
2 1，*
康美荣 ，宋河远 ，金福祥 ，陈静
（ 1．中国科学院兰州化学物理研究所，羰基合成与选择氧化国家重点实验室，甘肃 兰州 730000；
2．中国科学院大学，北京 100049）

摘 要： 聚甲氧基二甲醚（ H3 CO（ CH2 O） n CH3 ，PODE n 或 DM M n ，n ≥ 2） 具有独特的物理化学性质； 作为一种柴油添加剂，可

以有效提高油品燃烧效率并达到节能减排的目的。首先合成了一系列聚合度 n 为 2、
3、4 和 5 单一组分的聚甲氧基二甲醚，采
用 NM Ｒ、FT-IＲ、Ｒaman 和 DFT 计算等手段对每个聚甲氧基二甲醚单体的化学结构进行表征，并对其在 298．15－323．15 K温度
的密度和黏度进行了测试。结果表明，聚甲氧基二甲醚的密度和黏度随着温度的升高而逐渐降低，随着聚合度的增加而逐渐
升高。同时，聚甲氧基二甲醚 PODE n（ n = 2－5） 的闪点和倾点以及溶解热和凝固热均随着聚合度的增加而提高。
关键词： 聚甲氧基二甲醚； 合成； 结构表征； 物理化学性质
中图分类号： O621．2； TQ519 文献标识码： A