CN105777502A - Preparation method for double-terminated glycol ether - Google Patents
Preparation method for double-terminated glycol ether Download PDFInfo
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- CN105777502A CN105777502A CN201410812292.9A CN201410812292A CN105777502A CN 105777502 A CN105777502 A CN 105777502A CN 201410812292 A CN201410812292 A CN 201410812292A CN 105777502 A CN105777502 A CN 105777502A
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Abstract
The invention relates to a preparation method for double-terminated glycol ether. The preparation method comprises a step of introducing raw materials containing glycol monoether and monohydric ether alcohol into a reactor for contact and reaction with an acidic molecular sieve catalyst so as to produce double-terminated glycol ether, wherein reaction temperature is 50 to 300 DEG C, reaction pressure is 0.1 to 15 MPa, the mass space velocity of the glycol monoether in the raw materials is 0.01 to 15.0/h, and a mol ratio of monohydric ether alcohol to glycol monoether in the raw materials is 1-100: 1. The preparation method has the advantages that the catalyst has long single-pass life and can be repeatedly regenerated; the target product, i.e., double-terminated glycol ether has high yield and selectivity; energy consumption in separation of products is low; by-products have high economic value; production scale can be large or small; and application of the method is flexible.
Description
Technical field
The application belongs to chemical field, in particular to a kind of double end-blocking glycol ethers
Preparation method.
Background technology
Double end-blocking glycol ethers refer to that the hydrogen on two terminal hydroxy groups of ethylene glycol is replaced the second two of gained by alkyl
Alcohol ether.Double end-blocking glycol ethers do not have active hydrogen, and chemical stability is strong, pour point temperature change low, glutinous
Little, heat-resist, ph stability strengthens, emulsifying capacity is good, the low lipophile of foam strong, anti-coking
Property preferably, have relatively low viscosity and density etc..Therefore, double end-blocking polyglycol ethers are at high-speed spinning silk oil
The fields such as agent, low-foaming detergent, food processing and biofermentation have a wide range of applications.
The preparation of double end-blocking glycol ethers mainly have halogenated hydrocarbons and sodium alkoxide (Williamson synthesis) method and
Directly etherification method, wherein Williamson synthetic method refers to that halogenated hydrocarbons is the most anti-with sodium alkoxide
Should generate ether, it is seriously polluted, operational hazards, economy are relatively low;Directly etherification method refers to by second two
The method that alcohol or ethylene glycol mono-ether are directly etherified with monohydric alcohol or unitary alcohol ether.As glycol monoethyl ether with
Dimethyl ether utilizes anion exchange resin can prepare glycol dimethyl ether (US as catalyst
4321413);Ethylene glycol and methanol utilize perfluorinated sulfonic resin to prepare glycol dimethyl ether as catalyst
(US 2004/0044253).The yield of catalyst, selectivity and life-span that these methods use are the most not
Height, and resin catalyst is difficult to regenerate, and is easily formed substantial amounts of Isosorbide-5-Nitrae-dioxane and high boiling simultaneously
The by-products such as many ethylene glycol bis end-blocking ether of point.
Summary of the invention
An aspect according to the application, it is provided that a kind of method preparing double end-blocking glycol ether, should
Method has catalyst single pass life length and can be with repeated regeneration, the yield of target product and selectivity
Separating energy consumption high, product is low, by-product economic worth height, production scale size, application are clever
The advantage lived.
The method of described preparation double end-blocking glycol ether, it is characterised in that will containing ethylene glycol mono-ether and
The raw material of unitary alcohol ether is passed through reactor and contacts with the catalyst containing acidic molecular sieve and react, and produces
Double end-blocking glycol ethers;
Reaction temperature is 50~300 DEG C, and reaction pressure is 0.1~15MPa;
In described raw material, the mass space velocity of ethylene glycol mono-ether is 0.01~15.0h-1;
In described raw material, unitary alcohol ether is unitary alcohol ether with the mol ratio of ethylene glycol mono-ether: ethylene glycol mono-ether
=1~100:1.
In the application, double end-blocking glycol ethers refer to that the hydrogen on two hydroxyls of ethylene glycol is all replaced by alkyl
The glycol ether of gained.
Preferably, during described ethylene glycol mono-ether is selected from the compound with structural formula shown in formula I extremely
Few one:
R1-O-CH2-CH2-OH Formulas I;
Described unitary alcohol ether is selected from having at least one in the compound of structural formula as shown in Formula II:
R2-O-R2Formula II;
Described double end-blocking glycol ether is selected from having in the compound of structural formula as shown in formula III at least
A kind of:
R1-O-CH2-CH2-O-R2Formula III;
Wherein, R1One in the alkyl that carbon number is 1~20;R2Selected from carbon number it is
One in the alkyl of 1~20.Wherein R1With R2Can be identical, it is also possible to different.
In the application, carbon number be 1~20 alkyl refer to any straight chain alkane that carbon number is 1~20
On hydrocarbon, branched paraffin or naphthene hydrocarbon molecule, lose the group that any one hydrogen atom is formed.
The reaction equation of preparation double end-blocking glycol ether of the application is as follows:
R1-O-CH2-CH2-OH+R2-O-R2=R1-O-CH2-CH2-O-R2+R2-OH formula IV
In theory, ethylene glycol mono-ether and the substituent R of unitary alcohol ether in raw material1And R2Former for any carbon
The various alkyl of subnumber all can realize the reaction of preparation double end-blocking glycol ether in this reaction system.
Those skilled in the art, according to the kind demand of product double end-blocking glycol ether, can choose and have accordingly
Substituent R1、R2Raw material type.Preferably, R1And R2Little independently selected from carbon number
In the alkyl of 10.It is further preferred that R1And R2The alkane of 5 it is not more than independently selected from carbon number
Base.It is further preferred that R1And R2Independently selected from methyl, ethyl, n-pro-pyl, isopropyl,
Normal-butyl.
Preferably, described R1In methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl one
Kind.
Preferably, described R2In methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl one
Kind.
Preferably, described acidic molecular sieve selected from structure type be MWW, FER, MFI, MOR,
One or more in the molecular sieve of FAU, BEA.It is further preferred that the screening of described acidic molecular
From Hydrogen MCM-22 molecular sieve, Hydrogen ferrierite, Hydrogen ZSM-5 molecular sieve, Hydrogen mercerising
One or more in zeolite, Hydrogen Y zeolite, Hydrogen Beta molecular sieve.
Preferably, the atomic ratio of the silicon in described acidic molecular sieve and aluminum is Si/Al=4~140.
Preferably, the described range of reaction temperature upper limit is selected from 200 DEG C, 250 DEG C, 300 DEG C, and lower limit selects
From 50 DEG C, 90 DEG C, 100 DEG C.It is further preferred that described reaction temperature is 100~200 DEG C.
Preferably, described reaction pressure range limit is selected from 8MPa, 10MPa, 15MPa, lower limit
Selected from 0.1MPa, 0.9MPa, 2MPa, 3.5MPa, 4MPa.It is further preferred that it is described
Reaction pressure is 3.5~8MPa.
Preferably, in described raw material, the range limit of the mass space velocity of ethylene glycol mono-ether is selected from 5.0h-1、
10h-1、15h-1, lower limit selects 0.01h-1、0.5h-1、1.5h-1.It is further preferred that described raw material
The mass space velocity of middle ethylene glycol mono-ether is 0.5~5.0h-1。
Preferably, unitary alcohol ether and the mol ratio of ethylene glycol mono-ether, unitary alcohol ether: second in described raw material
The range limit of glycol monoethers is selected from 4:1,5:1,15:1,25:1,50:1,100:1, and lower limit is selected from
1:1、2:1.It is further preferred that unitary alcohol ether with the mol ratio of ethylene glycol mono-ether is in described raw material
Unitary alcohol ether: ethylene glycol mono-ether=1~5:1.
In the application, reaction system can not introduce carrier gas, it is also possible to introduces carrier gas.In reaction system
Introduce carrier gas, the reaction bed temperature fluctuation that the heat effect of reaction system is brought can be buffered, keep
More uniform temperature gradient, is beneficial to improve reaction stability and catalyst life.
Preferably, containing carrier gas in described raw material, described carrier gas is in nitrogen, helium, argon
One or more.
Preferably, described carrier gas volume space velocity is 0~10000h-1.It is further preferred that described load
Air volume air speed is 100~2000h-1。
Preferably, described reactor is one or more fixed bed reactors.Use the shape of successive reaction
Formula.Fixed bed reactors can be one, it is also possible to for multiple.When using multiple fixed bed reactors
Time, to be series, parallel or can connect and the form combined in parallel between reactor.
The beneficial effect that the application can produce at least includes:
A) method provided herein, uses acid molecular sieve catalyst, has single pass life long,
The advantage can reused through repeated regeneration.
B) method provided herein is compared with prior art, and the yield of target product, selectivity are equal
It is obviously improved.
C) method provided herein, does not has water to generate, greatly simplify the rectification of product in product
Purge process, has saved energy consumption.
D) method provided herein, by-product is mainly double end-blocking diethyls that economic worth is the highest
Glycol ethers, diethylene glycol monoether and ethylene glycol, Isosorbide-5-Nitrae-dioxane etc. that economic worth is low
By-product is little, has higher economy.
E) method provided herein, scale of investment scope is big, it is possible to be applicable to the little throwing of medium-sized and small enterprises
Money small-scale production, application is flexibly.
Detailed description of the invention
If no special instructions, the raw material in embodiment and catalyst are all bought by commercial sources.
Analyze method and conversion ratio in embodiment, selectivity is calculated as follows:
Utilize with gas automatic sampling device, fid detector and FFAP capillary column
Agilent7890 gas chromatograph carries out the composition of gas/liquid phase component and automatically analyzes.
In embodiments herein, ethylene glycol mono-ether conversion ratio and product double end-blocking glycol ether with
And by-product selectivity is all based on quality and calculates:
Ethylene glycol mono-ether conversion ratio=[(ethylene glycol mono-ether quality in charging)-(ethylene glycol mono-ether in discharging
Quality)] ÷ (ethylene glycol mono-ether quality in charging) × (100%)
Double end-blocking glycol ether selectivitys=(double end-blocking glycol ether quality in discharging) ÷ is [(in discharging
All ethylene glycol derivative quality)-(unreacted complete ethylene glycol mono-ether quality in discharging)] × (100%)
By-product selectivity=(by-product quality in discharging) ÷ [(all ethylene glycol derivative matter in discharging
Amount)-(unreacted complete ethylene glycol mono-ether quality in discharging)] × (100%)
Above-mentioned all ethylene glycol derivatives refer to containing containing-O-CH in molecular formula2-CH2-O-structure
Material, mainly include the complete ethylene glycol mono-ether of double end-blocking glycol ether, Isosorbide-5-Nitrae-dioxane, unreacted,
Double end-blocking diethylene glycol ethers, diethylene glycol monoether and ethylene glycol.
Below in conjunction with specific embodiment, the application is expanded on further.Only should be understood that these embodiments
For the application being described rather than limiting scope of the present application.
Embodiment 1
By the Hydrogen MCM-22 molecular sieve catalyst of 50g silica alumina ratio (Si:Al)=45:1 in Muffle
The lower 550 DEG C of roastings of air atmosphere of stove 5 hours, take a portion pressed powder pellet, are ground into
20~40 mesh, for active testing.Weigh this Hydrogen MCM-22 molecular sieve catalyst sample 10g,
Load in the stainless steel reaction pipe that internal diameter is 8.5mm, normal pressure, at 550 DEG C little with nitrogen activation 4
Time, then dropping to reaction temperature (being abbreviated as T)=50 DEG C, the mol ratio being passed through raw material is
CH3OCH3:CH3OCH2CH2OH=1:1, reaction pressure (being abbreviated as P)=0.1MPa, second in raw material
Mass space velocity (being abbreviated as the WHSV)=0.01h of glycol monoethers-1, no carrier gas, use gas chromatographic analysis
Product, after stable reaction, calculates ethylene glycol mono-ether conversion ratio and the selectivity of product, reaction condition and
The results are shown in Table 1.
Embodiment 2
Change the reaction condition in embodiment 1 into T=90 DEG C, P=0.9MPa, it is passed through rubbing of raw material
That ratio is CH3CH2OCH3CH2:CH3CH2OCH2CH2OH=2:1, WHSV=0.5h-1, carrier gas
Nitrogen volume space velocity (being abbreviated as GHSV)=100h-1, remaining experimental procedure is consistent with embodiment 1, instead
Answer condition and the results are shown in Table 1.
Embodiment 3
Catalyst in embodiment 1 is changed into Hydrogen ferrierite molecular sieve, Si:Al=15:1, T
=300 DEG C, P=15MPa, the mol ratio being passed through raw material is CH3OCH3:CH3OCH2CH2OH
=100:1, WHSV=15h-1, carrier gas is nitrogen, GHSV=10000h-1, remaining experimental procedure with
Embodiment 1 is consistent, reaction condition and the results are shown in Table 1.
Embodiment 4
Catalyst in embodiment 1 is changed into Hydrogen ferrierite molecular sieve, Si:Al=15:1, T
=250 DEG C, P=10MPa, the mol ratio being passed through raw material is CH3CH2CH2OCH2CH2CH3:
CH3CH2CH2OCH2CH2OH=50:1, WHSV=10h-1, carrier gas is argon, GHSV=5000
h-1, remaining experimental procedure is consistent with embodiment 1, reaction condition and the results are shown in Table 1.
Embodiment 5
Change the catalyst in embodiment 1 into Hydrogen ZSM-5 molecular sieve, Si:Al=140:1, T=
100 DEG C, P=3.5MPa, the mol ratio being passed through raw material is CH3OCH3:CH3OCH2CH2OH=1:1,
WHSV=0.5h-1, remaining experimental procedure is consistent with embodiment 1, and reaction result is shown in Table 1.
Embodiment 6
Change the catalyst in embodiment 1 into Hydrogen ZSM-5 molecular sieve, Si:Al=140:1, T=
150 DEG C, P=5MPa, the mol ratio being passed through raw material is (CH3)2CHOCH(CH3)2:
(CH3)2CHOCH2CH2OH=3:1, WHSV=2.5h-1, carrier gas is nitrogen, GHSV=1000h-1,
Remaining experimental procedure is consistent with embodiment 1, reaction condition and the results are shown in Table 1.
Embodiment 7
Change the catalyst in embodiment 1 into h-mordenite molecular sieve, Si:Al=4:1, T=
200 DEG C, P=8MPa, the mol ratio being passed through raw material is CH3OCH3:CH3OCH2CH2OH=5:1,
WHSV=5h-1, carrier gas is helium, GHSV=2000h-1, remaining experimental procedure and embodiment 1 one
Cause, reaction condition and the results are shown in Table 1.
Embodiment 8
Change the catalyst in embodiment 1 into h-mordenite molecular sieve, Si:Al=4:1, T
=180 DEG C, P=7MPa, the mol ratio being passed through raw material is CH3(CH2)3O(CH2)3CH3:
CH3(CH2)3OCH2CH2OH=4:1, WHSV=4h-1, carrier gas is helium, GHSV=1500h-1,
Remaining experimental procedure is consistent with embodiment 1, reaction condition and the results are shown in Table 1.
Embodiment 9
Catalyst in embodiment 1 is changed into Hydrogen Y molecular sieve, Si:Al=25:1, T=130 DEG C,
P=5MPa, the mol ratio being passed through raw material is CH3OCH3:CH3OCH2CH2OH=2:1, WHSV=2
h-1, no carrier gas, remaining experimental procedure is consistent with embodiment 1, reaction condition and the results are shown in Table 1.
Embodiment 10
Catalyst in embodiment 1 is changed into Hydrogen Y molecular sieve, Si:Al=25:1, T=140 DEG C,
P=6MPa, the mol ratio being passed through raw material is CH3CH2OCH2CH3:CH3CH2OCH2CH2OH
=2.5:1, WHSV=2.5h-1, carrier gas is nitrogen, GHSV=500h-1, remaining experimental procedure and reality
Execute example 1 consistent, reaction condition and the results are shown in Table 1.
Embodiment 11
Catalyst in embodiment 1 is changed into Hydrogen Beta molecular sieve, Si:Al=20:1, T=230 DEG C,
P=2MPa, the mol ratio being passed through raw material is CH3OCH3:CH3OCH2CH2OH=15:1,
WHSV=9h-1, carrier gas is nitrogen, GHSV=3000h-1, remaining experimental procedure and embodiment 1 one
Cause, reaction condition and the results are shown in Table 1.
Embodiment 12
Catalyst in embodiment 1 is changed into Hydrogen Beta molecular sieve, Si:Al=20:1, T=220 DEG C,
P=3MPa, the mol ratio being passed through raw material is CH3CH2OCH2CH3:CH3CH2OCH2CH2OH
=25:1, WHSV=6h-1, carrier gas is nitrogen, GHSV=1000h-1, remaining experimental procedure and enforcement
Example 1 is consistent, reaction condition and the results are shown in Table 1.
The catalytic reaction condition of table 1 embodiment 1~12 and result
Note: other by-products the most double end-blocking diethylene glycol ether, diethylene glycol monoether and ethylene glycol
Comparative example 1
50g is bought from E.I.Du Pont Company's perfluorinated sulfonic resin (Nafion-H) in air dry oven,
Air atmosphere lower 105 DEG C dry 12 hours, weigh after cooling 10g load internal diameter be 8.5mm not
For active testing in rust steel reaction tube, normal pressure, at 100 DEG C with nitrogen activation 1 hour, then
Reaction temperature (being abbreviated as T)=130 DEG C, being passed through material molar ratio is
CH3OCH3:CH3OCH2CH2OH=2:1, reaction pressure (being abbreviated as P)=5MPa, dimethoxym ethane quality
Air speed (being abbreviated as WHSV)=2h-1, no carrier gas, use gas chromatographic analysis product, after stable reaction,
Calculate ethylene glycol mono-ether conversion ratio and the selectivity of product, reaction condition and the results are shown in Table 2.
Comparative example 2
Change the reaction condition in comparative example 1 into T=140 DEG C, P=6MPa, it is passed through rubbing of raw material
That ratio is CH3CH2OCH2CH3:CH3CH2OCH2CH2OH=2.5:1, WHSV=2.5h-1, carry
Gas is nitrogen, GHSV=500h-1, remaining experimental procedure is consistent with comparative example 1, reaction condition and knot
Fruit is shown in Table 2.
Comparative example 3
Catalyst in comparative example 1 is changed into the styrene-two buying the sulfonation from Rhom and Hass
Ethenylbenzene copolymer (Amberlyst-15) resin, remaining experimental procedure is consistent with comparative example 1, instead
Answer condition and the results are shown in Table 2.
Comparative example 4
Catalyst in comparative example 2 is changed into the styrene-two buying the sulfonation from Rhom and Hass
Ethenylbenzene copolymer (Amberlyst-15) resin, remaining experimental procedure is consistent with comparative example 2, instead
Answer condition and the results are shown in Table 2.
Comparative example 5
Catalyst in comparative example 1 is changed into the sulfonation bought from Dandong Mingzhu Special Type Resin Co., Ltd.
Styrene-divinylbenzene copolymer storng-acid cation exchange resin (D005), remaining experimental procedure
Consistent with comparative example 1, reaction condition and the results are shown in Table 2.
Comparative example 6
Catalyst in comparative example 2 is changed into the sulfonation bought from Dandong Mingzhu Special Type Resin Co., Ltd.
Styrene-divinylbenzene copolymer storng-acid cation exchange resin (D005), remaining experimental procedure
Consistent with comparative example 2, reaction condition and the results are shown in Table 2.
The catalytic reaction condition of table 2 comparative example 1~6 and result
Note: other by-products the most double end-blocking diethylene glycol ether, diethylene glycol monoether and ethylene glycol
Embodiment 13
Respectively the catalyst after one way reaction inactivation in embodiment 1,3,5,7,9,11 is taken out again
Raw, regeneration condition is the lower 550 DEG C of roastings of air atmosphere 4 hours, and the catalyst after regeneration is pressed respectively
Reaction condition according to former embodiment repeats reaction.Reaction result is shown in Table 3.
Reaction result contrast before and after catalytic regeneration in table 3 embodiment
Resin catalyst in comparative example 1~6 cannot regenerate.
The above, be only several embodiments of the application, and the application not does any type of limit
System, although the application with preferred embodiment disclose as above, but and be not used to limit the application, any
Those skilled in the art, in the range of without departing from technical scheme, utilize above-mentioned taking off
The technology contents shown makes a little variation or modification is all equal to equivalence case study on implementation, belongs to technology
In aspects.
Claims (10)
1. the method producing double end-blocking glycol ether, it is characterised in that will be containing ethylene glycol list
Ether is passed through reactor with the raw material of unitary alcohol ether and contacts with the catalyst containing acidic molecular sieve and react,
Produce double end-blocking glycol ether;
Reaction temperature is 50~300 DEG C, and reaction pressure is 0.1~15MPa;
In described raw material, the mass space velocity of ethylene glycol mono-ether is 0.01~15.0h-1;
In described raw material, unitary alcohol ether is unitary alcohol ether with the mol ratio of ethylene glycol mono-ether: ethylene glycol mono-ether
=1~100:1.
Method the most according to claim 1, it is characterised in that
At least one in the compound with structural formula shown in formula I of described ethylene glycol mono-ether:
R1-O-CH2-CH2-OH Formulas I;
Described unitary alcohol ether is selected from having at least one in the compound of structural formula as shown in Formula II:
R2-O-R2Formula II;
Described double end-blocking glycol ether is selected from having in the compound of structural formula as shown in formula III at least
A kind of:
R1-O-CH2-CH2-O-R2Formula III;
Wherein, R1One in the alkyl that carbon number is 1~20;R2Selected from carbon number it is
One in the alkyl of 1~20.
Method the most according to claim 2, it is characterised in that described R1Selected from methyl, second
One in base, n-pro-pyl, isopropyl, normal-butyl;Described R2Selected from methyl, ethyl, positive third
Base, isopropyl, the one of normal-butyl.
Method the most according to claim 1, it is characterised in that described acidic molecular sieve is selected from
Structure type be the one in the molecular sieve of MWW, FER, MFI, MOR, FAU, BEA or
Multiple.
Method the most according to claim 1, it is characterised in that described acidic molecular sieve contains
Hydrogen MCM-22 molecular sieve, Hydrogen ferrierite, Hydrogen ZSM-5 molecular sieve, Hydrogen mercerising boil
One or more in stone, Hydrogen Y zeolite, Hydrogen Beta molecular sieve.
6. according to the method described in claim 1 or 4 or 5, it is characterised in that described acidity is divided
In son sieve, the atomic ratio of silicon and aluminum is Si/Al=4~140.
Method the most according to claim 1, it is characterised in that described reaction temperature be 100~
200 DEG C, described reaction pressure is 3.5~8MPa;
In described raw material, the mass space velocity of ethylene glycol mono-ether is 0.5~5.0h-1;
In described raw material, unitary alcohol ether is unitary alcohol ether with the mol ratio of ethylene glycol mono-ether: ethylene glycol mono-ether
=1~5:1.
Method the most according to claim 1, it is characterised in that containing carrier gas in described raw material,
Described carrier gas volume space velocity is 0~10000h-1;Described carrier gas is in nitrogen, helium, argon
One or more.
Method the most according to claim 8, it is characterised in that described carrier gas volume space velocity is
100~2000h-1。
Method the most according to claim 1, it is characterised in that described reactor be one or
Multiple fixed bed reactors.
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Cited By (1)
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CN111233638A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院大连化学物理研究所 | Synthesis method of end-capped glycol dimethyl ether |
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US4321413A (en) * | 1981-01-30 | 1982-03-23 | Texaco Inc. | Production of ethylene glycol dialkyl ethers using dialkyl ethers |
US4579980A (en) * | 1982-11-05 | 1986-04-01 | Nippon Soda Co. Ltd. | Process for producing ether compounds |
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US4321413A (en) * | 1981-01-30 | 1982-03-23 | Texaco Inc. | Production of ethylene glycol dialkyl ethers using dialkyl ethers |
US4579980A (en) * | 1982-11-05 | 1986-04-01 | Nippon Soda Co. Ltd. | Process for producing ether compounds |
JP2012149033A (en) * | 2010-12-27 | 2012-08-09 | Nippon Nyukazai Kk | Method for producing (poly)alkylene glycol diether |
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CN111233638A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院大连化学物理研究所 | Synthesis method of end-capped glycol dimethyl ether |
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