CN105294411B - The method that polyoxymethylene dimethyl ethers are produced by paraformaldehyde - Google Patents
The method that polyoxymethylene dimethyl ethers are produced by paraformaldehyde Download PDFInfo
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Abstract
The present invention relates to a kind of method that polyoxymethylene dimethyl ethers are produced by paraformaldehyde, mainly solve the problems, such as that conventional catalyst reaction efficiency is low, metaformaldehyde is that cost of material is higher.The present invention by with methyl alcohol, dimethoxym ethane and paraformaldehyde as raw material, wherein methyl alcohol：Dimethoxym ethane：The mass ratio of paraformaldehyde is (0~10): (0~10): 1, wherein methyl alcohol and the consumption of dimethoxym ethane can not be simultaneously 0, it it is 70~200 DEG C in reaction temperature, reaction pressure is under the conditions of 0.2~6MPa, raw material is contacted with catalyst, reaction generation polyoxymethylene dimethyl ether, catalyst amount for raw material weight 0.05~10%, wherein catalyst used in terms of weight fraction including following components：A) 30~80 parts of conjugation microporous polymer carrier (CMPs)；B) 20~70 parts of technical schemes of solid super-strong acid, preferably solve the problem, can be used in the industrial production of polyoxymethylene dimethyl ether.
Description
Technical field
The present invention relates to a kind of method that polyoxymethylene dimethyl ethers are produced by paraformaldehyde, especially with regard to one kind with poly
Formaldehyde is the method for Material synthesis polyoxymethylene dimethyl ether.
Background technology
In recent years, with industrial revolution influence increasingly deeply and China's distinctive " many coals, few oil, there is gas " resource grid
Office, China's oil resource growing tension, oil supply pressure unprecedentedly increases.It is estimated following 10~20 years, China's oil supply rate
Only~50%.How the energy crisis for solving China using the coal resources of China's abundant is become as researcher is badly in need of solving
Problem certainly.Therefore the attention that new oil product substitute is increasingly subject to people is developed by coal-based methanol.
Dimethyl ether is proposed as a kind of procetane earliest, yet with its own cold starting performance is poor, normal temperature
Lower vapour pressure is high, easy generation vapour lock causes that dimethyl ether is significantly raised as the cost of vehicle alternative fuel.Polyoxymethylene dimethyl ether,
That is Polyoxymethylene dimethyl ethers (PODE), are the common names of a class material, and its skeleton symbol can be expressed as
CH3O(CH2O)nCH3, with octane number higher (>30) with oxygen content (42~51%).When the value of n is 2~10, its thing
Rationality matter, combustibility and diesel oil closely, preferably resolve dimethyl ether as lacking that derv fuel blend component is present
Fall into.Therefore polyoxymethylene dimethyl ether can, can up to 30% (v/v) as new cleaning diesel component, the addition in diesel oil
To improve diesel oil combustion position within the engine, the thermal efficiency is improved, reduce particulate matter and CO in tail gasxAnd NOxRow
Put.It is reported that the CH of addition 5~30%3OCH2OCH3NO can be reducedx7~10%, PM of discharge reductions by 5~35%.By coal Ji Jia
Alcohol synthesis PODE can not only replace part diesel oil, moreover it is possible to improve the efficiency of combustion of diesel oil, reduce danger of the diesel combustion to environment
Evil, with important strategic importance and good economic worth.
π-π keys periodic arrangement between aromatic group in conjugation microporous polymer structure, the intrinsic rigidity of system is produced
Permanent micropore of the size less than 2nm, and under dry state, specific surface area high can mutually be tied with the Electronic Performance in system
Close., the small aryleneethynylenes (poly (aryleneethynylene), PAE) being combined into permanent micropore of Cooper in 2007
Network, its BET specific surface area is more than 834m2/g.2008, they reported BET specific surface area more than 1000m2The CMPs of/g.
This is first example with high-specific surface area CMPs.The branched network structure that acetylene connection is heat-treated at 350~900 DEG C is gathered
Compound obtains micropore pyrolytic polymer.The network design of prepolymer makes its produce micropore into degradable side chain is contained under thermal degradation.It is logical
Pyrolytic polymer often is thermally treated resulting at 400 DEG C, 900 DEG C is further heated to and is caused carbonization.By Sonogashira-Hgihara
Crosslinking, synthesizes a series of CMPs based on PAE cladodification skeletons, and BET specific surface area is more than 1000m2/g。
Polyoxymethylene dimethyl ether can be by oligomeric in 150~180 DEG C of heating in the presence of trace sulfuric acid or hydrochloric acid in laboratory
Right paraformaldehyde or paraformaldehyde are prepared with the method for methyl alcohol reaction.In recent years, polyoxymethylene dimethyl ether synthetic technology is achieved
Progress.
CN 102040491A are described using β zeolites, ZSM-5 molecular sieve, MCM-22, MCM-56 or UZM-8 molecular sieve etc.
It is the method for reactant synthesizing polyoxymethylene dimethyl ether by methyl alcohol, dimethoxym ethane and paraformaldehyde as catalyst.CN
102040490A is described and is used solid super acid catalyst, in 90~130 DEG C of reaction temperature, 0.4~4.0MPa of reaction pressure
When, conversion ratio and selectivity are all not as good as to be conjugated microporous polymer supported solid superacid acid as catalyst.
Although reported above, middle to use methyl alcohol, dimethoxym ethane and paraformaldehyde be reaction raw materials, molecular sieve and solid super-strong acid
Used as these synthesis techniques of catalyst, but the zeolite catalyst and solid super acid catalyst that are used separate difficult, raw material
Conversion ratio is low, selectivity of product is poor.Particularly, conjugation microporous polymer carrier (CMPs) has high specific surface area and space
Rate, CMPs is the unformed micropore organic material of the properties such as first adjustable aperture, therefore can as needed adjust product
Distribution composition.Most CMPs are higher to the stability of heat, can be used repeatedly during reaction.
The content of the invention
The technical problems to be solved by the invention are that prior art is closed by reaction raw materials of methyl alcohol, dimethoxym ethane and paraformaldehyde
There is a problem of that catalyst reaction efficiency is low, metaformaldehyde is that cost of material is higher into polyoxymethylene dimethyl ether technique, there is provided one
Plant new method and the new catalyst suitable for the technique by paraformaldehyde production polyoxymethylene dimethyl ethers.The method has
The advantage that catalyst low-temperature activity is high, selectivity is high, reaction condition is gentle.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：One kind produces poly- first by paraformaldehyde
The method of aldehyde dimethyl ether, with methyl alcohol, dimethoxym ethane and paraformaldehyde as raw material, wherein methyl alcohol: dimethoxym ethane: the quality of paraformaldehyde
Than being (0~10): (0~10): 1, methyl alcohol can not be simultaneously 0 with the consumption of dimethoxym ethane, be 70~200 DEG C in reaction temperature, instead
Pressure is answered under the conditions of 0.2~6MPa, raw material is contacted with catalyst, reaction generation polyoxymethylene dimethyl ether, catalyst amount is original
Material weight 0.05~10%, wherein catalyst used in terms of parts by weight including following components：A) 30~80 parts of carrier,
Carrier is selected from least one in CMP-0, CMP-1,4, CMP-5 superhigh cross-linking polymer in CMPs；Be loaded in b thereon) 20
~70 parts are selected from SO4 2-、Cl-、S2O8 2-In at least one solid super-strong acid, preferably simultaneously include SO4 2-And S2O8 2-Two kinds of solids
Super acids.
In above-mentioned technical proposal, catalyst amount preferred scope is the 0.1~5% of raw material weight.In reactant methyl alcohol with
The consumption sum of dimethoxym ethane is preferably (0.4~5) with the mass ratio of paraformaldehyde: 1；Methyl alcohol: dimethoxym ethane: the quality of paraformaldehyde
It is (0.2~10): (0.5~10): 1 than preferred scope.The preferred scope of reaction temperature is 90~130 DEG C.Reaction pressure is preferred
Scope is 0.4~4.0MPa.The degree of polymerization of the paraformaldehyde is preferably 2~8, more preferably 4~6.Catalytic reaction is obtained poly- first
Aldehyde dimethyl ether, can filter or centrifugation by way of separating catalyst and liquid phase reactor thing.
In above-mentioned technical proposal, from the invention technical problem to be solved, with prior art effect on year-on-year basis for, reaction
Time is not key point of the invention, but is considered from operational control and time efficiency other factorses, generally by the reaction time
It is controlled to 1 to 20 hour.The reaction time used in the embodiment of the present invention is 4~12 hours.
In above-mentioned technical proposal, SO4 2-/CMP-0、SO4 2-/CMP-1,4、SO4 2-/CMP-5、Cl-/CMP-0、Cl-/CMP-1,
4、Cl-/CMP-5、CMP-0、S2O8 2-/CMP-1,4、S2O8 2-/ CMP-5 is known substance, can be used for the present invention and solves this
Inventive technique problem.The mol ratio of covalent ion and part wherein in conjugation capillary copolymer material CMPs series is preferably 1:
Between 10 to 10: 1.
The degree of polymerization of paraformaldehyde uses Arbiso process or iodometric determination, and method comes from：Chen Yongjie, Zhao Hui, Shao Yong
The preparation of the polymerization degree measurement and low polymerization degree paraformaldehyde of the industrial paraformaldehydes of that waits so long, Shenyang Institute of Chemical Technology journal, 15 (2)：
2001。
Due to the use of conjugation capillary copolymer material CMPs supported solid superacid acid being catalyst in the present invention, can realize
Methyl alcohol, dimethoxym ethane and paraformaldehyde catalytic reaction synthesizing polyoxymethylene dimethyl ether, the metaformaldehyde in substitution traditional raw material.Due to this
Method can be inexpensive to make production cost relatively low with paraformaldehyde as raw material, and distribution of reaction products is uniform.To be conjugated microporous polymer
The acid of material C MPs supported solid superacids is catalyst, and conjugation microporous polymer CMPs carriers can make the catalyst have very big specific surface
With heat endurance and chemical stability higher while product and porosity, so as to improve the yield of polyoxymethylene dimethyl ether,
Extend the service life of catalyst.Used catalyst contains extremely strong acidity, by the method distilled from methyl alcohol and poly first
Obtain dimethoxym ethane in the product of aldehyde, make accessory substance dimethoxym ethane be recycled into acid catalytic systems again with polyformaldehyde reaction,
Therefore reaction conversion ratio and product yield higher can be kept.It is 70~200 DEG C in reaction temperature using the inventive method,
Reaction pressure is under the conditions of 0.2~6MPa, using methyl alcohol, dimethoxym ethane and polyformaldehyde reaction, its result is as follows：First, production
Cost is relatively low；Second, catalyst is separated simply with product, makes accessory substance circular response using the method for distillation, therefore produce
The yield of thing n=2~10 is good, and selectivity of product is up to 75.1%, achieves preferable technique effect.In addition, the catalyst makes
With 10 times, its catalytic performance is not decreased obviously.
Below by embodiment, the present invention is further elaborated, the raw material paraformaldehyde used in embodiment and comparative example
The degree of polymerization be 5, selectivity of product is that target is produced with the polyoxymethylene dimethyl ether that the degree of polymerization is 2~10 on the basis of paraformaldehyde
Thing is calculated.
Specific embodiment
【Embodiment 1】
2 grams of catalyst SO are added in 300 milliliters of tank reactors4 2-(covalent groups are /CMP-0 with the mol ratio of part
0.1), wherein solid super-strong acid and the mass fraction ratio of CMP-0 carriers is 20:80,100 grams of methyl alcohol and 100 grams of paraformaldehydes,
4h is reacted under 130 DEG C and 0.8MPa self-generated pressures, by gas chromatographic analysis after extraction sample centrifugation.Comprising poly- in product
Formaldehyde dimethyl ether and unreacted material benzenemethanol and paraformaldehyde, its composition distribution such as table 1.
【Embodiment 2】
2 grams of catalyst SO are added in 300 milliliters of tank reactors4 2-/ CMP-1,4 (the mol ratios of covalent groups and part
For 0.1), wherein solid super-strong acid and CMP-1, the mass fraction ratio of 4 carriers is 20:80,100 grams of methyl alcohol and 100 grams of poly first
Aldehyde, reacts 4h, by gas chromatographic analysis after extraction sample centrifugation under 130 DEG C and 0.6MPa self-generated pressures.Wrapped in product
Containing polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde, its composition distribution such as table 1.
【Embodiment 3】
2 grams of catalyst SO are added in 300 milliliters of tank reactors4 2-(covalent groups are /CMP-5 with the mol ratio of part
0.1), wherein solid super-strong acid and the mass fraction ratio of CMP-5 carriers is 20:80,100 grams of dimethoxym ethanes and 100 grams of paraformaldehydes,
4h is reacted under 130 DEG C and 0.6MPa self-generated pressures, by gas chromatographic analysis after extraction sample centrifugation.Comprising poly- in product
Formaldehyde dimethyl ether and unreacted raw material dimethoxym ethane and paraformaldehyde, its composition distribution such as table 1.
【Embodiment 4】
2 grams of catalyst Cl are added in 300 milliliters of tank reactors-(covalent groups are /CMP-0 with the mol ratio of part
0.1), wherein solid super-strong acid and the mass fraction ratio of CMP-0 carriers is 20:80,100 grams distillation sample (dimethoxym ethane of 87wt%,
Remaining is methyl alcohol) and 100 grams of paraformaldehydes, at 130 DEG C, 4h is reacted under 0.7MPa self-generated pressures, after extracting sample centrifugation
By through gas chromatographic analysis.Polyoxymethylene dimethyl ether and unreacted raw material dimethoxym ethane and paraformaldehyde, its group are included in product
Into distribution such as table 1.
【Embodiment 5】
2 grams of catalyst Cl are added in 300 milliliters of tank reactors-/ CMP-1,4 (the mol ratios of covalent groups and part
For 0.1), wherein solid super-strong acid and CMP-1, the mass fraction ratio of 4 carriers is 20:80,100 grams of methyl alcohol and 50 grams of poly first
Aldehyde, at 130 DEG C, reacts 4h, by through gas chromatographic analysis after extraction sample centrifugation under 0.7MPa self-generated pressures.Wrapped in product
Containing polyoxymethylene dimethyl ether and unreacted raw material dimethoxym ethane and paraformaldehyde, its composition distribution such as table 1.
【Embodiment 6】
2 grams of catalyst S are added in 300 milliliters of tank reactors2O8 2-/ CMP-5 (the mol ratios of covalent groups and part
For 0.1), wherein solid super-strong acid and the mass fraction ratio of CMP-5 carriers is 20:80,100 grams of dimethoxym ethanes and 100 grams of poly first
Aldehyde, at 130 DEG C, reacts 4h, by gas chromatographic analysis after extraction sample centrifugation under 0.6MPa self-generated pressures.Included in product
Polyoxymethylene dimethyl ether and unreacted raw material dimethoxym ethane and paraformaldehyde, its composition distribution such as table 1.
【Embodiment 7】
2 grams of catalyst SO are added in 300 milliliters of tank reactors4 2-(covalent groups are /CMP-0 with the mol ratio of part
10), wherein solid super-strong acid and the mass fraction ratio of CMP-0 carriers is 20:80,100 grams of methyl alcohol and 100 grams of paraformaldehydes,
12h is reacted under 130 DEG C and 2MPa self-generated pressures, is extracted after sample centrifugation by gas chromatographic analysis.Poly- first is included in product
Aldehyde dimethyl ether and unreacted material benzenemethanol and paraformaldehyde, its composition distribution such as table 1.
【Embodiment 8】
2 grams of catalyst SO are added in 300 milliliters of tank reactors4 2-(covalent groups are /CMP-0 with the mol ratio of part
10), wherein solid super-strong acid and the mass fraction ratio of CMP-0 carriers is 70:30,100 grams of dimethoxym ethanes and 100 grams of paraformaldehydes,
4h is reacted under 120 DEG C and 4MPa nitrogen pressures, by gas chromatographic analysis after extraction sample centrifugation.Poly- first is included in product
Aldehyde dimethyl ether and unreacted raw material dimethoxym ethane and paraformaldehyde, its composition distribution such as table 1.
【Embodiment 9】
0.5 gram of catalyst SO is added in 300 milliliters of tank reactors4 2-/ CMP-0 (the mol ratios of covalent groups and part
For 10), wherein solid super-strong acid and the mass fraction ratio of CMP-0 carriers is 20:80,100 grams of dimethoxym ethanes and 100 grams of poly first
Aldehyde, reacts 4h, by gas chromatographic analysis after extraction sample centrifugation under 120 DEG C and 4MPa nitrogen pressures.Included in product
Polyoxymethylene dimethyl ether and unreacted raw material dimethoxym ethane and paraformaldehyde, its composition distribution such as table 1.
【Embodiment 10】
2 grams of catalyst SO are added in 300 milliliters of tank reactors4 2-(covalent groups are /CMP-0 with the mol ratio of part
10), wherein solid super-strong acid and the mass fraction ratio of CMP-0 carriers is 20:80,100 grams of dimethoxym ethanes and 100 grams of paraformaldehydes,
4h is reacted under 90 DEG C and 4MPa nitrogen pressures, by gas chromatographic analysis after extraction sample centrifugation.Poly- first is included in product
Aldehyde dimethyl ether and unreacted raw material dimethoxym ethane and paraformaldehyde, its composition distribution such as table 1.
【Embodiment 11】
By the catalyst SO in embodiment 14 2-/ CMP-0 takes out after the completion of reaction, according to embodiment 1 after dried process
In reaction condition carry out 9 times reuse, extract sample centrifugation after by gas chromatographic analysis.Polyformaldehyde is included in product
Dimethyl ether and unreacted material benzenemethanol and paraformaldehyde, to investigate the heat endurance and chemical stability of the catalyst, its
Composition distribution such as table 2.
【Embodiment 12】
2 grams of catalyst SO are added in 300 milliliters of tank reactors4 2-/ CMP-0/SBA-15 (metal group and part
Mol ratio is that 0.1), wherein solid super-strong acid and the mass fraction ratio of carrier is 20:80, CMP-0 and molecular sieve carrier SBA-15
Weight ratio be 50:50.100 grams of dimethoxym ethanes and 100 grams of paraformaldehydes, 4h is reacted under 130 DEG C and 4MPa nitrogen pressures, is extracted
By gas chromatographic analysis after sample centrifugation.Comprising polyoxymethylene dimethyl ether and unreacted raw material dimethoxym ethane and many in product
Polyformaldehyde, its composition distribution such as table 1.
【Embodiment 13】
2 grams of catalyst SO are added in 300 milliliters of tank reactors4 2-/S2O8 2-(covalent groups rub/CMP-5 with part
You are than being 0.1；SO4 2-And S2O8 2-Mutual load is in P (DVB-VBC), SO4 2-Solid super-strong acid and S2O8 2-The matter of solid super-strong acid
Amount is than being 50:50), wherein solid super-strong acid gross mass and the mass fraction ratio of CMP-5 carriers is 20:80,100 grams of dimethoxym ethanes and
100 grams of paraformaldehydes, at 130 DEG C, react 4h under 0.6MPa self-generated pressures, divided by gas-chromatography after extracting sample centrifugation
Analysis.Polyoxymethylene dimethyl ether and unreacted raw material dimethoxym ethane and paraformaldehyde are included in product, its composition distribution such as table 1.
【Comparative example 1】
According to patent《The synthetic method of polyoxymethylene dimethyl ether》(number of patent application：201210325102.1) methods described,
2 grams of catalyst SO are added in 300 milliliters of tank reactors4 2-/ZrO2/ SBA-15 (wherein solid super-strong acid SO4 2-With carrier
(ZrO2And molecular sieve carrier SBA-15) total mass ratio be 20:80, wherein ZrO2It is 50 with the mass ratio of SBA-15:50), 100
Ml methanol and 100 grams of paraformaldehydes, react 4 hours under 130 DEG C and 0.8MPa self-generated pressures, after extracting sample centrifugation
By gas chromatographic analysis.Polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde, its group of composition are included in product
Cloth is following (being represented with weight %)：Dimethoxym ethane is 22.2%, and methyl alcohol is 5.1%, and paraformaldehyde is that 2.1%, n=2 is 25.1%,
N=3 is that 18.4%, n=4 is that 17.5%, n=5-10 is 9.6%, n>10, surplus, the selection to product n=2~10 selectivity
Property is 70.6%.
It is raw material that methyl alcohol, dimethoxym ethane and paraformaldehyde are used in comparative example, and molecular sieve carried solid super-strong acid is used as catalysis
Under equal conditions selectivity of product is relatively low for agent.The embodiment of the present invention 1 in contrast, the conversion ratio of reaction and product n=2~10
Selectivity is higher, is that paraformaldehyde content is relatively low in 75.1%, and product.Can obtain with zeolite molecular sieve as catalyst
When more preferable reaction result.
Table 1
N is the degree of polymerization, and product is CH3O(CH2O)nCH3
Table 2
N is the degree of polymerization, and product is CH3O(CH2O)nCH3 。
Claims (9)
1. it is a kind of by paraformaldehyde produce polyoxymethylene dimethyl ethers method, with methyl alcohol, dimethoxym ethane and paraformaldehyde as raw material, its
Middle methyl alcohol: dimethoxym ethane: the mass ratio of paraformaldehyde is (0~10): (0~10): 1, methyl alcohol can not be with the consumption of dimethoxym ethane simultaneously
It is 0, is 70~200 DEG C in reaction temperature, under the conditions of 0.2~6MPa, raw material is contacted with catalyst, reaction is generated reaction pressure
Polyoxymethylene dimethyl ether, catalyst amount is the 0.05~10% of raw material weight, wherein catalyst used is wrapped in terms of weight fraction
Include following components：A) 30~80 parts of carrier, carrier is selected from and is conjugated CMP-0, CMP-1 in microporous polymer CMPs series, 4,
At least one in CMP-5 superhigh cross-linking polymer；Be loaded in b thereon) 20~70 parts selected from SO4 2-、S2O8 2-In at least
A kind of solid super-strong acid.
2. it is according to claim 1 by paraformaldehyde produce polyoxymethylene dimethyl ethers method, it is characterised in that catalyst
Consumption is the 0.1~5% of raw material weight.
3. it is according to claim 1 by paraformaldehyde produce polyoxymethylene dimethyl ethers method, it is characterised in that reactant
Middle methyl alcohol is (0.4~5) with the mass ratio of paraformaldehyde with the consumption sum of dimethoxym ethane: 1；Methyl alcohol: dimethoxym ethane: paraformaldehyde
Mass ratio is (0.2~10): (0.5~10): 1.
4. it is according to claim 1 by paraformaldehyde produce polyoxymethylene dimethyl ethers method, it is characterised in that reaction temperature
Spend is 90~130 DEG C.
5. it is according to claim 1 by paraformaldehyde produce polyoxymethylene dimethyl ethers method, it is characterised in that reaction pressure
Power is 0.4~4.0MPa.
6. it is according to claim 1 by paraformaldehyde produce polyoxymethylene dimethyl ethers method, it is characterised in that it is described many
The degree of polymerization of polyformaldehyde is 2~8.
7. it is according to claim 6 by paraformaldehyde produce polyoxymethylene dimethyl ethers method, it is characterised in that it is described many
The degree of polymerization of polyformaldehyde is 4~6.
8. it is according to claim 1 by paraformaldehyde produce polyoxymethylene dimethyl ethers method, it is characterised in that during reaction
Between be 1 to 20 hour.
9. it is according to claim 8 by paraformaldehyde produce polyoxymethylene dimethyl ethers method, it is characterised in that during reaction
Between be 4 to 12 hours.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000029365A2 (en) * | 1998-11-12 | 2000-05-25 | Bp Amoco Corporation | Preparation of polyoxymethylene dimethyl ethers by acid-activated catalytic conversion of methanol with formaldehyde |
| CN102040490A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Synthesis method of polyformaldehyde dimethyl ether |
| CN103664549A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Polyformaldehyde dimethyl ether synthesis method |
| CN103772165A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Method for preparing polyoxymethylene dimethyl ether from paraformaldehyde |
-
2014
- 2014-07-24 CN CN201410355502.6A patent/CN105294411B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000029365A2 (en) * | 1998-11-12 | 2000-05-25 | Bp Amoco Corporation | Preparation of polyoxymethylene dimethyl ethers by acid-activated catalytic conversion of methanol with formaldehyde |
| CN102040490A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Synthesis method of polyformaldehyde dimethyl ether |
| CN103664549A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Polyformaldehyde dimethyl ether synthesis method |
| CN103772165A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Method for preparing polyoxymethylene dimethyl ether from paraformaldehyde |
Non-Patent Citations (2)
| Title |
|---|
| 新型微孔聚合物材料的制备及应用;李步怡;《中国博士学位论文全文数据库（电子期刊）工程科技Ⅰ辑》;20130516;4-178 * |
| 金属-有机骨架材料及其在催化反应中的应用;李庆远 等;《化学进展》;20120824;第24卷(第8期);1506-1518 * |
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