CN105439830A - A method of synthesizing polyoxymethylene dimethyl ether from polyoxymethylene - Google Patents

A method of synthesizing polyoxymethylene dimethyl ether from polyoxymethylene Download PDF

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CN105439830A
CN105439830A CN201410429331.7A CN201410429331A CN105439830A CN 105439830 A CN105439830 A CN 105439830A CN 201410429331 A CN201410429331 A CN 201410429331A CN 105439830 A CN105439830 A CN 105439830A
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paraformaldehyde
polyoxymethylene dimethyl
methylal
cof
reaction
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CN105439830B (en
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杨为民
高晓晨
高焕新
石竹
刘志成
杨贺勤
贾银娟
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The invention relates to a method of synthesizing polyoxymethylene dimethyl ether from polyoxymethylene, and mainly overcomes problems in the past, namely a low catalyst reaction efficiency and a high cost when trioxymethylene is adopted as a raw material. According to a technical scheme adopted by the method, methanol, methylal and the polyoxymethylene are adopted as raw materials of the method, the mass ratio of the methanol, the methylal and the polyoxymethylene is (0-10):(0-10):1, the using amount of the methanol and the using amount of the methylal cannot be zero at the same time, the raw materials are brought into contact with a catalyst at 70-200 DEG C under 0.2-6 MPa and react to generate the polyoxymethylene dimethyl ether, the catalyst is 0.05-10% by mass of the raw materials, and the catalyst comprises a) 30-80 parts by weight of a covalent organic framework carrier (COFs) and b) 20-70 parts by weight of a solid superacid. The problems are overcome by adoption of the technical scheme. The method can be used for industrial production of the polyoxymethylene dimethyl ether.

Description

With the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers
Technical field
The present invention relates to a kind of with the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, particularly about a kind of take paraformaldehyde as the method for Material synthesis polyoxymethylene dimethyl ether.
Background technology
In recent years, along with Industrial Revolution impact increasingly deeply and the resource general layout of China's distinctive " many coals, few oil, have gas ", China's oil resource growing tension, oil supplies pressure and unprecedentedly increases.Estimate following 10 ~ 20 years, China's oil supply rate only has ~ and 50%.The energy dilemma how utilizing the coal resources of China's abundant to solve China just becomes researcher urgent problem.Therefore be day by day subject to people's attention by the oil product substitute of coal-based methanol development of new.
Dme is suggested the earliest as a kind of procetane, but high, the easy generation vapour lock of vapour pressure makes dme obviously raise as the cost of vehicle alternative fuel because himself cold starting performance is poor, under normal temperature.Polyoxymethylene dimethyl ether, i.e. Polyoxymethylenedimethylethers (PODE), be the common name of a class material, its skeleton symbol can be expressed as CH 3o (CH 2o) ncH 3, there is higher octane value (>30) and oxygen level (42 ~ 51%).When the value of n is 2 ~ 10, its physical properties, combustionproperty and diesel oil closely, preferably resolve the defect that dme exists as derv fuel oil blend component.Therefore polyoxymethylene dimethyl ether can be used as novel clean diesel component, and the addition in diesel oil can reach 30% (v/v), can improve diesel oil combustion position within the engine, improves thermo-efficiency, reduces the particulate matter in tail gas and CO xand NO xdischarge.It is reported, add the CH of 5 ~ 30% 3oCH 2oCH 3nO can be reduced xdischarge 7 ~ 10%, PM reduces by 5 ~ 35%.Synthesize PODE by coal-based methanol and not only can replace part diesel oil, the efficiency of combustion of diesel oil can also be improved, reduce diesel combustion to the harm of environment, there is important strategic importance and good economic worth.
The skeleton of COFs is all made up of light element (H, B, O, C, Si etc.), and crystalline density is much lower compared with MOFs.Light element couples together the vesicular structure that can form one dimension or three-dimensional by very strong covalence key (C-C, C-O, B-O, Si-C etc.), there is very high specific surface area, as the hydrogen storage material that a class is novel, COFs has a lot of advantages, porous, surface-area are large, the surface-area of the most COFs reported in pertinent literature more reaches 3472m more than the specific surface area of 1000m2/g, COF-102 and COF-103 2/ g and 4210m 2/ g.Density is low, not containing metal element in COFs structure, and therefore its crystalline density is much lower compared with MOFs, and the density of COF-108 is 0.17g/cm3, is that crystalline density is minimum in report at present.The Modulatory character of structure, the same with most porous material with MOFs, its crystalline structure can be controlled by conversion parent.Very high thermostability, the stability of most COFs to heat has exceeded 500 DEG C.The synthesis of COFs is based on the dehydration condensation in molecule between hydroxyl.Between same molecular, dehydration can form the six-membered ring structure of a B3O3, and the dehydration reaction between differing molecular can form the five-membered ring structure of BO2C2.COFs can be summarised as two large class: two-dimentional COFs (2D-COFs) and three-dimensional COFs (3D-COFs) according to structural dimensions.2D-COFs, as COF-1, COF-10, COF-18 etc., has skeleton structure and the one-dimensional channels of two dimension.3D-COFs refers to the covalency organic compound with three dimensional skeletal structure and 3 D pore canal, studies more to comprise COF-102 ,-103 ,-105 ,-108 etc.Due to the singularity of its structure, 3D-COFs has higher surface-area and lower crystalline density compared with 2D-COFs.
Prepared by the method that in laboratory, polyoxymethylene dimethyl ether is reacted in 150 ~ 180 DEG C of heating low polymerization degree paraformaldehyde or paraformaldehyde and methyl alcohol under can being existed by trace sulfuric acid or hydrochloric acid.In recent years, polyoxymethylene dimethyl ether synthetic technology achieves progress.
CN102040491A describes and adopts β zeolite, ZSM-5 molecular sieve, MCM-22, MCM-56 or UZM-8 molecular sieve etc. as catalyzer, is the method for reactant synthesizing polyoxymethylene dme by methyl alcohol, methylal and paraformaldehyde.CN102040490A describes employing solid super acid catalyst, and temperature of reaction 90 ~ 130 DEG C, during reaction pressure 0.4 ~ 4.0MPa, transformation efficiency and selectivity are all too late using the carrier loaded solid super-strong acid of covalent organic framework as catalyzer.
Although more than adopt methyl alcohol, methylal and paraformaldehyde to be reaction raw materials in report, molecular sieve and solid super-strong acid are as these synthesis techniques of catalyzer, but the zeolite catalyst adopted and solid super acid catalyst separation difficulty, feed stock conversion is low, selectivity of product is poor.Especially, covalent organic framework carrier (COFs) has high thermostability, specific surface area and voidage, is considered to crystalline-state mesoporous material.The stability of most COFs to heat has exceeded 500 DEG C, can be used repeatedly in the process of reaction.
Summary of the invention
Technical problem to be solved by this invention be prior art with methyl alcohol, methylal and paraformaldehyde in order to exist in reaction raw materials synthesizing polyoxymethylene dme technique, catalyst reaction efficiency is low, trioxymethylene for the higher problem of raw materials cost, provide a kind of newly with the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers and the new catalyst being applicable to this technique.The method has the advantage that catalyst low-temperature activity is high, selectivity is high, reaction conditions is gentle.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of with the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, with methyl alcohol, methylal and paraformaldehyde are raw material, wherein methyl alcohol: methylal: the mass ratio of paraformaldehyde is (0 ~ 10): (0 ~ 10): 1, the consumption of methyl alcohol and methylal can not be 0 simultaneously, it is 70 ~ 200 DEG C in temperature of reaction, reaction pressure is under 0.2 ~ 6MPa condition, raw material and catalyst exposure, reaction generates polyoxymethylene dimethyl ether, catalyst levels is 0.05 ~ 10% of raw material weight, catalyzer wherein used comprises following component with weight parts: a) carrier of 30 ~ 80 parts, carrier is selected from COF-102 in COFs, COF-105, at least one in COF-108 covalent organic framework, with carry b thereon) 20 ~ 70 parts be selected from SO 4 2-, Cl -, S 2o 8 2-in at least one solid super-strong acid, preferably comprise SO simultaneously 4 2-and S 2o 8 2-in two kinds of solid super-strong acids.
In technique scheme, catalyst levels preferable range is 0.1 ~ 5% of raw material weight.In reactant, the consumption sum of methyl alcohol and methylal and the mass ratio of paraformaldehyde are preferably (0.4 ~ 5): 1; Methyl alcohol: methylal: the quality of paraformaldehyde is (0.2 ~ 10) than preferable range: (0.5 ~ 10): 1.The preferable range of temperature of reaction is 90 ~ 130 DEG C.Reaction pressure preferable range is 0.4 ~ 4.0MPa.The polymerization degree of described paraformaldehyde is preferably 2 ~ 8, and more preferably 4 ~ 6.Catalyzed reaction obtains polyoxymethylene dimethyl ether, by filtering or centrifugal mode separating catalyst and liquid phase reaction thing.
In technique scheme, from inventing the technical problem that will solve, with prior art effect on year-on-year basis, the reaction times is not key point of the present invention, but control and the consideration of time efficiency other factors from operation, usually will control in the reaction times is 1 to 20 hour.The reaction times adopted in the embodiment of the present invention is 4 ~ 12 hours.
In technique scheme, SO 4 2-/ COF-102, SO 4 2-/ COF-105, SO 4 2-/ COF-108, Cl -/ COF-102, Cl -/ COF-105, Cl -/ COF-108, S 2o 8 2-/ COF-102, S 2o 8 2-/ COF-105, S 2o 8 2-/ COF-108 is known substance, can be used for the present invention and solve the technology of the present invention problem.Covalency ion wherein in covalent organic framework material C OFs series and the mol ratio of part are preferably between 1: 10 to 10: 1.
In technique scheme, as the most preferred scheme,
The polymerization degree of paraformaldehyde adopts Arbiso process or iodometric determination, method comes from: Chen Yongjie, Zhao Hui, Shao Yong wait so long. the polymerization degree measurement of industrial paraformaldehyde and the preparation of low polymerization degree paraformaldehyde, Shenyang Institute of Chemical Technology journal, 15 (2): 2001.
Owing to using the acid of covalent organic framework material C OFs supported solid superacid to be catalyzer in the present invention, methyl alcohol, methylal and paraformaldehyde catalyzed reaction synthesizing polyoxymethylene dme can be realized, replace the trioxymethylene in traditional raw material.Because the method can paraformaldehyde be raw material, the inexpensive production cost that makes is lower, and distribution of reaction products is even.With the acid of covalent organic framework material C OFs supported solid superacid for catalyzer, covalent organic framework material C OFs carrier has higher thermostability and chemical stability while catalyzer can be made to have very big specific surface area and porosity, thus improve the productive rate of polyoxymethylene dimethyl ether, extend the work-ing life of catalyzer.Used catalyst contains extremely strong acidity, from the reaction product of methyl alcohol and paraformaldehyde, methylal is obtained by the method for distillation, make by product methylal circulate enter acid catalytic systems again with polyformaldehyde reaction, therefore can keep higher reaction conversion ratio and product yield.Use the inventive method, be 70 ~ 200 DEG C in temperature of reaction, reaction pressure is under 0.2 ~ 6MPa condition, and use methyl alcohol, methylal and polyformaldehyde reaction, its result is as follows: the first, and production cost is lower; The second, catalyzer is separated with reaction product simply, and adopt the way of distillation to make by product circulating reaction, therefore the yield of product n=2 ~ 10 is good, and selectivity of product, up to 73.9%, achieves good technique effect.In addition, this catalyzer uses 10 times, and its catalytic performance does not obviously decline.
Below by embodiment, the present invention is further elaborated, and the polymerization degree of the raw material paraformaldehyde adopted in embodiment and comparative example is 5, selectivity of product to take paraformaldehyde as benchmark with the polymerization degree be 2 ~ 10 polyoxymethylene dimethyl ether calculate for target product.
Embodiment
[embodiment 1]
2 grams of catalyst S O are added in 300 milliliters of tank reactors 4 2-/ COF-102 (mol ratio of covalent groups and part is 0.1), wherein solid super-strong acid and the massfraction of COF-102 carrier are than being 20:80,100 grams of methyl alcohol and 100 grams of paraformaldehydes, 4h is reacted, by gas chromatographic analysis after the centrifugation of extraction sample under 130 DEG C and 0.8MPa autogenous pressure.Comprise polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde in product, its composition distribution is as table 1.
[embodiment 2]
2 grams of catalyst S O are added in 300 milliliters of tank reactors 4 2-/ COF-105 (mol ratio of covalent groups and part is 0.1), wherein solid super-strong acid and the massfraction of COF-105 carrier are than being 20:80,100 grams of methyl alcohol and 100 grams of paraformaldehydes, 4h is reacted, by gas chromatographic analysis after the centrifugation of extraction sample under 130 DEG C and 0.6MPa autogenous pressure.Comprise polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde in product, its composition distribution is as table 1.
[embodiment 3]
2 grams of catalyst S O are added in 300 milliliters of tank reactors 4 2-/ COF-108 (mol ratio of covalent groups and part is 0.1), wherein solid super-strong acid and the massfraction of COF-108 carrier are than being 20:80,100 grams of methylals and 100 grams of paraformaldehydes, 4h is reacted, by gas chromatographic analysis after the centrifugation of extraction sample under 130 DEG C and 0.6MPa autogenous pressure.Comprise polyoxymethylene dimethyl ether and unreacted raw material methylal and paraformaldehyde in product, its composition distribution is as table 1.
[embodiment 4]
2 grams of catalyzer Cl are added in 300 milliliters of tank reactors -/ COF-102 (mol ratio of covalent groups and part is 0.1), wherein solid super-strong acid and the massfraction of COF-102 carrier are than being 20:80,100 grams of distillation sample (methylals of 87wt%, all the other are methyl alcohol) and 100 grams of paraformaldehydes, at 130 DEG C, react 4h under 0.7MPa autogenous pressure, extract after sample centrifugation by through gas chromatographic analysis.Comprise polyoxymethylene dimethyl ether and unreacted raw material methylal and paraformaldehyde in product, its composition distribution is as table 1.
[embodiment 5]
2 grams of catalyzer Cl are added in 300 milliliters of tank reactors -/ COF-105 (mol ratio of covalent groups and part is 0.1), wherein solid super-strong acid and the massfraction of COF-105 carrier are than being 20:80,100 grams of methyl alcohol and 50 grams of paraformaldehydes, at 130 DEG C, react 4h under 0.7MPa autogenous pressure, extract after sample centrifugation by through gas chromatographic analysis.Comprise polyoxymethylene dimethyl ether and unreacted raw material methylal and paraformaldehyde in product, its composition distribution is as table 1.
[embodiment 6]
2 grams of catalyst S are added in 300 milliliters of tank reactors 2o 8 2-/ COF-108 (mol ratio of covalent groups and part is 0.1), wherein solid super-strong acid and the massfraction of COF-108 carrier are than being 20:80,100 grams of methylals and 100 grams of paraformaldehydes, at 130 DEG C, 4h is reacted, by gas chromatographic analysis after the centrifugation of extraction sample under 0.6MPa autogenous pressure.Comprise polyoxymethylene dimethyl ether and unreacted raw material methylal and paraformaldehyde in product, its composition distribution is as table 1.
[embodiment 7]
2 grams of catalyst S O are added in 300 milliliters of tank reactors 4 2-/ COF-102 (mol ratio of covalent groups and part is 10), wherein solid super-strong acid and the massfraction of COF-102 carrier are than being 20:80,100 grams of methyl alcohol and 100 grams of paraformaldehydes, 12h is reacted, by gas chromatographic analysis after the centrifugation of extraction sample under 130 DEG C and 2MPa autogenous pressure.Comprise polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde in product, its composition distribution is as table 1.
[embodiment 8]
2 grams of catalyst S O are added in 300 milliliters of tank reactors 4 2-/ COF-102 (mol ratio of covalent groups and part is 10), wherein solid super-strong acid and the massfraction of COF-102 carrier are than being 70:30,100 grams of methylals and 100 grams of paraformaldehydes, 4h is reacted, by gas chromatographic analysis after the centrifugation of extraction sample under 120 DEG C and 4MPa nitrogen pressure.Comprise polyoxymethylene dimethyl ether and unreacted raw material methylal and paraformaldehyde in product, its composition distribution is as table 1.
[embodiment 9]
0.5 gram of catalyst S O is added in 300 milliliters of tank reactors 4 2-/ COF-102 (mol ratio of covalent groups and part is 10), wherein solid super-strong acid and the massfraction of COF-102 carrier are than being 20:80,100 grams of methylals and 100 grams of paraformaldehydes, 4h is reacted, by gas chromatographic analysis after the centrifugation of extraction sample under 120 DEG C and 4MPa nitrogen pressure.Comprise polyoxymethylene dimethyl ether and unreacted raw material methylal and paraformaldehyde in product, its composition distribution is as table 1.
[embodiment 10]
2 grams of catalyst S O are added in 300 milliliters of tank reactors 4 2-/ COF-102 (mol ratio of covalent groups and part is 10), wherein solid super-strong acid and the massfraction of COF-102 carrier are than being 20:80,100 grams of methylals and 100 grams of paraformaldehydes, 4h is reacted, by gas chromatographic analysis after the centrifugation of extraction sample under 90 DEG C and 4MPa nitrogen pressure.Comprise polyoxymethylene dimethyl ether and unreacted raw material methylal and paraformaldehyde in product, its composition distribution is as table 1.
[embodiment 11]
By the catalyst S O in embodiment 1 4 2-/ COF-102 takes out after the completion of reaction, carries out 9 times reuse after drying process according to the reaction conditions in embodiment 1, by gas chromatographic analysis after the centrifugation of extraction sample.Comprise polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde in product, to investigate thermostability and the chemical stability of this catalyzer, its composition distribution is as table 2.
[embodiment 12]
2 grams of catalyst S O are added in 300 milliliters of tank reactors 4 2-/ COF-102/SBA-15 (mol ratio of metal ion and part is 0.1), the weight ratio that wherein solid super-strong acid and the massfraction ratio of carrier are 20:80, COF-102 and molecular sieve carrier SBA-15 is 50:50.100 grams of methylals and 100 grams of paraformaldehydes, react 4h under 130 DEG C and 4MPa nitrogen pressure, by gas chromatographic analysis after the centrifugation of extraction sample.Comprise polyoxymethylene dimethyl ether and unreacted raw material methylal and paraformaldehyde in product, its composition distribution is as table 1.
[embodiment 13]
2 grams of catalyst S O are added in 300 milliliters of tank reactors 4 2-/ S 2o 8 2-(mol ratio of covalent groups and part is 0.1, SO to/COF-108 4 2-and S 2o 8 2-mutual load in COF-108 carrier, SO 4 2-solid super-strong acid and S 2o 8 2-the mass ratio of solid super-strong acid is 50:50), wherein solid super-strong acid total mass and the massfraction of COF-108 carrier are than being 20:80,100 grams of methylals and 100 grams of paraformaldehydes, at 130 DEG C, under 0.6MPa autogenous pressure, react 4h, by gas chromatographic analysis after the centrifugation of extraction sample.Comprise polyoxymethylene dimethyl ether and unreacted raw material methylal and paraformaldehyde in product, its composition distribution is as table 1.
[comparative example 1]
According to patent " synthetic method of polyoxymethylene dimethyl ether ", (number of patent application: 201210325102.1) described method, adds 2 grams of catalyst S O in 300 milliliters of tank reactors 4 2-/ ZrO 2/ SBA-15 (wherein solid super-strong acid SO 4 2-with carrier (ZrO 2and molecular sieve carrier SBA-15) total mass ratio be 20:80, wherein ZrO 2be 50:50 with the mass ratio of SBA-15), 100 ml methanol and 100 grams of paraformaldehydes, reaction 4 hours under 130 DEG C and 0.8MPa autogenous pressure, extracts after sample centrifugation by gas chromatographic analysis.Polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde is comprised in product, its composition distribution following (representing with % by weight): methylal is 22.2%, methyl alcohol is 5.1%, and paraformaldehyde is 2.1%, n=2 is 25.1%, n=3 is 18.4%, n=4 is 17.5%, n=5-10 is 9.6%, n>10, surplus, to product n=2 ~ 10 optionally selectivity be 70.6%.
Use methyl alcohol, methylal and paraformaldehyde for raw material in comparative example, under equal conditions selectivity of product is lower as catalyzer for molecular sieve carried solid super-strong acid.In contrast, transformation efficiency and product n=2 ~ 10 selectivity of reaction are higher, be 73.9%, and in product, paraformaldehyde content are lower for the embodiment of the present invention 1.Can obtain with zeolite molecular sieve as reaction result better during catalyzer.
Table 1
N is the polymerization degree, and product is CH 3o (CH 2o) ncH 3
Table 2
N is the polymerization degree, and product is CH 3o (CH 2o) ncH 3.

Claims (9)

1. with the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, with methyl alcohol, methylal and paraformaldehyde are raw material, wherein methyl alcohol: methylal: the mass ratio of paraformaldehyde is (0 ~ 10): (0 ~ 10): 1, the consumption of methyl alcohol and methylal can not be 0 simultaneously, it is 70 ~ 200 DEG C in temperature of reaction, reaction pressure is under 0.2 ~ 6MPa condition, raw material and catalyst exposure, reaction generates polyoxymethylene dimethyl ether, catalyst levels is 0.05 ~ 10% of raw material weight, catalyzer wherein used comprises following component in weight fraction: a) carrier of 30 ~ 80 parts, carrier is selected from COF-102 in covalent organic framework material C OFs series, COF-105, at least one in COF-108 covalent organic framework, with carry b thereon) 20 ~ 70 parts be selected from SO 4 2-, Cl -, S 2o 8 2-in at least one solid super-strong acid.
2. according to claim 1 with the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, it is characterized in that catalyst levels is 0.1 ~ 5% of raw material weight.
3. according to claim 1 with the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, it is characterized in that the consumption sum of methyl alcohol and methylal in reactant and the mass ratio of paraformaldehyde are (0.4 ~ 5): 1; Methyl alcohol: methylal: the mass ratio of paraformaldehyde is (0.2 ~ 10): (0.5 ~ 10): 1.
4. according to claim 1 with the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, it is characterized in that temperature of reaction is 90 ~ 130 DEG C.
5. according to claim 1 with the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, it is characterized in that reaction pressure is 0.4 ~ 4.0MPa.
6. according to claim 1 with the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, it is characterized in that the polymerization degree of described paraformaldehyde is 2 ~ 8.
7. according to claim 6 with the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, it is characterized in that the polymerization degree of described paraformaldehyde is 4 ~ 6.
8. according to claim 1 with the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, it is characterized in that the reaction times is 1 to 20 hour.
9. according to claim 8 with the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, it is characterized in that the reaction times is 4 to 12 hours.
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梁丽芸等: "多孔聚合物贮氢材料的研究进展", 《高分子通报》 *

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CN112958155A (en) * 2021-02-03 2021-06-15 中国科学院兰州化学物理研究所 Phthalocyanine polymer catalyst and preparation method and application thereof

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