CN105367393A - Method for synthesizing polyoxymethylene dimethyl ether through paraformaldehyde - Google Patents

Method for synthesizing polyoxymethylene dimethyl ether through paraformaldehyde Download PDF

Info

Publication number
CN105367393A
CN105367393A CN201410428102.3A CN201410428102A CN105367393A CN 105367393 A CN105367393 A CN 105367393A CN 201410428102 A CN201410428102 A CN 201410428102A CN 105367393 A CN105367393 A CN 105367393A
Authority
CN
China
Prior art keywords
paraformaldehyde
polyoxymethylene dimethyl
methylal
reaction
methyl alcohol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201410428102.3A
Other languages
Chinese (zh)
Other versions
CN105367393B (en
Inventor
杨为民
高晓晨
高焕新
石竹
刘志成
杨贺勤
贾银娟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Original Assignee
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Shanghai Research Institute of Petrochemical Technology filed Critical China Petroleum and Chemical Corp
Priority to CN201410428102.3A priority Critical patent/CN105367393B/en
Publication of CN105367393A publication Critical patent/CN105367393A/en
Application granted granted Critical
Publication of CN105367393B publication Critical patent/CN105367393B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a method for synthesizing polyoxymethylene dimethyl ether through paraformaldehyde. The method mainly solves the problems that catalysts in the past are low in reaction efficiency, and cost is high as trioxymethylene serves as a raw material. According to the method, methyl alcohol, methylal and paraformaldehyde are used as raw materials, the mass ratio of methyl alcohol to methylal to paraformaldehyde is (0-10):(0-10):1, the amount of adopted methyl alcohol and the amount of adopted methylal can not be zero at the same time, the reaction time is 70 DEG C-200 DEG C, reaction pressure is 0.2-6 MPa, the raw materials make contact with a catalyst to react to generate polyoxymethylene dimethyl ether, the amount of the adopted catalyst is 0.05-10% of the weight of the raw materials, and the adopted catalyst is prepared from, by weight, 30-80 parts of inherent microporous polymer carrier (PIMs) and 20-70 parts of solid super acid. The problems are solved well, and the catalyst can be applied to industrial production of polyoxymethylene dimethyl ether.

Description

By the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers
Technical field
The present invention relates to a kind of method by paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, particularly about a kind of be the method for Material synthesis polyoxymethylene dimethyl ether by paraformaldehyde.
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.
McKeown and the Budd group of Univ Manchester UK has developed a kind of organic microporous polymer newly, the intrinsic microporous polymer of called after (PIMs).These materials by comprising rigidity, non-rectilinear molecule of functional group is interconnected by covalent linkage.This rigidity, the polymkeric substance that reverses effectively can not occupy space between molecular chain, therefore these " free volumes " define microvoid structure.The molecule obtained after polymerization effectively cannot occupy the space between molecular chain, and molecule serious distortion forms intermolecular free volume, and PIM-1 specific surface area reaches 1000m 2/ g.
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 not as good as sour as catalyzer using intrinsic microporous polymer supported solid superacid.
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, intrinsic microporous polymer carrier (PIMs) has high specific surface area and voidage, can be reaction product " customized " its pore passage structure, be considered to unformed poromerics.The stability of most PIMs to heat is higher, 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 by paraformaldehyde synthesizing polyoxymethylene dimethyl ethers method and be applicable to the new catalyst of 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 method by 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 PIM-1 in PIMs, PIM-2, at least one in the intrinsic microporous polymer of PIM-6, 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-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-/ PIM-1, SO 4 2-/ PIM-2, SO 4 2-/ PIM-6, Cl -/ PIM-1, Cl -/ PIM-2, Cl -/ PIM-6, S 2o 8 2-/ PIM-1, S 2o 8 2-/ PIM-2, S 2o 8 2-/ PIM-6 is known substance, can be used for the present invention and solve the technology of the present invention problem.Covalency ion wherein in intrinsic capillary copolymer material COFs series and the mol ratio of part are preferably between 1: 10 to 10: 1.
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 intrinsic capillary copolymer material PIMs 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 intrinsic capillary copolymer material PIMs supported solid superacid acid for catalyzer, while intrinsic microporous polymer PIMs carrier can make catalyzer have very big specific surface area and porosity, there is higher thermostability and chemical stability, 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 75.1%, 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 by paraformaldehyde to be 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-/ PIM-1 (mol ratio of covalent groups and part is 0.1), wherein solid super-strong acid and the massfraction of PIM-1 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-/ PIM-2 (mol ratio of covalent groups and part is 0.1), wherein solid super-strong acid and the massfraction of PIM-2 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-/ PIM-6 (mol ratio of covalent groups and part is 0.1), wherein solid super-strong acid and the massfraction of PIM-6 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 -/ PIM-1 (mol ratio of covalent groups and part is 0.1), wherein solid super-strong acid and the massfraction of PIM-1 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 -/ PIM-2 (mol ratio of covalent groups and part is 0.1), wherein solid super-strong acid and the massfraction of PIM-2 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-/ PIM-6 (mol ratio of covalent groups and part is 0.1), wherein solid super-strong acid and the massfraction of PIM-6 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-/ PIM-1 (mol ratio of covalent groups and part is 10), wherein solid super-strong acid and the massfraction of PIM-1 carrier are than being 20:80,100 grams of methyl alcohol and 100 grams of paraformaldehydes, react 12h under 130 DEG C and 2MPa autogenous pressure, by gas chromatographic analysis after the centrifugation of extraction sample.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-/ PIM-1 (mol ratio of covalent groups and part is 10), wherein solid super-strong acid and the massfraction of PIM-1 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-/ PIM-1 (mol ratio of covalent groups and part is 10), wherein solid super-strong acid and the massfraction of PIM-1 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-/ PIM-1 (mol ratio of covalent groups and part is 10), wherein solid super-strong acid and the massfraction of PIM-1 carrier are than being 20:80,100 grams of methylals and 100 grams of paraformaldehydes, react 4h under 90 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 11]
By the catalyst S O in embodiment 1 4 2-/ PIM-1 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-/ PIM-1/SBA-15 (mol ratio of metal group and part is 0.1), the weight ratio that wherein solid super-strong acid and the massfraction ratio of carrier are 20:80, PIM-1 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 to/PIM-6; SO 4 2-and S 2o 8 2-mutual load is in PIM-6, 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 PIM-6 carrier are than being 20:80, and 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.
[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 75.1%, 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. the method by 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 PIM-1 in intrinsic microporous polymer PIMs series, PIM-2, at least one in the intrinsic microporous polymer of PIM-6, 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. the method by paraformaldehyde synthesizing polyoxymethylene dimethyl ethers according to claim 1, is characterized in that catalyst levels is 0.1 ~ 5% of raw material weight.
3. the method by paraformaldehyde synthesizing polyoxymethylene dimethyl ethers according to claim 1, 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. the method by paraformaldehyde synthesizing polyoxymethylene dimethyl ethers according to claim 1, is characterized in that temperature of reaction is 90 ~ 130 DEG C.
5. the method by paraformaldehyde synthesizing polyoxymethylene dimethyl ethers according to claim 1, is characterized in that reaction pressure is 0.4 ~ 4.0MPa.
6. the method by paraformaldehyde synthesizing polyoxymethylene dimethyl ethers according to claim 1, is characterized in that the polymerization degree of described paraformaldehyde is 2 ~ 8.
7. the method by paraformaldehyde synthesizing polyoxymethylene dimethyl ethers according to claim 6, is characterized in that the polymerization degree of described paraformaldehyde is 4 ~ 6.
8. the method by paraformaldehyde synthesizing polyoxymethylene dimethyl ethers according to claim 1, is characterized in that the reaction times is 1 to 20 hour.
9. the method by paraformaldehyde synthesizing polyoxymethylene dimethyl ethers according to claim 8, is characterized in that the reaction times is 4 to 12 hours.
CN201410428102.3A 2014-08-27 2014-08-27 By the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers Active CN105367393B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410428102.3A CN105367393B (en) 2014-08-27 2014-08-27 By the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410428102.3A CN105367393B (en) 2014-08-27 2014-08-27 By the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers

Publications (2)

Publication Number Publication Date
CN105367393A true CN105367393A (en) 2016-03-02
CN105367393B CN105367393B (en) 2017-09-15

Family

ID=55370092

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410428102.3A Active CN105367393B (en) 2014-08-27 2014-08-27 By the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers

Country Status (1)

Country Link
CN (1) CN105367393B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107522602A (en) * 2017-09-08 2017-12-29 青岛迈特达新材料有限公司 A kind of technique and system for preparing DMM2

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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)

* Cited by examiner, † Cited by third party
Title
史倩等: "共轭微孔聚合物材料的研究进展", 《现代化工》 *
李步怡: "新型微孔聚合物材料的制备及应用", 《中国博士学位论文全文数据库（电子期刊）工程科技Ⅰ辑》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107522602A (en) * 2017-09-08 2017-12-29 青岛迈特达新材料有限公司 A kind of technique and system for preparing DMM2
CN107522602B (en) * 2017-09-08 2022-07-22 青岛迈特达新材料有限公司 Process and system for preparing DMM2

Also Published As

Publication number Publication date
CN105367393B (en) 2017-09-15

Similar Documents

Publication Publication Date Title
CN102040491B (en) Catalytic synthesis method for polyoxymethylene dimethyl ethers (PODE) by molecular sieves
CN103880612B (en) By the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers
CN101768058B (en) Method for preparing polyoxymethylene dimethyl ether
CN102040488B (en) Method for synthesizing PODE (polyformaldehyde dimethyl ether)
CN104058940B (en) Methyl alcohol synthesizes the method for polymethoxy dimethyl ether through condensation, oxidation, polycondensation and etherificate
CN104151148B (en) Prepared the method for polyoxymethylene dimethyl ethers by paraformaldehyde
CN102295734B (en) Method for synthesizing polyoxymethylene dimethyl ether
CN102040490A (en) Synthesis method of polyformaldehyde dimethyl ether
CN103664545B (en) By the method for methyl alcohol, methylal and paraformaldehyde synthesizing polyoxymethylene dme
CN103664549B (en) The synthetic method of polyoxymethylene dimethyl ether
CN104230684A (en) Process for synthesis of polyoxymethylene dimethyl ether from methyl
CN103664543B (en) The method of polyoxymethylene dimethyl ether is prepared by paraformaldehyde
CN102295539B (en) Method for catalytically synthesizing polyformaldehyde dimethyl ether
CN104151147B (en) With the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers
CN104276932A (en) Preparation method of paraform dimethyl ether
CN105294411A (en) Method for producing PODE (polyoxymethylene dimethyl ethers) through paraformaldehyde
CN103772161A (en) Method for preparing polyoxymethylene dimethyl ethers
CN105367393A (en) Method for synthesizing polyoxymethylene dimethyl ether through paraformaldehyde
CN103880613B (en) Prepare the method for polyoxymethylene dimethyl ethers
CN103772165B (en) By the method for paraformaldehyde polyoxymethylene dimethyl ethers processed
CN105237368B (en) The synthetic method of polyoxymethylene dimethyl ethers
EP2810928B1 (en) A method for synthesizing polyoxymethylene dimethyl ethers
CN105439830A (en) A method of synthesizing polyoxymethylene dimethyl ether from polyoxymethylene
CN105085196A (en) Synthesis method of polyoxymethylene dimethyl ether from paraformaldehyde
CN103880614B (en) The synthetic method of polyoxymethylene dimethyl ether

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant