CN105294411A - Method for producing PODE (polyoxymethylene dimethyl ethers) through paraformaldehyde - Google Patents
Method for producing PODE (polyoxymethylene dimethyl ethers) through paraformaldehyde Download PDFInfo
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Abstract
The invention relates to a method for producing PODE (polyoxymethylene dimethyl ethers) through paraformaldehyde, and mainly solves the problem that a catalyst is low in reaction efficiency and the cost is relatively high as trioxymethylene is adopted as the raw material in the prior art. With methyl alcohol, methylal and paraformaldehyde as the raw materials, the method comprises the step of enabling the raw materials to be in contact with a catalyst for reaction at the temperature of 70-200 DEG C and the reaction pressure of 0.2-6 MPa, so as to generate PODE, wherein the mass ratio of methyl alcohol to methylal to paraformaldehyde is (0-10): (0-10): 1; the dosages of methyl alcohol and methylal cannot be 0 at the same time; the dosage of the catalyst is 0.05-10% of the weight of the raw materials; the used catalyst comprises the following components in parts by weight: a) 30-80 parts of a CMPs (conjugated microporous polymers) carrier, and b) 20-70 parts of solid super acid. Through the adoption of the technical scheme, the problem is well solved, and the method can be applied to industrial production of PODE.
Description
Technical field
The present invention relates to and a kind ofly produce the method for polyoxymethylene dimethyl ethers by paraformaldehyde, 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.
π-π key periodic arrangement between aromatic group in conjugation microporous polymer structure, the intrinsic rigidity generation size of system is less than the permanent micropore of 2nm, and under dry state, high specific surface area can be combined with the Electronic Performance in system.2007, Cooper is little was combined into aryleneethynylene (poly (aryleneethynylene), the PAE) network with permanent micropore, and its BET specific surface area is more than 834m
2/ g.2008, they reported BET specific surface area more than 1000m
2the CMPs of/g.This is first example with high-specific surface area CMPs.The branched network structural polymer connected at 350 ~ 900 DEG C of thermal treatment acetylene obtains micropore heat polymers.The network design of prepolymer becomes containing degradable side chain, under thermal destruction, make it produce micropore.Usually at 400 DEG C, thermal treatment obtains thermopolymer, is heated to 900 DEG C further and causes carbonization.Be cross-linked by Sonogashira-Hgihara, synthesize a series of CMPs based on PAE cladodification skeleton, BET specific surface area is greater than 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 conjugation 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, conjugation microporous polymer carrier (CMPs) has high specific surface area and voidage, and CMPs is the unformed micropore organic materials of the character such as first adjustable aperture, and the distribution of product therefore can be regulated as required to form.The stability of most CMPs 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, a kind of producing the method for polyoxymethylene dimethyl ethers by paraformaldehyde and being applicable to the new catalyst of this technique is newly provided.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 of being produced polyoxymethylene dimethyl ethers by paraformaldehyde, 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 CMP-0 in CMPs, CMP-1, 4, at least one in CMP-5 superhigh cross-linking polymkeric substance, 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-/ CMP-0, SO
4 2-/ CMP-1,4, SO
4 2-/ CMP-5, Cl
-/ CMP-0, Cl
-/ CMP-1,4, Cl
-/ CMP-5, CMP-0, S
2o
8 2-/ CMP-1,4, S
2o
8 2-/ CMP-5 is known substance, can be used for the present invention and solve the technology of the present invention problem.Covalency ion wherein in conjugation capillary copolymer material CMPs 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 conjugation capillary copolymer material CMPs 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 conjugation capillary copolymer material CMPs supported solid superacid for catalyzer, while conjugation microporous polymer CMPs 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 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-/ CMP-0 (mol ratio of covalent groups and part is 0.1), wherein solid super-strong acid and the massfraction of CMP-0 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-/ CMP-1,4 (mol ratio of covalent groups and part is 0.1), wherein solid super-strong acid and CMP-1, the massfraction of 4 carriers is 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-/ CMP-5 (mol ratio of covalent groups and part is 0.1), wherein solid super-strong acid and the massfraction of CMP-5 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
-/ CMP-0 (mol ratio of covalent groups and part is 0.1), wherein solid super-strong acid and the massfraction of CMP-0 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
-/ CMP-1,4 (mol ratio of covalent groups and part is 0.1), wherein solid super-strong acid and CMP-1, the massfraction of 4 carriers is than being 20:80,100 grams of methyl alcohol and 50 grams of paraformaldehydes, at 130 DEG C, under 0.7MPa autogenous pressure, react 4h, 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-/ CMP-5 (mol ratio of covalent groups and part is 0.1), wherein solid super-strong acid and the massfraction of CMP-5 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-/ CMP-0 (mol ratio of covalent groups and part is 10), wherein solid super-strong acid and the massfraction of CMP-0 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-/ CMP-0 (mol ratio of covalent groups and part is 10), wherein solid super-strong acid and the massfraction of CMP-0 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-/ CMP-0 (mol ratio of covalent groups and part is 10), wherein solid super-strong acid and the massfraction of CMP-0 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-/ CMP-0 (mol ratio of covalent groups and part is 10), wherein solid super-strong acid and the massfraction of CMP-0 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-/ CMP-0 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-/ CMP-0/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, CMP-0 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/CMP-5; SO
4 2-and S
2o
8 2-mutual load in P (DVB-VBC), 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 CMP-5 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. produced the method for polyoxymethylene dimethyl ethers by paraformaldehyde for one kind, 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 CMP-0 in conjugation microporous polymer CMPs series, CMP-1, 4, at least one in CMP-5 superhigh cross-linking polymkeric substance, 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. method of being produced polyoxymethylene dimethyl ethers by paraformaldehyde according to claim 1, is characterized in that catalyst levels is 0.1 ~ 5% of raw material weight.
3. method of being produced polyoxymethylene dimethyl ethers by paraformaldehyde 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. method of being produced polyoxymethylene dimethyl ethers by paraformaldehyde according to claim 1, is characterized in that temperature of reaction is 90 ~ 130 DEG C.
5. method of being produced polyoxymethylene dimethyl ethers by paraformaldehyde according to claim 1, is characterized in that reaction pressure is 0.4 ~ 4.0MPa.
6. method of being produced polyoxymethylene dimethyl ethers by paraformaldehyde according to claim 1, is characterized in that the polymerization degree of described paraformaldehyde is 2 ~ 8.
7. method of being produced polyoxymethylene dimethyl ethers by paraformaldehyde according to claim 6, is characterized in that the polymerization degree of described paraformaldehyde is 4 ~ 6.
8. method of being produced polyoxymethylene dimethyl ethers by paraformaldehyde according to claim 1, is characterized in that the reaction times is 1 to 20 hour.
9. method of being produced polyoxymethylene dimethyl ethers by paraformaldehyde according to claim 8, is characterized in that the reaction times is 4 to 12 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106565481A (en) * | 2016-11-08 | 2017-04-19 | 南安创友日化有限公司 | Method for preparing diphenyl carbonate |
| CN106565506A (en) * | 2016-11-08 | 2017-04-19 | 南安创友日化有限公司 | Method for preparing polyhydric alcohol amine ester |
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 |
|---|
| 李庆远 等: "金属-有机骨架材料及其在催化反应中的应用", 《化学进展》 * |
| 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)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106565481A (en) * | 2016-11-08 | 2017-04-19 | 南安创友日化有限公司 | Method for preparing diphenyl carbonate |
| CN106565506A (en) * | 2016-11-08 | 2017-04-19 | 南安创友日化有限公司 | Method for preparing polyhydric alcohol amine ester |
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