CN105585460B - The method of synthesizing polyoxymethylene dimethyl ethers - Google Patents
The method of synthesizing polyoxymethylene dimethyl ethers Download PDFInfo
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Abstract
The present invention relates to the method for synthesizing polyoxymethylene dimethyl ethers, mainly solve the problems, such as prior art using methanol, dimethoxym ethane and paraformaldehyde as reaction raw materials synthesizing polyoxymethylene dimethyl ether technique in exist catalyst activity it is low, selectivity it is low, by using the method for synthesizing polyoxymethylene dimethyl ethers, using methanol, dimethoxym ethane and paraformaldehyde as raw material, raw material contacts with catalyst, reaction generation polyoxymethylene dimethyl ether, the catalyst are the sulfonic acid polystyrene cationic ion-exchange resin of metal oxide modified；The metal oxide is selected from the technical scheme of at least one of manganese oxide, molybdenum oxide, tungsten oxide, preferably solves the problem, available in the industrial production of polyoxymethylene dimethyl ether.
Description
Technical field
The present invention relates to the method using paraformaldehyde as Material synthesis polyoxymethylene dimethyl ether.
Background technology
In recent years, as the industrial revolution influences to go deep into increasingly and the resource grid of China distinctive " more coals, less oil, having gas "
Office, China's oil resource growing tension, oil supply pressure unprecedentedly increase.It is expected that 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 urgent need solution
Certainly the problem of.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, easily produces vapour lock make it 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 kind of material, and its skeleton symbol can be expressed as
CH3O(CH2O)nCH3, have higher octane number (>And oxygen content (42~51%) 30).When n value is 2~10, its thing
Rationality matter, combustibility and diesel oil are very close, preferably resolve dimethyl ether and are lacked as existing for derv fuel blend component
Fall into.Therefore polyoxymethylene dimethyl ether can be as new cleaning diesel component, and the addition in diesel oil, can up to 30% (v/v)
To improve the combustion position of diesel oil within the engine, the thermal efficiency is improved, reduces particulate matter and CO in tail gasxAnd NOxRow
Put.It is reported that the CH of addition 5~30%3OCH2OCH3NO can be reducedxDischarging 7~10%, PM reduces by 5~35%.By coal Ji Jia
Alcohol synthesis PODE can not only substitute 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, has important strategic importance and good economic value.
Composite is the trend of modern material development, by the compound of multiple material function, realizes performance complement and optimization,
It is expected the excellent material of processability, an organic inorganic hybrid material is nova most dazzling in compositional material families, the material
Combined by forms such as chemical bonds between middle organic phase and inorganic phase, the advantages of having organic and inorganic materials concurrently, such as maintained
On the basis of the good characteristics such as machine macromolecule filming, the transparency, flexibility, there is noninflammability, the scratch resistance of inorganic material again
The advantages that property, solvent resistance, high rigidity, and small-size effect, skin effect, quantum size effect due to nano material etc.
Make the performance of material there is specificity, and can be adjusted in sizable scope.Present document relates to polystyrene-metal oxide
Hybrid material is using polystyrene as organic matter, and metal oxide is the hybrid material of inorganic matter, is carried out by situ aggregation method
Synthesis.Metal oxide is present in the form of amorphous in hybrid material, and polystyrene is by being grafted from being used as crosslinking agent
Onto aluminum oxide, for metal oxide particle with 10nm or so particle diameter distribution in hybrid material, the hybrid material is resistant to 328
DEG C or so high temperature, while there is excellent solvent resistance and mechanical property.
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
It is prepared by right paraformaldehyde or paraformaldehyde and the method for methanol reaction.In recent years, polyoxymethylene dimethyl ether synthetic technology achieves
Progress.
CN 101048357A are described using inorganic acid, sulfonic acid, heteropoly acid, acid-exchange resin, zeolite, oxidation
Aluminium etc. is used as catalyst, the method by dimethoxym ethane and metaformaldehyde for reactant synthesizing polyoxymethylene dimethyl ether.But using existing
The conversion ratio of catalyst and selectivity all up for improving, and acid-exchange resin solvent resistance and mechanical property also compared with
Difference.
The content of the invention
One of technical problems to be solved by the invention are that prior art is former by reaction of methanol, dimethoxym ethane and paraformaldehyde
Have that catalyst reaction efficiency is low, metaformaldehyde is the problem of cost of material is higher in material synthesizing polyoxymethylene dimethyl ether technique, carry
For a kind of new method with paraformaldehyde synthesizing polyoxymethylene dimethyl ethers.This method has catalyst low-temperature activity height, selection
Property high and catalyst be more suitable for reusing.
The two of the technical problems to be solved by the invention are the preparation methods of catalyst described in one of technical problem.
The three of the technical problems to be solved by the invention are the catalyst that the preparation method described in one of technical problem obtains.
One of in order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：Synthesizing polyoxymethylene dimethyl ethers
Method, using methanol, dimethoxym ethane and paraformaldehyde as raw material, wherein methanol: dimethoxym ethane: the mass ratio of paraformaldehyde for (0~
10): (0~10): 1, the dosage of methanol and dimethoxym ethane can not be simultaneously 0, and raw material contacts with catalyst, and reaction generates polyformaldehyde two
Methyl ether, the catalyst are the sulfonic acid polystyrene cationic ion-exchange resin of metal oxide modified；The metal oxide
Selected from least one of manganese oxide, molybdenum oxide, tungsten oxide.
In above-mentioned technical proposal, catalyst amount is preferably the 0.05~10% of raw material weight, more preferably raw material weight
0.1~5%.
In above-mentioned technical proposal, the mass ratio of the dosage sum and paraformaldehyde of methanol and dimethoxym ethane is preferred in the raw material
For (0.4~5): 1；Methanol: dimethoxym ethane: the quality of paraformaldehyde is (0.2~10): (0.5~10): 1 than preferred scope.
In above-mentioned technical proposal, reaction temperature is preferably 70~200 DEG C, more preferably 90~130 DEG C.
In above-mentioned technical proposal, reaction pressure is preferably 0.2~6MPa, more preferably 0.4~4.0MPa.
In above-mentioned technical proposal, the degree of polymerization of the paraformaldehyde is preferably 2~8, and more preferably 4~6.
In above-mentioned technical proposal, from invention technical problems to be solved, with prior art effect it is year-on-year for, reaction
Time is not the key point of the present invention, but considered from operational control and time efficiency other factorses, generally by the reaction time
Control as 1 to 20 hour.The reaction time used in the embodiment of the present invention is 4~12 hour.
To solve the two of above-mentioned technical problem, technical scheme is as follows：The preparation method of catalyst described above,
Comprise the following steps：
(1) polymerization and hydridization：Under the initiation of radical initiator, styrene, divinylbenzene, the oxide powder and
The mixture of aromatic solvent, in aqueous phase carry out suspension polymerisation obtain coccoid product；Continue to use H after being cleaned with ethanol2O is clear
Wash, be dried to obtain catalyst precarsor I；
(2) sulfonation：Catalyst precarsor I is swelled with 1,2- dichloroethanes, and then sulfonating agent carries out sulfonation again, in being washed to
The heart, it is dried to obtain the catalyst；
Wherein, using the oxide, styrene and divinylbenzene three's parts by weight sum as 100 and with weight ratio meter,
The oxide:(styrene+divinylbenzene) is (30~80):(70~20).
Described sulfonating agent be it is commonly used in the prior art those, such as the concentrated sulfuric acid or oleum.
To solve the three of above-mentioned technical problem, the present invention also provides the catalyst that the preparation method of above-mentioned catalyst obtains.
Due to the use of polystyrene-metal oxide hybrid material being catalyst in the present invention, methanol, first contracting can be realized
Aldehyde and paraformaldehyde catalytic reaction synthesizing polyoxymethylene dimethyl ether, substitute the metaformaldehyde in traditional raw material.Because this method can be with
Paraformaldehyde is raw material, inexpensive to make production cost relatively low, and distribution of reaction products is uniform.It is miscellaneous with polystyrene-metal oxide
Change material is catalyst, metal oxide hybrid material can make catalyst with very big specific surface area and while porosity with
Higher excellent solvent resistance and mechanical property, so as to improve the yield of polyoxymethylene dimethyl ether, extend catalyst
Service life.Used catalyst contains extremely strong acidity, by the method for distillation from the reaction product of methanol and paraformaldehyde
Obtain dimethoxym ethane, make accessory substance dimethoxym ethane be recycled into acid catalytic systems again with polyformaldehyde reaction, therefore can keep compared with
High reaction conversion ratio and product yield.
Using the inventive method, it is 70~200 DEG C in reaction temperature, under the conditions of reaction pressure is 0.2~6MPa, uses first
Alcohol, dimethoxym ethane and polyformaldehyde reaction, the yield of product n=2~10 is good, and selectivity of product is up to 75.6%, achieves preferably
Technique effect.In addition, the catalyst uses 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 be by 2~10 polyoxymethylene dimethyl ether of the degree of polymerization on the basis of paraformaldehyde target production
Thing calculates.
Embodiment
【Embodiment 1】
1st, the preparation of catalyst
(1) polymerization and hydridization：At room temperature, 144 grams of styrene, divinylbenzene 16 are added into 1000 milliliters of three-necked flasks
Gram, 40 grams of 1 gram of BPO and toluene stir, then add 40 grams of the manganese oxide of 500 mesh, stir, adding 1.0w%
300 grams of the PVA aqueous solution, then stir under at 70 DEG C, react 3h, 80 DEG C reaction 1h, 95 DEG C reaction 45min, obtain coccoid
Product, stop stirring, kept for 95 DEG C and boil bead 30min.Product in three-necked flask is all poured into water and cleaned.Product
Continue to use H after being cleaned with ethanol2O is cleaned, and is placed in 80 DEG C of dry 4h in baking oven and is obtained 200 grams of catalyst precarsor I.
(2) sulfonation：200 grams of catalyst precarsor I are added into room temperature swelling 4h in 400 grams of 1,2- dichloroethanes, add 100 afterwards
Gram purity is 98w% H2SO4, 85 DEG C of sustained response 3h are downloaded in stirring, then in 110 DEG C of reaction 2h.With a large amount of after Temperature fall
It is neutrality that deionized water, which is washed to pH, and 80 DEG C of dryings to water content are 50w%, obtain the catalyst.
The quality full exchange capacity of the catalyst is 4.10mmol/g, and scope granularity is 0.31~1.25mm (＞
95w%).
2nd, the synthesis of polyoxymethylene dimethyl ether
Add 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and
4h is reacted under 0.8MPa self-generated pressures, is extracted after sample centrifuges by gas chromatographic analysis.Polyformaldehyde diformazan is included in product
Ether and unreacted material benzenemethanol and paraformaldehyde, it forms distribution such as table 1.
3rd, catalyst reuses experiment
Catalyst in embodiment 1 is taken out after the completion of reaction, according to the reaction bar in embodiment 1 after drying process
Part carries out 9 reuses, extracts after sample centrifuges by gas chromatographic analysis.In product comprising polyoxymethylene dimethyl ether and
Unreacted material benzenemethanol and paraformaldehyde, to investigate the heat endurance of the catalyst and chemical stability, it forms distribution such as
Table 2.
【Embodiment 2】
1st, the preparation of catalyst
(1) polymerization and hydridization：At room temperature, 144 grams of styrene, divinylbenzene 16 are added into 1000 milliliters of three-necked flasks
Gram, 40 grams of 1 gram of BPO and toluene stir, then add 40 grams of the molybdenum oxide of 500 mesh, stir, adding 1.0w%
300 grams of the PVA aqueous solution, then stir under at 70 DEG C, react 3h, 80 DEG C reaction 1h, 95 DEG C reaction 45min, obtain coccoid
Product, stop stirring, kept for 95 DEG C and boil bead 30min.Product in three-necked flask is all poured into water and cleaned.Product
Continue to use H after being cleaned with ethanol2O is cleaned, and is placed in 80 DEG C of dry 4h in baking oven and is obtained 200 grams of catalyst precarsor I.
(2) sulfonation：200 grams of catalyst precarsor I are added into room temperature swelling 4h in 400 grams of 1,2- dichloroethanes, add 100 afterwards
Gram purity is 98w% H2SO4, 85 DEG C of sustained response 3h are downloaded in stirring, then in 110 DEG C of reaction 2h.With a large amount of after Temperature fall
It is neutrality that deionized water, which is washed to pH, and 80 DEG C of dryings to water content are 50w%, obtain the catalyst.
The quality full exchange capacity of the catalyst is 4.20mmol/g, and scope granularity is 0.32~1.25mm (＞
95w%).
2nd, the synthesis of polyoxymethylene dimethyl ether
Add 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and
4h is reacted under 0.6MPa self-generated pressures, is extracted after sample centrifuges by gas chromatographic analysis.Polyformaldehyde diformazan is included in product
Ether and unreacted material benzenemethanol and paraformaldehyde, it forms distribution such as table 1.
【Embodiment 3】
1st, the preparation of catalyst
(1) polymerization and hydridization：At room temperature, 144 grams of styrene, divinylbenzene 16 are added into 1000 milliliters of three-necked flasks
Gram, 40 grams of 1 gram of BPO and toluene stir, then add 40 grams of the tungsten oxide of 500 mesh, stir, adding 1.0w%
300 grams of the PVA aqueous solution, then stir under at 70 DEG C, react 3h, 80 DEG C reaction 1h, 95 DEG C reaction 45min, obtain coccoid
Product, stop stirring, kept for 95 DEG C and boil bead 30min.Product in three-necked flask is all poured into water and cleaned.Product
Continue to use H after being cleaned with ethanol2O is cleaned, and is placed in 80 DEG C of dry 4h in baking oven and is obtained 200 grams of catalyst precarsor I.
(2) sulfonation：200 grams of catalyst precarsor I are added into room temperature swelling 4h in 400 grams of 1,2- dichloroethanes, add 100 afterwards
Gram purity is 98w% H2SO4, 85 DEG C of sustained response 3h are downloaded in stirring, then in 110 DEG C of reaction 2h.With a large amount of after Temperature fall
It is neutrality that deionized water, which is washed to pH, and 80 DEG C of dryings to water content are 50w%, obtain the catalyst.
The quality full exchange capacity of the catalyst is 4.30mmol/g, and scope granularity is 0.33~1.25mm (＞
95w%).
2nd, the synthesis of polyoxymethylene dimethyl ether
Add 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and
4h is reacted under 0.8MPa self-generated pressures, is extracted after sample centrifuges by gas chromatographic analysis.Polyformaldehyde diformazan is included in product
Ether and unreacted material benzenemethanol and paraformaldehyde, it forms distribution such as table 1.
【Embodiment 4】
1st, the preparation of catalyst
(1) polymerization and hydridization：At room temperature, 144 grams of styrene, divinylbenzene 16 are added into 1000 milliliters of three-necked flasks
Gram, 40 grams of 1 gram of BPO and toluene stir, then add 40 grams of the manganese oxide of 500 mesh, stir, adding 1.0w%
300 grams of the PVA aqueous solution, then stir under at 70 DEG C, react 3h, 80 DEG C reaction 1h, 95 DEG C reaction 45min, obtain coccoid
Product, stop stirring, kept for 95 DEG C and boil bead 30min.Product in three-necked flask is all poured into water and cleaned.Product
Continue to use H after being cleaned with ethanol2O is cleaned, and is placed in 80 DEG C of dry 4h in baking oven and is obtained 200 grams of catalyst precarsor I.
(2) sulfonation：200 grams of catalyst precarsor I are added into room temperature swelling 4h in 400 grams of 1,2- dichloroethanes, add 100 afterwards
Gram purity is 98w% H2SO4, 85 DEG C of sustained response 3h are downloaded in stirring, then in 110 DEG C of reaction 2h.With a large amount of after Temperature fall
It is neutrality that deionized water, which is washed to pH, and 80 DEG C of dryings to water content are 50w%, obtain the catalyst..
The quality full exchange capacity of the catalyst is 4.40mmol/g, and scope granularity is 0.34~1.25mm (＞
95w%).
2nd, the synthesis of polyoxymethylene dimethyl ether
Add 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and
4h is reacted under 0.7MPa self-generated pressures, is extracted after sample centrifuges by gas chromatographic analysis.Polyformaldehyde diformazan is included in product
Ether and unreacted material benzenemethanol and paraformaldehyde, it forms distribution such as table 1.
【Embodiment 5】
1st, the preparation of catalyst
(1) polymerization and hydridization：At room temperature, 144 grams of styrene, divinylbenzene 16 are added into 1000 milliliters of three-necked flasks
Gram, 40 grams of 1 gram of BPO and toluene stir, then add 40 grams of the manganese oxide of 500 mesh, stir, adding 1.0w%
300 grams of the PVA aqueous solution, then stir under at 70 DEG C, react 3h, 80 DEG C reaction 1h, 95 DEG C reaction 45min, obtain coccoid
Product, stop stirring, kept for 95 DEG C and boil bead 30min.Product in three-necked flask is all poured into water and cleaned.Product
Continue to use H after being cleaned with ethanol2O is cleaned, and is placed in 80 DEG C of dry 4h in baking oven and is obtained 200 grams of catalyst precarsor I.
(2) sulfonation：200 grams of catalyst precarsor I are added into room temperature swelling 4h in 400 grams of 1,2- dichloroethanes, add 100 afterwards
Gram purity is 98w% H2SO4, 85 DEG C of sustained response 3h are downloaded in stirring, then in 110 DEG C of reaction 2h.With a large amount of after Temperature fall
It is neutrality that deionized water, which is washed to pH, and 80 DEG C of dryings to water content are 50w%, obtain the catalyst.
The quality full exchange capacity of the catalyst is 4.50mmol/g, and scope granularity is 0.35~1.25mm (＞
95w%).
2nd, the synthesis of polyoxymethylene dimethyl ether
Add 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and
4h is reacted under 0.7MPa self-generated pressures, is extracted after sample centrifuges by gas chromatographic analysis.Polyformaldehyde diformazan is included in product
Ether and unreacted material benzenemethanol and paraformaldehyde, it forms distribution such as table 1.
【Embodiment 6】
1st, the preparation of catalyst
(1) polymerization and hydridization：At room temperature, 144 grams of styrene, divinylbenzene 16 are added into 1000 milliliters of three-necked flasks
Gram, 40 grams of 1 gram of BPO and toluene stir, then add 40 grams of the molybdenum oxide of 500 mesh, stir, adding 1.0w%
300 grams of the PVA aqueous solution, then stir under at 70 DEG C, react 3h, 80 DEG C reaction 1h, 95 DEG C reaction 45min, obtain coccoid
Product, stop stirring, kept for 95 DEG C and boil bead 30min.Product in three-necked flask is all poured into water and cleaned.Product
Continue to use H after being cleaned with ethanol2O is cleaned, and is placed in 80 DEG C of dry 4h in baking oven and is obtained 200 grams of catalyst precarsor I.
(2) sulfonation：200 grams of catalyst precarsor I are added into room temperature swelling 4h in 400 grams of 1,2- dichloroethanes, add 100 afterwards
Gram purity is 98w% H2SO4, 85 DEG C of sustained response 3h are downloaded in stirring, then in 110 DEG C of reaction 2h.With a large amount of after Temperature fall
It is neutrality that deionized water, which is washed to pH, and 80 DEG C of dryings to water content are 50w%, obtain the catalyst.
The quality full exchange capacity of the catalyst is 4.16mmol/g, and scope granularity is 0.36~1.25mm (＞
95w%).
2nd, the synthesis of polyoxymethylene dimethyl ether
Add 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and
4h is reacted under 0.7MPa self-generated pressures, is extracted after sample centrifuges by gas chromatographic analysis.Polyformaldehyde diformazan is included in product
Ether and unreacted material benzenemethanol and paraformaldehyde, it forms distribution such as table 1.
【Embodiment 7】
1st, the preparation of catalyst
(1) polymerization and hydridization：At room temperature, 144 grams of styrene, divinylbenzene 16 are added into 1000 milliliters of three-necked flasks
Gram, 40 grams of 1 gram of BPO and toluene stir, then add 40 grams of the tungsten oxide of 500 mesh, stir, adding 1.0w%
300 grams of the PVA aqueous solution, then stir under at 70 DEG C, react 3h, 80 DEG C reaction 1h, 95 DEG C reaction 45min, obtain coccoid
Product, stop stirring, kept for 95 DEG C and boil bead 30min.Product in three-necked flask is all poured into water and cleaned.Product
Continue to use H after being cleaned with ethanol2O is cleaned, and is placed in 80 DEG C of dry 4h in baking oven and is obtained 200 grams of catalyst precarsor I.
(2) sulfonation：200 grams of catalyst precarsor I are added into room temperature swelling 4h in 400 grams of 1,2- dichloroethanes, add 100 afterwards
Gram purity is 98w% H2SO4, 85 DEG C of sustained response 3h are downloaded in stirring, then in 110 DEG C of reaction 2h.With a large amount of after Temperature fall
It is neutrality that deionized water, which is washed to pH, and 80 DEG C of dryings to water content are 50w%, obtain the catalyst.
The quality full exchange capacity of the catalyst is 4.70mmol/g, and scope granularity is 0.37~1.25mm (＞
95w%).
2nd, the synthesis of polyoxymethylene dimethyl ether
Add 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and
12h is reacted under 2MPa self-generated pressures, is extracted after sample centrifuges by gas chromatographic analysis.Polyoxymethylene dimethyl ether is included in product
And unreacted material benzenemethanol and paraformaldehyde, it forms distribution such as table 1.
【Embodiment 8】
1st, the preparation of catalyst
(1) polymerization and hydridization：At room temperature, 144 grams of styrene, divinylbenzene 16 are added into 1000 milliliters of three-necked flasks
Gram, 40 grams of 1 gram of BPO and toluene stir, then add 40 grams of the manganese oxide of 500 mesh, stir, adding 1.0w%
300 grams of the PVA aqueous solution, then stir under at 70 DEG C, react 3h, 80 DEG C reaction 1h, 95 DEG C reaction 45min, obtain coccoid
Product, stop stirring, kept for 95 DEG C and boil bead 30min.Product in three-necked flask is all poured into water and cleaned.Production
Thing continues to use H after being cleaned with ethanol2O is cleaned, and is placed in 80 DEG C of dry 4h in baking oven and is obtained 200 grams of catalyst precarsor I.
(2) sulfonation：200 grams of catalyst precarsor I are added into room temperature swelling 4h in 400 grams of 1,2- dichloroethanes, add 100 afterwards
Gram purity is 98w% H2SO4, 85 DEG C of sustained response 3h are downloaded in stirring, then in 110 DEG C of reaction 2h.With a large amount of after Temperature fall
It is neutrality that deionized water, which is washed to pH, and 80 DEG C of dryings to water content are 50w%, obtain the catalyst.
The quality full exchange capacity of the catalyst is 4.10mmol/g, and scope granularity is 0.31~1.25mm (＞
95w%).
2nd, the synthesis of polyoxymethylene dimethyl ether
Add 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 90 DEG C and
4h is reacted under 4MPa self-generated pressures, is extracted after sample centrifuges by gas chromatographic analysis.Polyoxymethylene dimethyl ether is included in product
And unreacted material benzenemethanol and paraformaldehyde, it forms distribution such as table 1.
【Embodiment 9】
1st, the preparation of catalyst
(1) polymerization and hydridization：At room temperature, 144 grams of styrene, divinylbenzene 16 are added into 1000 milliliters of three-necked flasks
Gram, 40 grams of 1 gram of BPO and toluene stir, then add 40 grams of the manganese oxide of 500 mesh, stir, adding 1.0w%
300 grams of the PVA aqueous solution, then stir under at 70 DEG C, react 3h, 80 DEG C reaction 1h, 95 DEG C reaction 45min, obtain coccoid
Product, stop stirring, kept for 95 DEG C and boil bead 30min.Product in three-necked flask is all poured into water and cleaned.Product
Continue to use H after being cleaned with ethanol2O is cleaned, and is placed in 80 DEG C of dry 4h in baking oven and is obtained 200 grams of catalyst precarsor I.
(2) sulfonation：200 grams of catalyst precarsor I are added into room temperature swelling 4h in 400 grams of 1,2- dichloroethanes, add 100 afterwards
Gram purity is 98w% H2SO4, 85 DEG C of sustained response 3h are downloaded in stirring, then in 110 DEG C of reaction 2h.With a large amount of after Temperature fall
It is neutrality that deionized water, which is washed to pH, and 80 DEG C of dryings to water content are 50w%, obtain the catalyst.
The quality full exchange capacity of the catalyst is 4.10mmol/g, and scope granularity is 0.31~1.25mm (＞
95w%).
2nd, the synthesis of polyoxymethylene dimethyl ether
Add 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 120 DEG C and
4h is reacted under 1.5MPa self-generated pressures, is extracted after sample centrifuges by gas chromatographic analysis.Polyformaldehyde diformazan is included in product
Ether and unreacted material benzenemethanol and paraformaldehyde, it forms distribution such as table 1.
【Embodiment 10】
1st, the preparation of catalyst
(1) polymerization and hydridization：At room temperature, 144 grams of styrene, divinylbenzene 16 are added into 1000 milliliters of three-necked flasks
Gram, 40 grams of 1 gram of BPO and toluene stir, then add 40 grams of the manganese oxide of 500 mesh, stir, adding 1.0w%
300 grams of the PVA aqueous solution, then stir under at 70 DEG C, react 3h, 80 DEG C reaction 1h, 95 DEG C reaction 45min, obtain coccoid
Product, stop stirring, kept for 95 DEG C and boil bead 30min.Product in three-necked flask is all poured into water and cleaned.Product
Continue to use H after being cleaned with ethanol2O is cleaned, and is placed in 80 DEG C of dry 4h in baking oven and is obtained 200 grams of catalyst precarsor I.
(2) sulfonation：200 grams of catalyst precarsor I are added into room temperature swelling 4h in 400 grams of 1,2- dichloroethanes, add 100 afterwards
Gram purity is 98w% H2SO4, 85 DEG C of sustained response 3h are downloaded in stirring, then in 110 DEG C of reaction 2h.With a large amount of after Temperature fall
It is neutrality that deionized water, which is washed to pH, and 80 DEG C of dryings to water content are 50w%, obtain the catalyst.
The quality full exchange capacity of the catalyst is 4.10mmol/g, and scope granularity is 0.31~1.25mm (＞
95w%).
2nd, the synthesis of polyoxymethylene dimethyl ether
0.5 gram of catalyst, 100 grams of methanol and 100 grams of paraformaldehydes are added in 300 milliliters of tank reactors, at 130 DEG C
With react 4h under 0.8MPa self-generated pressures, extract after sample centrifuges by gas chromatographic analysis.Polyformaldehyde two is included in product
Methyl ether and unreacted material benzenemethanol and paraformaldehyde, it forms distribution such as table 1.
【Embodiment 11】
1st, the preparation of catalyst
(1) polymerization and hydridization：At room temperature, 144 grams of styrene, divinylbenzene 16 are added into 1000 milliliters of three-necked flasks
Gram, 40 grams of 1 gram of BPO and toluene stir, then add 20 grams of the manganese oxide of 500 mesh, 20 grams of molybdenum oxide stirs,
1.0w% 300 grams of the PVA aqueous solution is added, at 70 DEG C under then stirring, reacts 3h, 80 DEG C of reactions 1h, 95 DEG C of reaction 45min,
Coccoid product is obtained, stops stirring, is kept for 95 DEG C and boils bead 30min.By the product in three-necked flask be all poured into water into
Row cleaning.Product continues to use H after being cleaned with ethanol2O is cleaned, and is placed in 80 DEG C of dry 4h in baking oven and is obtained 200 grams of catalyst precarsors
I。
(2) sulfonation：200 grams of catalyst precarsor I are added into room temperature swelling 4h in 400 grams of 1,2- dichloroethanes, add 100 afterwards
Gram purity is 98w% H2SO4, 85 DEG C of sustained response 3h are downloaded in stirring, then in 110 DEG C of reaction 2h.With a large amount of after Temperature fall
It is neutrality that deionized water, which is washed to pH, and 80 DEG C of dryings to water content are 50w%, obtain the catalyst.
The quality full exchange capacity of the catalyst is 4.90mmol/g, and scope granularity is 0.39~1.25mm (＞
95w%).
2nd, the synthesis of polyoxymethylene dimethyl ether
Add 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and
4h is reacted under 0.6MPa self-generated pressures, is extracted after sample centrifuges by gas chromatographic analysis.Polyformaldehyde diformazan is included in product
Ether and unreacted material benzenemethanol and paraformaldehyde, it forms distribution such as table 1.
【Comparative example 1】
For embodiment 1 in proportion.
1st, the synthesis of polyoxymethylene dimethyl ether
According to patent《The method for preparing polyoxymethylene dimethyl ether》(published application number：CN 101048357A) methods described,
2 grams of catalyst Amberlite IR15 are added in 300 milliliters of tank reactors, and (ROHM AND HAAS, polystyryl cation exchange tree
Fat, exchange capacity 4.10mmol/g), 100 grams of methanol and 100 grams of paraformaldehydes are anti-under 130 DEG C and 0.8MPa self-generated pressures
Answer 4 hours, extract after sample centrifuges by gas chromatographic analysis.Polyoxymethylene dimethyl ether and unreacted original are included in product
Expect methanol and paraformaldehyde, it is following (being represented with weight %) that it forms distribution：Dimethoxym ethane is 48.2%, methanol 5.1%, poly
Formaldehyde is 2.1%, n=2 23.1%, n=3 12.4%, n=4 5.5%, n=5-10 3.6%, n>10, surplus is right
The selectivity of product n=2~10 is 44.6%.
2nd, catalyst reuses experiment
Catalyst Amberlite IR15 in comparative example 1 (ROHM AND HAAS, polystyrol cation exchange resin, are handed over
It is 4.10mmol/g to change capacity) take out after the completion of reaction, carry out 9 according to the reaction condition in comparative example 1 after drying process
Secondary reuse, extract after sample centrifuges by gas chromatographic analysis.Polyoxymethylene dimethyl ether and unreacted are included in product
Material benzenemethanol and paraformaldehyde, to investigate the heat endurance of the catalyst and chemical stability, it forms distribution such as table 3.
【Comparative example 2】
For embodiment 1 in proportion.
1st, the synthesis of polyoxymethylene dimethyl ether
Add 2 grams of manganese oxide in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and
React 4 hours, extracted after sample centrifuges by gas chromatographic analysis under 0.8MPa self-generated pressures.Polyformaldehyde two is included in product
Methyl ether and unreacted material benzenemethanol and paraformaldehyde, it is following (being represented with weight %) that it forms distribution：Dimethoxym ethane is
39.1%, methanol 10.2%, paraformaldehyde 4.6%, n=2 23.4%, n=3 13.5%, n=4 6.4%, n=
5-10 is 2.8%, n>10, surplus, the selectivity to product n=2~10 is 46.1%.
2nd, catalyst reuses experiment
Catalyst manganese oxide in comparative example 1 is taken out after the completion of reaction, according in comparative example 1 after drying process
Reaction condition carries out 9 reuses, extracts after sample centrifuges by gas chromatographic analysis.Polyformaldehyde diformazan is included in product
Ether and unreacted material benzenemethanol and paraformaldehyde, to investigate the heat endurance of the catalyst and chemical stability, it is formed
Distribution such as table 4.
The use of methanol, dimethoxym ethane and paraformaldehyde is raw material in comparative example, manganese oxide as catalyst under equal conditions
Selectivity of product is relatively low.In contrast, the conversion ratio and product n=2~10 selectivity of reaction are higher, are for the embodiment of the present invention 1
74.5%, and paraformaldehyde content is relatively low in product.More preferable reaction result during as catalyst can be obtained with manganese oxide.
Table 1
N is the degree of polymerization, product CH3O(CH2O)nCH3
Table 2
N is the degree of polymerization, product CH3O(CH2O)nCH3
Table 3
N is the degree of polymerization, product CH3O(CH2O)nCH3
Table 4
N is the degree of polymerization, product CH3O(CH2O)nCH3 。
Claims (10)
1. the method for synthesizing polyoxymethylene dimethyl ethers, using methanol, dimethoxym ethane and paraformaldehyde as raw material, wherein methanol: dimethoxym ethane:
The mass ratio of paraformaldehyde is (0~10): (0~10): 1, the dosage of methanol and dimethoxym ethane can not be 0 simultaneously, raw material and catalysis
Agent contacts, and reaction generation polyoxymethylene dimethyl ether, the catalyst is the sulfonic acid polystyrene cation of metal oxide modified
Exchanger resin；The metal oxide is the mixture of manganese oxide and molybdenum oxide.
2. according to the method for claim 1, it is characterised in that catalyst amount is the 0.05~10% of raw material weight.
3. according to the method for claim 1, it is characterised in that the dosage sum of methanol and dimethoxym ethane and poly first in raw material
The mass ratio of aldehyde is (0.4~5): 1；Methanol: dimethoxym ethane: the mass ratio of paraformaldehyde is (0.2~10): (0.5~10): 1.
4. according to the method for claim 1, it is characterised in that reaction temperature is 70~200 DEG C.
5. according to the method for claim 1, it is characterised in that reaction pressure is 0.2~6MPa.
6. according to the method for claim 1, it is characterised in that the degree of polymerization of the paraformaldehyde is 2~8.
7. according to the method for claim 6, it is characterised in that the degree of polymerization of the paraformaldehyde is 4~6.
8. according to the method for claim 1, it is characterised in that the reaction time is 1 to 20 hour.
9. the preparation method of catalyst described in claim 1, comprises the following steps：
(1) polymerization and hydridization：Under the initiation of radical initiator, styrene, divinylbenzene, the oxide powder and aromatic hydrocarbons
The mixture of solvent, in aqueous phase carry out suspension polymerisation obtain coccoid product；Continue to use H after being cleaned with ethanol2O is cleaned,
It is dried to obtain catalyst precarsor I；
(2) sulfonation：Catalyst precarsor I is swelled with 1,2- dichloroethanes, and then sulfonating agent carries out sulfonation again, is washed to neutral, dry
It is dry to obtain the catalyst；
Wherein, it is described using the oxide, styrene and divinylbenzene three's parts by weight sum as 100 and with weight ratio meter
Oxide:(styrene+divinylbenzene) is (30~80):(70~20).
10. the catalyst that the preparation method described in claim 9 obtains.
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| CN102964227A (en) * | 2012-09-18 | 2013-03-13 | 中国海洋石油总公司 | Method for preparation of polyoxymethylene dimethyl ether from paraformaldehyde |
| CN103506171A (en) * | 2012-06-15 | 2014-01-15 | 华东理工大学 | Modified acidic cation exchange resin and applications thereof |
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| CN103506171A (en) * | 2012-06-15 | 2014-01-15 | 华东理工大学 | Modified acidic cation exchange resin and applications thereof |
| CN102964227A (en) * | 2012-09-18 | 2013-03-13 | 中国海洋石油总公司 | Method for preparation of polyoxymethylene dimethyl ether from paraformaldehyde |
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| 柴油添加剂聚甲醛二甲醚的合成研究;刘奕;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20140615;B017-29 * |
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