CN107915601B - Method for synthesizing polyoxymethylene dimethyl ether - Google Patents
Method for synthesizing polyoxymethylene dimethyl ether Download PDFInfo
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- CN107915601B CN107915601B CN201610880559.7A CN201610880559A CN107915601B CN 107915601 B CN107915601 B CN 107915601B CN 201610880559 A CN201610880559 A CN 201610880559A CN 107915601 B CN107915601 B CN 107915601B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
- C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4288—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using O nucleophiles, e.g. alcohols, carboxylates, esters
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Abstract
The invention relates to a method for synthesizing polyoxymethylene dimethyl ethers, which mainly solves the problems of low catalyst activity and low selectivity in the process of synthesizing polyoxymethylene dimethyl ethers by taking methylal and paraformaldehyde as reaction raw materials in the prior art; the catalyst is modified metal ion modified sulfonic polystyrene cation exchange resin, and the sulfonic polystyrene cation exchange resin comprises a crosslinked polystyrene skeleton and sulfonic acid groups; the technical scheme that the modified metal comprises at least one metal selected from IIA can be used in the industrial production of polyoxymethylene dimethyl ether.
Description
Technical Field
The invention relates to a method for synthesizing polyoxymethylene dimethyl ethers.
Background
In recent years, with the influence of industrial revolution, the petroleum resources in China are increasingly tense and the pressure of petroleum supply is unprecedentedly increased along with the unique resource pattern of 'more coal, less oil and gas'. The petroleum supply rate in China is only 50% in the future 10-20 years. How to solve the energy crisis of China by using abundant coal resources of China becomes a problem which needs to be solved urgently by researchers. Therefore, people pay more attention to the development of novel oil substitutes from coal-based methanol.
Dimethyl ether was first proposed as an additive to diesel fuel, but due to its poor cold start properties, high vapor pressure at ambient temperature, and capacityThe gas resistance is easy to generate, so that the cost of the dimethyl ether as the vehicle alternative fuel is obviously increased. Polyoxymethylene dimethyl ethers (PODE) is a generic term for a class of substances, and can be represented by the general formula CH3O(CH2O)nCH3Having a higher octane number (>30) And oxygen content (42-51%). When the value of n is 2-10, the physical property and the combustion performance of the dimethyl ether are very close to those of diesel oil, and the defects of dimethyl ether as a blending component of the vehicle diesel oil are overcome. Therefore, the polyoxymethylene dimethyl ether can be used as a novel clean diesel component, the addition amount in the diesel can reach 30% (v/v), the combustion condition of the diesel in an engine can be improved, the thermal efficiency is improved, and particulate matters and CO in tail gas are reducedxAnd NOxAnd (4) discharging. Reportedly, 5-30% CH is added3OCH2OCH3Can reduce NOxThe emission is 7-10%, and the PM is reduced by 5-35%. The PODE synthesized by the coal-based methanol can replace part of diesel oil, improve the combustion efficiency of the diesel oil, reduce the harm of the combustion of the diesel oil to the environment, and has important strategic significance and good economic value.
CN 101048357a (method for preparing polyoxymethylene dimethyl ether) introduces a method for synthesizing polyoxymethylene dimethyl ether by using methylal and trioxymethylene as reactants and using inorganic acid, sulfonic acid, heteropoly acid, acidic ion exchange resin, zeolite, alumina, etc. as catalysts. However, the conversion and selectivity of the existing catalysts are to be improved.
The cation exchange resin as solid acid catalyst shows excellent catalytic reaction performance in esterification and etherification reaction of water-containing system, but the acid strength is lower. It is common to prepare supported resins, the activity of which is enhanced by increasing the acidity of the catalyst. The metal modified resin can be adopted to form a new acid center on the catalyst, and the new acid center can not be exchanged by other metal ions, so that the problem that the acidity of the catalyst can not be replaced by metal ions contained in raw materials to be inactivated under the condition that the catalyst keeps high activity in industrial application of polyformaldehyde dimethyl ether synthesis is solved.
Disclosure of Invention
The invention aims to solve the technical problem that the product selectivity of n-2-10 is low in the process of synthesizing polyoxymethylene dimethyl ether by taking methylal and paraformaldehyde as reaction raw materials in the prior art, and provides a novel method for synthesizing polyoxymethylene dimethyl ether. The catalyst has the advantage of high product selectivity of n-2-10.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a method for synthesizing polyoxymethylene dimethyl ether comprises the steps of taking methylal and paraformaldehyde as raw materials, contacting the raw materials with a polyoxymethylene dimethyl ether catalyst, and reacting to generate polyoxymethylene dimethyl ether; the catalyst is modified metal ion modified sulfonic polystyrene cation exchange resin, and the sulfonic polystyrene cation exchange resin comprises a crosslinked polystyrene skeleton and sulfonic acid groups; the modifying metal comprises at least one selected from IIA metals.
Through IIA metal modified sulfonic acid type polystyrene cation exchange resin, the selectivity of PODE (potassium peroxidase) with n being 2-10 is remarkably improved.
In the above technical solution, the IIA metal is preferably at least one selected from Ra, Be, Mg, Ca, Sr, and Ba.
In the technical scheme, the modified metal further comprises copper, and Cu and IIA metal have a synergistic effect in the aspect of improving the selectivity of PODE (potassium peroxidase) with n being 2-10. The ratio between Cu and IIA metals is not particularly limited, as long as a comparable synergistic effect is achieved with both Cu and IIA metals present in the catalyst.
The mass ratio of Cu to IIA metal is, by way of non-limiting example, 0.01 to 100, and further non-limiting examples within this range include 0.1, 0.5, 0.8, 1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, and the like.
In the technical scheme, the modified metal comprises at least two of IIA metals, such as but not limited to Ra and Be, Mg and Ca, Sr and Ba, and every two of the IIA metals have synergistic effect on improving selectivity of PODE (potassium peroxidase) on n-2-10. At this time, the ratio between Ra and Be, Mg and Ca, Sr and Ba is not particularly limited as long as the above-mentioned two IIA metal elements are present in the catalyst at the same time to obtain a comparable synergistic effect.
The mass ratio of the two IIA metal elements is 0.01 to 100, and further non-limiting examples within this range include 0.1, 0.5, 0.8, 1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, etc.
In the above-mentioned technical solution, the content of the modified metal in the catalyst is not particularly limited, but is not limited to, for example, more than 0 and not more than 10 w%.
In the technical scheme, the total exchange capacity of the resin is 3.0-6.0 mmol/g.
In the above technical solution, the resin may be of a gel type or a macroporous type.
The polyoxymethylene dimethyl ether catalyst used in the present invention may be prepared by a method comprising the step of contacting the sulfonic acid type polystyrene cation exchange resin with a suspension containing the modified metal oxide and/or hydroxide in the presence of a catalytic amount of an acid to effect ion exchange.
In the above technical scheme, the acid is not particularly limited as long as the salt obtained by the reaction with the modified metal oxide and/or hydroxide can be dissolved in the solvent used for the suspension, and in this principle, for example, but not limited to, at least one of hydrochloric acid, nitric acid, and C2 to C10 carboxylic acids.
In the above technical scheme, the carboxylic acid may be a hydroxy-substituted carboxylic acid, such as but not limited to glycolic acid, lactic acid, tartaric acid, citric acid, and the like.
In the above technical scheme, the carboxylic acid may be a C2-C10 monobasic acid, such as but not limited to acetic acid and the like.
In the above technical solution, the mass ratio of methylal to paraformaldehyde is preferably (0.01 to 100) to 1, more preferably 0.1 to 10, and still more preferably 0.2 to 5.
In the technical scheme, the dosage of the catalyst is preferably 0.05-10% of the weight of the raw materials, and more preferably 0.1-5% of the weight of the raw materials.
In the technical scheme, the reaction temperature is preferably 70-200 ℃.
In the technical scheme, the reaction pressure is preferably 0.2-6 MPa.
In the above technical scheme, the reaction time is preferably 1 to 20 hours, more preferably 4 to 12 hours.
In the case where the composition of the catalyst of the present invention has been clarified, the preparation of the catalyst is not particularly limited and can be carried out by referring to an ion exchange method which is generally used in the prior art. For example, the following steps can be included: washing the sodium sulfonate type polystyrene cation exchange resin with deionized water until clear water flows out, soaking the resin in 0.5-20% strong acid (such as hydrochloric acid or sulfuric acid) for 1-12 h, soaking the resin in deionized water or an ethanol solution for 1-12 h, and then washing the resin with deionized water until the pH value is 6, thus obtaining the sulfonic acid type polystyrene cation exchange resin. While the sulfonic acid type polystyrene cation exchange resin of the present invention is also directly available from commercial sources, it can be used for the preparation of the catalyst of the present invention, rather than the sodium sulfonate type.
By adopting the catalyst, the yield of PODE with n-2-10 is good, the selectivity of the product with n-2-10 is as high as 89.6%, and a better technical effect is achieved.
The total exchange capacity in the present invention is based on dry resin.
The present invention is further illustrated by the following examples, wherein the polymerization degree of the raw material paraformaldehyde used in the examples and comparative examples is 5, and the product selectivity is calculated by taking paraformaldehyde as a reference and taking polyoxymethylene dimethyl ether with the polymerization degree of 2-10 as a target product.
Detailed Description
[ example 1 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking with 4 w% hydrochloric acid for four times, soaking with 4 w% hydrochloric acid each time, washing with deionized water until the eluate has no chloride ion, and drying at 60 deg.C to obtain the sulfonic type polystyrene cation exchange resin with full exchange capacity of 4.10 mmol/iong. 98 g of sulfonic acid type polystyrene cation exchange resin corresponding to the dry resin was taken in combination with 300ml of Cu (OH) containing 2 g of Cu2Mixing the water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Cu content of 2 w%.
2. Synthesis of polyformaldehyde dimethyl ether
2 g of catalyst, 100 g of methylal and 100 g of paraformaldehyde are charged into a 300ml tank reactor, reacted at 130 ℃ under 0.5MPa autogenous pressure for 4 hours, and a sample is extracted, centrifuged and analyzed by gas chromatography. The product contains the paraformaldehyde dimethyl ether as well as unreacted raw materials of methylal and paraformaldehyde, and the composition distribution is shown in the table 1.
[ example 2 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking for four times with 4 w% hydrochloric acid, soaking for 4h each time with 4 w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, washing with deionized water until the eluate has no chloride ions, and drying at 60 ℃ to obtain the sulfonic type polystyrene cation exchange resin with the full exchange capacity of 4.10 mmol/g. 98 g of sulfonic acid polystyrene cation exchange resin corresponding to dry resin was taken and mixed with 300ml of Ra (OH) 2 g of Ra under nitrogen protection2Mixing the water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with Ra content of 2 w%.
2. Synthesis of polyformaldehyde dimethyl ether
2 g of catalyst, 100 g of methylal and 100 g of paraformaldehyde are charged into a 300ml tank reactor, reacted at 130 ℃ under 0.5MPa autogenous pressure for 4 hours, and a sample is extracted, centrifuged and analyzed by gas chromatography. The product contains the paraformaldehyde dimethyl ether as well as unreacted raw materials of methylal and paraformaldehyde, and the composition distribution is shown in the table 1.
[ example 3 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking for four times with 4 w% hydrochloric acid, soaking for 4h each time with 4 w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, washing with deionized water until the eluate has no chloride ions, and drying at 60 ℃ to obtain the sulfonic type polystyrene cation exchange resin with the full exchange capacity of 4.10 mmol/g. Taking 98 g of sulfonic acid type polystyrene cation exchange resin corresponding to the dry resin, and mixing with 300ml of Be (OH) containing 2 g of Be under the protection of nitrogen2Mixing the water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Be content of 2 w%.
2. Synthesis of polyformaldehyde dimethyl ether
2 g of catalyst, 100 g of methylal and 100 g of paraformaldehyde are charged into a 300ml tank reactor, reacted at 130 ℃ under 0.5MPa autogenous pressure for 4 hours, and a sample is extracted, centrifuged and analyzed by gas chromatography. The product contains the paraformaldehyde dimethyl ether as well as unreacted raw materials of methylal and paraformaldehyde, and the composition distribution is shown in the table 1.
[ example 4 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking for four times with 4 w% hydrochloric acid, soaking for 4h each time with 4 w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, washing with deionized water until the eluate has no chloride ions, and drying at 60 ℃ to obtain the sulfonic type polystyrene cation exchange resin with the full exchange capacity of 4.10 mmol/g. 98 g of sulfonic polystyrene cation exchange resin corresponding to dry resin was taken and mixed with 300ml of 2 g Mg (OH) under nitrogen2Mixing the water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Mg content of 2 w%.
2. Synthesis of polyformaldehyde dimethyl ether
2 g of catalyst, 100 g of methylal and 100 g of paraformaldehyde are charged into a 300ml tank reactor, reacted at 130 ℃ under 0.5MPa autogenous pressure for 4 hours, and a sample is extracted, centrifuged and analyzed by gas chromatography. The product contains the paraformaldehyde dimethyl ether as well as unreacted raw materials of methylal and paraformaldehyde, and the composition distribution is shown in the table 1.
[ example 5 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking for four times with 4 w% hydrochloric acid, soaking for 4h each time with 4 w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, washing with deionized water until the eluate has no chloride ions, and drying at 60 ℃ to obtain the sulfonic type polystyrene cation exchange resin with the full exchange capacity of 4.10 mmol/g. 98 g of sulfonic polystyrene cation exchange resin corresponding to dry resin was taken and mixed with 300ml of Ca (OH) containing 2 g of Ca under nitrogen protection2Mixing the water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Ca content of 2 w%.
2. Synthesis of polyformaldehyde dimethyl ether
2 g of catalyst, 100 g of methylal and 100 g of paraformaldehyde are charged into a 300ml tank reactor, reacted at 130 ℃ under 0.5MPa autogenous pressure for 4 hours, and a sample is extracted, centrifuged and analyzed by gas chromatography. The product contains the paraformaldehyde dimethyl ether as well as unreacted raw materials of methylal and paraformaldehyde, and the composition distribution is shown in the table 1.
[ example 6 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking the resin with 4 w% hydrochloric acid for four times, soaking the resin with 4 w% hydrochloric acid for 4h each time, washing the resin with deionized water until the eluate has no chloride ions, and drying the resin at 60 ℃ to obtain the sulfonic type polystyrene cation exchange resin 7320The resin had a total exchange capacity of 4.10 mmol/g. 98 g of sulfonic acid type polystyrene cation exchange resin corresponding to the dry resin is taken and mixed with 300ml of Sr (OH) containing 2 g of Sr under the protection of nitrogen2Mixing the water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Sr content of 2 w%.
2. Synthesis of polyformaldehyde dimethyl ether
2 g of catalyst, 100 g of methylal and 100 g of paraformaldehyde are charged into a 300ml tank reactor, reacted at 130 ℃ under 0.5MPa autogenous pressure for 4 hours, and a sample is extracted, centrifuged and analyzed by gas chromatography. The product contains the paraformaldehyde dimethyl ether as well as unreacted raw materials of methylal and paraformaldehyde, and the composition distribution is shown in the table 1.
[ example 7 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking for four times with 4 w% hydrochloric acid, soaking for 4h each time with 4 w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, washing with deionized water until the eluate has no chloride ions, and drying at 60 ℃ to obtain the sulfonic type polystyrene cation exchange resin with the full exchange capacity of 4.10 mmol/g. 98 g of sulfonic acid polystyrene cation exchange resin corresponding to the dry resin was taken and mixed with 300ml of Ba (OH) containing 2 g of Ba under nitrogen protection2Mixing the water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Ba content of 2 w%.
2. Synthesis of polyformaldehyde dimethyl ether
2 g of catalyst, 100 g of methylal and 100 g of paraformaldehyde are charged into a 300ml tank reactor, reacted at 130 ℃ under 0.5MPa autogenous pressure for 4 hours, and a sample is extracted, centrifuged and analyzed by gas chromatography. The product contains the paraformaldehyde dimethyl ether as well as unreacted raw materials of methylal and paraformaldehyde, and the composition distribution is shown in the table 1.
[ example 8 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking for four times with 4 w% hydrochloric acid, soaking for 4h each time with 4 w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, washing with deionized water until the eluate has no chloride ions, and drying at 60 ℃ to obtain the sulfonic type polystyrene cation exchange resin with the full exchange capacity of 4.10 mmol/g. Taking 98 g of sulfonic acid type polystyrene cation exchange resin corresponding to dry resin, and mixing with 300ml of Cu (OH) containing 1 g of Cu and 1 g of Ra under the protection of nitrogen2And Ra (OH)2Mixing the mixed water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Cu content of 1 w% and the Ra content of 1 w%.
2. Synthesis of polyformaldehyde dimethyl ether
2 g of catalyst, 100 g of methylal and 100 g of paraformaldehyde are charged into a 300ml tank reactor, reacted at 130 ℃ under 0.5MPa autogenous pressure for 4 hours, and a sample is extracted, centrifuged and analyzed by gas chromatography. The product contains the paraformaldehyde dimethyl ether as well as unreacted raw materials of methylal and paraformaldehyde, and the composition distribution is shown in the table 1.
[ example 9 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking for four times with 4 w% hydrochloric acid, soaking for 4h each time with 4 w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, washing with deionized water until the eluate has no chloride ions, and drying at 60 ℃ to obtain the sulfonic type polystyrene cation exchange resin with the full exchange capacity of 4.10 mmol/g. Taking 98 g of sulfonic acid type polystyrene cation exchange resin corresponding to dry resin, and mixing with 300ml of Cu (OH) containing 1 g of Cu and 1 g of Be under the protection of nitrogen2And Be (OH)2Mixing the mixed aqueous suspensions, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hr, and drying in vacuum drying ovenTo constant weight, the catalyst with 1w percent of Cu and 1w percent of Be is prepared.
2. Synthesis of polyformaldehyde dimethyl ether
2 g of catalyst, 100 g of methylal and 100 g of paraformaldehyde are charged into a 300ml tank reactor, reacted at 130 ℃ under 0.5MPa autogenous pressure for 4 hours, and a sample is extracted, centrifuged and analyzed by gas chromatography. The product contains the paraformaldehyde dimethyl ether as well as unreacted raw materials of methylal and paraformaldehyde, and the composition distribution is shown in the table 1.
[ example 10 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking for four times with 4 w% hydrochloric acid, soaking for 4h each time with 4 w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, washing with deionized water until the eluate has no chloride ions, and drying at 60 ℃ to obtain the sulfonic type polystyrene cation exchange resin with the full exchange capacity of 4.10 mmol/g. Taking 98 g of sulfonic acid type polystyrene cation exchange resin corresponding to dry resin, and mixing with 300ml of Cu (OH) containing 1 g of Cu and 1 g of Mg under the protection of nitrogen2And Mg (OH)2Mixing the mixed water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Cu content of 1 w% and the Mg content of 1 w%.
2. Synthesis of polyformaldehyde dimethyl ether
2 g of catalyst, 100 g of methylal and 100 g of paraformaldehyde are charged into a 300ml tank reactor, reacted at 130 ℃ under 0.5MPa autogenous pressure for 4 hours, and a sample is extracted, centrifuged and analyzed by gas chromatography. The product contains the paraformaldehyde dimethyl ether as well as unreacted raw materials of methylal and paraformaldehyde, and the composition distribution is shown in the table 1.
[ example 11 ]
1. Preparation of the catalyst
Washing sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until the clear water flows out, soaking with 4 w% hydrochloric acid for four times, and using each time4 w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate polystyrene cation exchange resin 7320 is soaked for 4h each time, then the obtained solution is washed by deionized water until no chloride ion exists in the eluate, and the obtained product is dried at 60 ℃ to obtain the sulfonic polystyrene cation exchange resin, wherein the total exchange capacity of the resin is 4.10 mmol/g. Taking 98 g of sulfonic acid type polystyrene cation exchange resin corresponding to dry resin, and mixing with 300ml of Cu (OH) containing 1 g of Cu and 1 g of Ca under the protection of nitrogen2And Ca (OH)2Mixing the mixed water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Cu content of 1 w% and the Ca content of 1 w%.
2. Synthesis of polyformaldehyde dimethyl ether
2 g of catalyst, 100 g of methylal and 100 g of paraformaldehyde are charged into a 300ml tank reactor, reacted at 130 ℃ under 0.5MPa autogenous pressure for 4 hours, and a sample is extracted, centrifuged and analyzed by gas chromatography. The product contains the paraformaldehyde dimethyl ether as well as unreacted raw materials of methylal and paraformaldehyde, and the composition distribution is shown in the table 1.
[ example 12 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking for four times with 4 w% hydrochloric acid, soaking for 4h each time with 4 w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, washing with deionized water until the eluate has no chloride ions, and drying at 60 ℃ to obtain the sulfonic type polystyrene cation exchange resin with the full exchange capacity of 4.10 mmol/g. Taking 98 g of sulfonic acid type polystyrene cation exchange resin corresponding to dry resin, and mixing with 300ml of Cu (OH) containing 1 g of Cu and 1 g of Sr under the protection of nitrogen2And Sr (OH)2Mixing the mixed water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Cu content of 1 w% and the Sr content of 1 w%.
2. Synthesis of polyformaldehyde dimethyl ether
2 g of catalyst, 100 g of methylal and 100 g of paraformaldehyde are charged into a 300ml tank reactor, reacted at 130 ℃ under 0.5MPa autogenous pressure for 4 hours, and a sample is extracted, centrifuged and analyzed by gas chromatography. The product contains the paraformaldehyde dimethyl ether as well as unreacted raw materials of methylal and paraformaldehyde, and the composition distribution is shown in the table 1.
[ example 13 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking for four times with 4 w% hydrochloric acid, soaking for 4h each time with 4 w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, washing with deionized water until the eluate has no chloride ions, and drying at 60 ℃ to obtain the sulfonic type polystyrene cation exchange resin with the full exchange capacity of 4.10 mmol/g. Taking 98 g of sulfonic acid type polystyrene cation exchange resin corresponding to dry resin, and mixing with 300ml of Cu (OH) containing 1 g of Cu and 1 g of Ba under the protection of nitrogen2And Ba (OH)2Mixing the mixed water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Cu content of 1 w% and the Ba content of 1 w%.
2. Synthesis of polyformaldehyde dimethyl ether
2 g of catalyst, 100 g of methylal and 100 g of paraformaldehyde are charged into a 300ml tank reactor, reacted at 130 ℃ under 0.5MPa autogenous pressure for 4 hours, and a sample is extracted, centrifuged and analyzed by gas chromatography. The product contains the paraformaldehyde dimethyl ether as well as unreacted raw materials of methylal and paraformaldehyde, and the composition distribution is shown in the table 1.
[ example 14 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking for four times with 4 w% hydrochloric acid, soaking for 4h each time with 4 w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, washing with deionized water until the eluate has no chloride ions, and drying at 60 deg.C to obtain the sulfonic acidType polystyrene cation exchange resin having a total exchange capacity of 4.10 mmol/g. 98 g of sulfonic polystyrene cation exchange resin corresponding to dry resin was taken and mixed with 300ml of Cu (OH) containing 1 g of Cu, 0.5 g of Ra and 0.5 g of Be under nitrogen protection2、Ra(OH)2And Be (OH)2Mixing the mixed water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Cu content of 1 w%, the Ra content of 0.5 w% and the Be content of 0.5 w%.
2. Synthesis of polyformaldehyde dimethyl ether
2 g of catalyst, 100 g of methylal and 100 g of paraformaldehyde are charged into a 300ml tank reactor, reacted at 130 ℃ under 0.5MPa autogenous pressure for 4 hours, and a sample is extracted, centrifuged and analyzed by gas chromatography. The product contains the paraformaldehyde dimethyl ether as well as unreacted raw materials of methylal and paraformaldehyde, and the composition distribution is shown in the table 1.
[ example 15 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking for four times with 4 w% hydrochloric acid, soaking for 4h each time with 4 w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, washing with deionized water until the eluate has no chloride ions, and drying at 60 ℃ to obtain the sulfonic type polystyrene cation exchange resin with the full exchange capacity of 4.10 mmol/g. Taking 98 g of sulfonic acid type polystyrene cation exchange resin corresponding to dry resin, and mixing with 300ml of Cu (OH) containing 1 g of Cu, 0.5 g of Mg and 0.5 g of Ca under the protection of nitrogen2、Mg(OH)2And Ca (OH)2Mixing the mixed water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Cu content of 1 w%, the Mg content of 0.5 w% and the Ca content of 0.5 w%.
2. Synthesis of polyformaldehyde dimethyl ether
2 g of catalyst, 100 g of methylal and 100 g of paraformaldehyde are charged into a 300ml tank reactor, reacted at 130 ℃ under 0.5MPa autogenous pressure for 4 hours, and a sample is extracted, centrifuged and analyzed by gas chromatography. The product contains the paraformaldehyde dimethyl ether as well as unreacted raw materials of methylal and paraformaldehyde, and the composition distribution is shown in the table 1.
[ example 16 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking for four times with 4 w% hydrochloric acid, soaking for 4h each time with 4 w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, washing with deionized water until the eluate has no chloride ions, and drying at 60 ℃ to obtain the sulfonic type polystyrene cation exchange resin with the full exchange capacity of 4.10 mmol/g. Taking 98 g of sulfonic acid type polystyrene cation exchange resin corresponding to dry resin, and mixing with 300ml of Cu (OH) containing 1 g of Cu, 0.5 g of Sr and 0.5 g of Ba under the protection of nitrogen2、Sr(OH)2And Ba (OH)2Mixing the mixed water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Cu content of 1 w%, the Sr content of 0.5 w% and the Ba content of 0.5 w%.
2. Synthesis of polyformaldehyde dimethyl ether
2 g of catalyst, 100 g of methylal and 100 g of paraformaldehyde are charged into a 300ml tank reactor, reacted at 130 ℃ under 0.5MPa autogenous pressure for 4 hours, and a sample is extracted, centrifuged and analyzed by gas chromatography. The product contains the paraformaldehyde dimethyl ether as well as unreacted raw materials of methylal and paraformaldehyde, and the composition distribution is shown in the table 1.
[ example 17 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking for four times with 4 w% hydrochloric acid, soaking for 4h each time with 4 w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, washing with deionized water until the eluate has no chloride ions, and drying at 60 deg.C to obtain the sulfonic polystyrene cation exchange resin 7320The total exchange capacity of the exchange resin was 4.10 mmol/g. The sulfonic acid type polystyrene cation exchange resin corresponding to 98 g of the dry resin was mixed with 300ml of Cu (OH) containing 1 g of Cu, 0.4 g of Ra, 0.3 g of Be and 0.3 g of Mg under nitrogen protection2、Ra(OH)2、Be(OH)2And Mg (OH)2Mixing the mixed water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Cu content of 1 w%, the Ra content of 0.4 w%, the Be content of 0.3 w% and the Mg content of 0.3 w%.
2. Synthesis of polyformaldehyde dimethyl ether
2 g of catalyst, 100 g of methylal and 100 g of paraformaldehyde are charged into a 300ml tank reactor, reacted at 130 ℃ under 0.5MPa autogenous pressure for 4 hours, and a sample is extracted, centrifuged and analyzed by gas chromatography. The product contains the paraformaldehyde dimethyl ether as well as unreacted raw materials of methylal and paraformaldehyde, and the composition distribution is shown in the table 1.
[ example 18 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking for four times with 4 w% hydrochloric acid, soaking for 4h each time with 4 w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, washing with deionized water until the eluate has no chloride ions, and drying at 60 ℃ to obtain the sulfonic type polystyrene cation exchange resin with the full exchange capacity of 4.10 mmol/g. Taking 98 g of sulfonic acid type polystyrene cation exchange resin corresponding to dry resin, and mixing with 300ml of Cu (OH) containing 1 g of Cu, 0.4 g of Ca, 0.3 g of Sr and 0.3 g of Ba under the protection of nitrogen2、Ca(OH)2、Sr(OH)2And Ba (OH)2Mixing the mixed water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Cu content of 1 w%, the Ca content of 0.4 w%, the Sr content of 0.3 w% and the Ba content of 0.3 w%.
2. Synthesis of polyformaldehyde dimethyl ether
2 g of catalyst, 100 g of methylal and 100 g of paraformaldehyde are charged into a 300ml tank reactor, reacted at 130 ℃ under 0.5MPa autogenous pressure for 4 hours, and a sample is extracted, centrifuged and analyzed by gas chromatography. The product contains the paraformaldehyde dimethyl ether as well as unreacted raw materials of methylal and paraformaldehyde, and the composition distribution is shown in the table 1.
[ example 19 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking for four times with 4 w% hydrochloric acid, soaking for 4h each time with 4 w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, washing with deionized water until the eluate has no chloride ions, and drying at 60 ℃ to obtain the sulfonic type polystyrene cation exchange resin with the full exchange capacity of 4.10 mmol/g. 98 g of sulfonic polystyrene cation exchange resin corresponding to dry resin was mixed with 300ml of Cu (OH) containing 1 g of Cu, 0.25 g of Ra, 0.25 g of Be, 0.25 g of Mg and 0.25 g of Ca under nitrogen2、Ra(OH)2、Be(OH)2、Mg(OH)2And Ca (OH)2Mixing the mixed water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Cu content of 1 w%, the Ra content of 0.25 w%, the Be content of 0.25 w%, the Mg content of 0.25 w% and the Ca content of 0.25 w%.
2. Synthesis of polyformaldehyde dimethyl ether
2 g of catalyst, 100 g of methylal and 100 g of paraformaldehyde are charged into a 300ml tank reactor, reacted at 130 ℃ under 0.5MPa autogenous pressure for 4 hours, and a sample is extracted, centrifuged and analyzed by gas chromatography. The product contains the paraformaldehyde dimethyl ether as well as unreacted raw materials of methylal and paraformaldehyde, and the composition distribution is shown in the table 1.
[ example 20 ]
1. Preparation of the catalyst
Washing sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until the clear water flows out, soaking with 4 w% hydrochloric acid for four times, each time using the resin equivalent to sulfur4 w% hydrochloric acid 10 times of the dry weight of the sodium polystyrene cation exchange resin 7320, soaking for 4h each time, washing with deionized water until no chloride ion exists in the eluate, and drying at 60 deg.C to obtain sulfonic acid polystyrene cation exchange resin with total exchange capacity of 4.10 mmol/g. 98 g of sulfonic polystyrene cation exchange resin corresponding to the dry resin is taken and mixed with 300ml of Cu (OH) containing 1 g of Cu, 0.25 g of Ra, 0.25 g of Be, 0.25 g of Sr and 0.25 g of Ba under the protection of nitrogen2、Ra(OH)2、Be(OH)2、Sr(OH)2And Ba (OH)2Mixing the mixed water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Cu content of 1 w%, the Ra content of 0.25 w%, the Be content of 0.25 w%, the Sr content of 0.25 w% and the Ba content of 0.25 w%.
2. Synthesis of polyformaldehyde dimethyl ether
2 g of catalyst, 100 g of methylal and 100 g of paraformaldehyde are charged into a 300ml tank reactor, reacted at 130 ℃ under 0.5MPa autogenous pressure for 4 hours, and a sample is extracted, centrifuged and analyzed by gas chromatography. The product contains the paraformaldehyde dimethyl ether as well as unreacted raw materials of methylal and paraformaldehyde, and the composition distribution is shown in the table 1.
[ example 21 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking for four times with 4 w% hydrochloric acid, soaking for 4h each time with 4 w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, washing with deionized water until the eluate has no chloride ions, and drying at 60 ℃ to obtain the sulfonic type polystyrene cation exchange resin with the full exchange capacity of 4.10 mmol/g. The sulfonic acid type polystyrene cation exchange resin which is equivalent to 98 grams of dry resin is taken and mixed with 300ml of Cu (OH) containing 1 gram of Cu, 0.25 gram of Mg, 0.25 gram of Ca, 0.25 gram of Sr and 0.25 gram of Ba under the protection of nitrogen2、Mg(OH)2、Ca(OH)2、Sr(OH)2And Ba (OH)2Mixing the mixed aqueous suspension, addingAdding 1 drop of glacial acetic acid, mixing, standing for 24 hours at room temperature, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Cu content of 1 w%, the Mg content of 0.25 w%, the Ca content of 0.25 w%, the Sr content of 0.25 w% and the Ba content of 0.25 w%.
2. Synthesis of polyformaldehyde dimethyl ether
2 g of catalyst, 100 g of methylal and 100 g of paraformaldehyde are charged into a 300ml tank reactor, reacted at 130 ℃ under 0.5MPa autogenous pressure for 4 hours, and a sample is extracted, centrifuged and analyzed by gas chromatography. The product contains the paraformaldehyde dimethyl ether as well as unreacted raw materials of methylal and paraformaldehyde, and the composition distribution is shown in the table 1.
[ example 22 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking for four times with 4 w% hydrochloric acid, soaking for 4h each time with 4 w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, washing with deionized water until the eluate has no chloride ions, and drying at 60 ℃ to obtain the sulfonic type polystyrene cation exchange resin with the full exchange capacity of 4.10 mmol/g. 98 g of sulfonic polystyrene cation exchange resin corresponding to the dry resin was mixed with 300ml of Cu (OH) containing 1 g of Cu, 0.2 g of Ra, 0.2 g of Be, 0.2 g of Mg, 0.2 g of Ca and 0.2 g of Sr under nitrogen protection2、Ra(OH)2、Be(OH)2、Mg(OH)2、Ca(OH)2And Sr (OH)2Mixing the mixed water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Cu content of 1 w%, the Ra content of 0.2 w%, the Be content of 0.2 w%, the Mg content of 0.2 w%, the Ca content of 0.2 w% and the Sr content of 0.2 w%.
2. Synthesis of polyformaldehyde dimethyl ether
2 g of catalyst, 100 g of methylal and 100 g of paraformaldehyde are charged into a 300ml tank reactor, reacted at 130 ℃ under 0.5MPa autogenous pressure for 4 hours, and a sample is extracted, centrifuged and analyzed by gas chromatography. The product contains the paraformaldehyde dimethyl ether as well as unreacted raw materials of methylal and paraformaldehyde, and the composition distribution is shown in the table 1.
[ example 23 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking for four times with 4 w% hydrochloric acid, soaking for 4h each time with 4 w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, washing with deionized water until the eluate has no chloride ions, and drying at 60 ℃ to obtain the sulfonic type polystyrene cation exchange resin with the full exchange capacity of 4.10 mmol/g. The sulfonic acid type polystyrene cation exchange resin corresponding to 98 g of the dry resin is mixed with 300ml of Cu (OH) containing 1 g of Cu, 0.2 g of Ra, 0.2 g of Be, 0.2 g of Mg, 0.2 g of Ca and 0.2 g of Ba under the protection of nitrogen2、Ra(OH)2、Be(OH)2、Mg(OH)2、Ca(OH)2And Ba (OH)2Mixing the mixed water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Cu content of 1 w%, the Ra content of 0.2 w%, the Be content of 0.2 w%, the Mg content of 0.2 w%, the Ca content of 0.2 w% and the Ba content of 0.2 w%.
2. Synthesis of polyformaldehyde dimethyl ether
2 g of catalyst, 100 g of methylal and 100 g of paraformaldehyde are charged into a 300ml tank reactor, reacted at 130 ℃ under 0.5MPa autogenous pressure for 4 hours, and a sample is extracted, centrifuged and analyzed by gas chromatography. The product contains the paraformaldehyde dimethyl ether as well as unreacted raw materials of methylal and paraformaldehyde, and the composition distribution is shown in the table 1.
[ example 24 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking with 4 w% hydrochloric acid for four times, each time using 4 w% hydrochloric acid 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, each time for 4h, and washing with deionized water until eluateNo chloride ion exists, and the sulfonic acid type polystyrene cation exchange resin is obtained after drying at the temperature of 60 ℃, and the total exchange capacity of the sulfonic acid type polystyrene cation exchange resin is 4.10 mmol/g. 98 g of sulfonic polystyrene cation exchange resin corresponding to dry resin is taken and mixed with 300ml of Cu (OH) containing 1 g of Cu, 0.2 g of Ra, 0.2 g of Be, 0.15 g of Mg, 0.15 g of Ca, 0.15 g of Sr and 0.15 g of Ba under the protection of nitrogen2、Ra(OH)2、Be(OH)2、Mg(OH)2、Ca(OH)2、Sr(OH)2And Ba (OH)2Mixing the mixed water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Cu content of 1 w%, the Ra content of 0.2 w%, the Be content of 0.2 w%, the Mg content of 0.15 w%, the Ca content of 0.15 w%, the Sr content of 0.15 w% and the Ba content of 0.15 w%.
2. Synthesis of polyformaldehyde dimethyl ether
2 g of catalyst, 100 g of methylal and 100 g of paraformaldehyde are charged into a 300ml tank reactor, reacted at 130 ℃ under 0.5MPa autogenous pressure for 4 hours, and a sample is extracted, centrifuged and analyzed by gas chromatography. The product contains the paraformaldehyde dimethyl ether as well as unreacted raw materials of methylal and paraformaldehyde, and the composition distribution is shown in the table 1.
[ COMPARATIVE EXAMPLE 1 ]
The same ratio as in example 1 was used except that the catalyst used was 2 g of the dry sulfonic acid type polystyrene cation exchange resin described in example 1 and the other process conditions were the same as in example 1, and the results are shown in Table 1.
TABLE 1
n is polymerization degree, and the product is CH3O(CH2O)nCH3。
Claims (9)
1. A method for synthesizing polyoxymethylene dimethyl ether comprises the steps of taking methylal and paraformaldehyde as raw materials, contacting the raw materials with a polyoxymethylene dimethyl ether catalyst, and reacting to generate polyoxymethylene dimethyl ether; the catalyst is modified metal ion modified sulfonic polystyrene cation exchange resin, and the sulfonic polystyrene cation exchange resin comprises a crosslinked polystyrene skeleton and sulfonic acid groups; the modified metal comprises Cu and IIA metals; the IIA metal is selected from at least two of Be, Mg, Ca, Sr and Ba;
wherein the mass ratio of Cu to IIA metal is 0.8-1.5.
2. The method as set forth in claim 1, wherein the content of the modifying metal in the catalyst is more than 0 and 10 w% or less.
3. The method of claim 1, wherein the resin has a total exchange capacity of 3.0 to 6.0 mmol/g.
4. The method of claim 1, wherein the resin is of the gel type or macroporous type.
5. The method according to claim 1, wherein the mass ratio of methylal to paraformaldehyde is 0.01 to 100: 1.
6. The method of claim 1, wherein the amount of the catalyst is 0.05 to 10% by weight based on the weight of the raw material.
7. The method according to claim 1, wherein the reaction temperature is 70 to 200 ℃.
8. The method according to claim 1, wherein the reaction pressure is 0.2 to 6 MPa.
9. The process as claimed in claim 1, wherein the reaction time is from 1 to 20 hours.
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