CN102643265A - Preparation method of trioxymethylene - Google Patents
Preparation method of trioxymethylene Download PDFInfo
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- CN102643265A CN102643265A CN201210111829XA CN201210111829A CN102643265A CN 102643265 A CN102643265 A CN 102643265A CN 201210111829X A CN201210111829X A CN 201210111829XA CN 201210111829 A CN201210111829 A CN 201210111829A CN 102643265 A CN102643265 A CN 102643265A
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- trioxymethylene
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- 0 *N(CCCCC1)C1=O Chemical compound *N(CCCCC1)C1=O 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N O=C1NCCCCC1 Chemical compound O=C1NCCCCC1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- BUGOPWGPQGYYGR-UHFFFAOYSA-N O=S1(CCCCC1)=O Chemical compound O=S1(CCCCC1)=O BUGOPWGPQGYYGR-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a preparation method of trioxymethylene. The preparation method comprises the following step that: formalin is reacted in the presence of a catalyst, and then the trioxymethylene is obtained, wherein the catalyst is Br phi nsted acidic ionic liquid; and the percentage by weight of the formalin is 30-70%. The Br phi nsted acidic ionic liquid adopted in the preparation method disclosed by the invention has the acidity of the ionic liquid and is liquid at a room temperature, so that the synthetic ionic liquid has great potential to be used as a reaction medium in trioxymethylene transformation. The Br phi nsted acidic ion liquid adopted in the preparation method is used as the catalyst, the dosage of the catalyst is small, the catalytic activity and the transformation rate are high, the catalyst and a product can be automatically separated after the reaction, the ionic liquid can be reused after being recovered, and the activity of the ionic liquid is slightly reduced.
Description
Technical field
The present invention relates to a kind of preparation method of trioxymethylene.
Background technology
The trioxymethylene purposes very extensively; It is not only the raw material monomer of synthesizing engineering plastic polyoxymethylene; Also can prepare anhydrous formaldehyde and stablizer, sticker, sterilant, formed material, smoke fumigant, antimicrobial drug, sterilizing agent etc., trioxymethylene simultaneously also can depolymerization generate formaldehyde, so can be applied to formaldehyde be in the reaction of raw material for it; Particularly when the needs anhydrous formaldehyde was made reagent, its application had more value.
The compound method of trioxymethylene is normally with 36% industrial formol dehydration by evaporation; Be concentrated into about 65%, synthesizing triformol under the effect of an acidic catalyst vitriolic, trioxymethylene content is up to about 2.8% in the reactor product; But this technology exists corrosive equipment; Product selectivity is poor, and sub product formic acid (in acid number) is up to 20950ppm, and product such as separates at shortcoming with the catalyzer difficulty.Therefore it is very necessary researching and developing the environmentally friendly catalyzer of a kind of high-activity high-selectivity.
Ionic liquid has been widely used in the catalyzed reaction as a kind of new catalyst, and to ionic liquid-catalyzed synthesizing triformol, up to the present, people mainly are to concentrate on types such as imidazoles, pyridines to ion liquid research.People such as Xia Chungu (CN 1978438A) have studied imidazoles and pyridines synthesizing tripoly aldehyde by ionic liquid catalysis of aldehyde.The old people of waiting quietly (CN 102020629A) has reported the research of the ionic liquid-catalyzed formaldehyde cyclisation of a kind of dumbbell shape synthesizing triformol.But the application in the catalysis synthesizing triformol does not appear in the newspapers as yet about Br φ nsted acidic ion liquid.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of trioxymethylene can overcome shortcomings such as the ionic liquid building-up process that exists in the prior art is complicated, cost height.
The preparation method of a kind of trioxymethylene provided by the present invention comprises the steps: that formalin reacts promptly to get under the condition that catalyzer exists; Said catalyzer is a Br φ nsted acidic ion liquid.
Among the above-mentioned preparation method, the structural formula of said Br φ nsted acidic ion liquid is suc as formula shown in the I,
Formula I
In the formula, n is 3 or 4; B
-Be bisulfate ion, formate, phosphate radical, acetate, tosic acid root or hexafluoro-phosphate radical.
Among the above-mentioned preparation method, the quality percentage composition of said formalin can be 30%～70%, specifically can be 35%, 48%, 50%, 60%, 68% or 70%.
Among the above-mentioned preparation method, said catalyst consumption can be said formalin quality 0.1%～10%, specifically can be 0.2%, 0.5%, 1.0%, 2.0%, 3.0%, 3.5%, 5.0%, 7.0% or 8.0%.
Among the above-mentioned preparation method, the temperature of said reaction can be 90 ℃～120 ℃, specifically can be 90 ℃, 95 ℃, 100 ℃, 102 ℃ or 105 ℃, and the time is 0.5h～3h, specifically can be 0.5h, 1.5h or 2h.
The present invention has following beneficial effect:
1, the Br φ nsted acidic ion liquid of the present invention's employing, taking into account under ion liquid acidity and the room temperature is liquid, thereby makes the synthetic ionic liquid very big potentiality arranged as the reaction medium in the trioxymethylene conversion.
2, the Br φ nsted acidic ion liquid that adopts of the present invention is as catalyzer, and catalyst consumption is few, and catalytic activity is high, and transformation efficiency is high, can catalyzer and product phase-splitting automatically after reaction finishes, after the ionic liquid recovery, can reuse, and activity slightly descends.
3, be reflected under the normal pressure and carry out, the requirement that compares reaction unit with condition under the high pressure is lower, because ion liquid characteristic, reaction corrodibility is less.
4, the preparation method is simple, easy handling, and the reaction times is short, and the yield height is little to equipment corrosion, promptly can reduce the energy, can reduce cost again, and is environmentally friendly, can realize that cleaning is green synthetic.
Embodiment
Employed experimental technique is ordinary method like no specified otherwise among the following embodiment.
Used material, reagent etc. like no specified otherwise, all can obtain from commercial sources among the following embodiment.
The structure of Br φ nsted acidic ion liquid shown in used formula I-1～I-12 is following among the following embodiment:
Above-mentioned ion can be that 201110003473.3 patented claim disclosed methods prepare according to application number all; Synthesize example explanation (other several kinds of preparation method of ionic liquid are identical with ion liquid shown in the formula I-1; As long as change negatively charged ion) the preparation process: hexanolactam is earlier with 1; The reaction of 4-butane sultone, reaction equation is following:
Obtain ionic-liquid catalyst I-1 after product that generates and the pairing of bisulfate ion negatively charged ion.
Concrete steps are:
(1) with hexanolactam and 1, the 4-butane sultone adds and is furnished with in the churned mechanically four-hole boiling flask by behind 1: 1.1 molar ratio weighing; Add and 1: 4 absolute ethyl alcohol of hexanolactam mol ratio again, 80 ℃ of following stirring and refluxing, reaction 24h; Reaction finishes, and steams ethanol;
(2) use the constant voltage feed hopper slowly to add to be 1: 1 the vitriol oil, guarantee temperature-stable about 80 ℃ with the hexanolactam mol ratio, treat that the vitriol oil adds fully after, stirring reaction continues 6h and finishes, product is ionic-liquid catalyst I-1.
The preparation of embodiment 1, trioxymethylene
The formalin (formaldehyde content 60.0%) that in reaction vessel, adds 60g adds Br φ nsted acidic ion liquid shown in the formula I-1 of 2% (with the mass ratio of formalin) again; Be heated to 100 ℃, stirring reaction 1.5h, through gas chromatographic analysis, the trioxymethylene content in the synthetic liquid is 2.44%, formic acid content (in acid number) is 3328ppm.
The preparation of embodiment 2, trioxymethylene
Other uses the nsted of Br φ shown in formula I-2 acidic ion liquid to be catalyzer with embodiment 1, and consumption is 5.0% (with the mass ratio of formalin) of formalin (formaldehyde content 48.0%); Be heated to 95 ℃, stirring reaction 1.5h, the trioxymethylene content in the synthetic liquid is 1.35%, formic acid content is 2433ppm.
The preparation of embodiment 3, trioxymethylene
Other is with embodiment 1; Use the nsted of Br φ shown in formula I-3 acidic ion liquid to be catalyzer; Consumption is 3.0% (with the mass ratio of formalin) of formalin (formaldehyde content 68.0%), is heated to 100 ℃, stirring reaction 2h; Trioxymethylene content in the synthetic liquid is 1.43%, and formic acid content is 2547ppm.
The preparation of embodiment 4, trioxymethylene
Other is with embodiment 1; Use the nsted of Br φ shown in formula I-4 acidic ion liquid to be catalyzer; Consumption is 8.0% (with the mass ratio of formalin) of formalin (formaldehyde content 35.0%), is heated to 105 ℃, stirring reaction 0.5h; Trioxymethylene content in the synthetic liquid is 1.88%, and formic acid content is 1962ppm.
The preparation of embodiment 5, trioxymethylene
Other is with embodiment 1; Use the nsted of Br φ shown in formula I-5 acidic ion liquid to be catalyzer; Consumption is 7.0% (with the mass ratio of formalin) of formalin (formaldehyde content 60.0%), is heated to 100 ℃, stirring reaction 1.5h; Trioxymethylene content in the synthetic liquid is 2.39%, and formic acid content is 2912ppm.
The preparation of embodiment 6, trioxymethylene
Other is with embodiment 1; Use the nsted of Br φ shown in formula I-6 acidic ion liquid to be catalyzer; Consumption is 5.0% (with the mass ratio of formalin) of formalin (formaldehyde content 50.0%), is heated to 90 ℃, stirring reaction 1.5h; Trioxymethylene content in the synthetic liquid is 1.64%, and formic acid content is 2030ppm.
The preparation of embodiment 7, trioxymethylene
Other is with embodiment 6; Use the nsted of Br φ shown in formula I-7 acidic ion liquid to be catalyzer; Consumption is 5.0% (with the mass ratio of formalin) of formalin (formaldehyde content 60.0%), is heated to 105 ℃, stirring reaction 1.5h; Trioxymethylene content in the synthetic liquid is 1.78%, and formic acid content is 2756ppm.
The preparation of embodiment 8, trioxymethylene
Other is with embodiment 1; Use the nsted of Br φ shown in formula I-8 acidic ion liquid to be catalyzer; Consumption is 1.0% (with the mass ratio of formalin) of formalin (formaldehyde content 60.0%), is heated to 95 ℃, stirring reaction 1.5h; Trioxymethylene content in the synthetic liquid is 1.36%, and formic acid content is 2402ppm.
The preparation of embodiment 9, trioxymethylene
Other is with embodiment 1; Use the nsted of Br φ shown in formula I-9 acidic ion liquid to be catalyzer; Consumption is 0.5% (with the mass ratio of formalin) of formalin (formaldehyde content 60.0%), is heated to 100 ℃, stirring reaction 3h; Trioxymethylene content in the synthetic liquid is 0.73%, and formic acid content is 2063ppm.
The preparation of embodiment 10, trioxymethylene
Other is with embodiment 1; Use the nsted of Br φ shown in formula I-10 acidic ion liquid to be catalyzer; Consumption is 2.0% (with the mass ratio of formalin) of formalin (formaldehyde content 60.0%), is heated to 95 ℃, stirring reaction 1.5h; Trioxymethylene content in the synthetic liquid is 1.42%, and formic acid content is 2534ppm.
The preparation of embodiment 11, trioxymethylene
Other is with embodiment 1; Use the nsted of Br φ shown in formula I-11 acidic ion liquid to be catalyzer; Consumption is 3.5% (with the mass ratio of formalin) of formalin (formaldehyde content 70.0%), is heated to 102 ℃, stirring reaction 1.5h; Trioxymethylene content in the synthetic liquid is 1.98%, and formic acid content is 2988ppm.
The preparation of embodiment 12, trioxymethylene
Other is with embodiment 1; Use the nsted of Br φ shown in formula I-12 acidic ion liquid to be catalyzer; Consumption is 0.2% (with the mass ratio of formalin) of formalin (formaldehyde content 70.0%), is heated to 100 ℃, stirring reaction 1.5h; Trioxymethylene content in the synthetic liquid is 0.67%, and formic acid content is 2066ppm.
The preparation of Comparative Examples, trioxymethylene
The formalin (formaldehyde content 60.0%) that in reaction vessel, adds 60g adds the vitriol oil (98%, commercially available) of 2% (with the mass ratio of formalin) again; Be heated to 102 ℃, stirring reaction 1.5h, through gas chromatographic analysis, the trioxymethylene content in the synthetic liquid is 2.81%, sub product formic acid content (in acid number) is 20950ppm.
Claims (5)
1. the preparation method of a trioxymethylene comprises the steps: that formalin reacts promptly to get under the condition that catalyzer exists; Said catalyzer is a Br φ nsted acidic ion liquid.
2. preparation method according to claim 1 is characterized in that: the structural formula of said Br φ nsted acidic ion liquid is suc as formula shown in the I,
In the formula, n is 3 or 4; B
-Be bisulfate ion, formate, phosphate radical, acetate, tosic acid root or hexafluoro-phosphate radical.
3. preparation method according to claim 1 and 2 is characterized in that: the quality percentage composition of said formalin is 30%～70%.
4. according to arbitrary described preparation method among the claim 1-3, it is characterized in that: said catalyst consumption be said formalin quality 0.1%～10%.
5. according to arbitrary described preparation method among the claim 1-4, it is characterized in that: the temperature of said reaction is 90 ℃～120 ℃, and the time is 0.5h～3h.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1978438A (en) * | 2005-12-09 | 2007-06-13 | 中国科学院兰州化学物理研究所 | Method for synthesizing tripoly aldehyde by ionic liquid catalysis of aldehyde |
| CN101311154A (en) * | 2007-05-22 | 2008-11-26 | 富艺国际工程有限公司 | Process for synthesizing triformol using ionic liquid |
| CN102120728A (en) * | 2011-01-10 | 2011-07-13 | 常州大学 | Sulfonic- functionalized caprolactam acidic ion liquid and preparation method thereof |
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- 2012-04-16 CN CN201210111829XA patent/CN102643265A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1978438A (en) * | 2005-12-09 | 2007-06-13 | 中国科学院兰州化学物理研究所 | Method for synthesizing tripoly aldehyde by ionic liquid catalysis of aldehyde |
| CN101311154A (en) * | 2007-05-22 | 2008-11-26 | 富艺国际工程有限公司 | Process for synthesizing triformol using ionic liquid |
| CN102120728A (en) * | 2011-01-10 | 2011-07-13 | 常州大学 | Sulfonic- functionalized caprolactam acidic ion liquid and preparation method thereof |
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Application publication date: 20120822 |