CN101665409A - Method for catalytic synthesis of 1,3-dibasic alcohol or cyclic acetal of 1,3-dibasic alcohol by using ionic liquid - Google Patents
Method for catalytic synthesis of 1,3-dibasic alcohol or cyclic acetal of 1,3-dibasic alcohol by using ionic liquid Download PDFInfo
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- dibasic alcohol
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Abstract
The invention discloses a method for synthesizing 1,3-dibasic alcohol or cyclic acetal of 1,3-dibasic alcohol(1,3-dioxane derivative)by using a functional acid ionic liquid serving as a catalyst to catalyze the condensation reaction of formaldehyde and alkene. In the method, the aqueous solution of formaldehyde and the alkene are used as reactants to the 1,3-dibasic alcohol or cyclic acetal of 1,3-dibasic alcohol(1,3-dioxane derivative) under a mild reaction condition in the presence of the functional acid ionic liquid serving as the catalyst. The method has the advantages of readily availablereaction materials, low-corrosivity high-catalytic activity reusable catalyst, high product selectivity, simple reaction process, easy operation and strong controllability.
Description
Technical field
The present invention relates to a kind of is catalyzer with the functionalization acidic ionic liquid body, and catalysis formaldehyde and alkene condensation reaction synthesize 1, the method for 3-dibasic alcohol or its cyclic acetal (1, the 3-3-dioxane derivatives).
Background technology
1, the 3-dibasic alcohol has characteristics such as odorless, low toxicity, good water solubility, mainly as monomer and solvent, antifreezing agent or the protective material etc. of polyester and urethane, also can directly be used as wetting agent and softening agent.In fields such as fine chemistry industry, medicine, dyestuffs purposes is widely arranged.Particularly 1, ammediol as the main raw material of production Poly(Trimethylene Terephthalate) (PTT), is a synthon hot of research and development in the world at present.PTT is a kind of new polyester material, has excellent rebound resilience, dyeability, and pollution resistance has broad application prospects in fields such as carpet, engineering plastics, garment materials.
With aldehydes and alkene condensation reaction synthesis of cyclic acetals (1, the 3-3-dioxane derivatives) under the acid catalyst effect such as formaldehyde, hydrolysis preparation 1,3-dibasic alcohol.In the olefine aldehyde condensation reaction process, the synthesis of cyclic acetal is the core procedure of this reaction.Catalyzer commonly used has sulfuric acid, AlCl
3, SnCl
4Deng.The seventies,, inquired into by the formaldehyde preparation 1 of setting out, this technological line of 3-dibasic alcohol based on Japanese Supreme Being people company.Find BF
3(JP51146405-A), BiI
3(US 4338290-A), SnO
2(JP 53103406-A) etc. all can be used as the olefine aldehyde condensation catalyst for reaction, and 1, the yield of ammediol can reach 74%.Above-mentioned catalyzer has that corrodibility is strong, side reaction is many, aftertreatment technology is complicated, particularly easily cause problems such as environmental pollution.As improvement, also having with tosic acid (JP 51143606-A), phospho-wolframic acid (JP 51113809-A) is that catalyzer is studied the olefine aldehyde condensation reaction, but still has defectives such as catalyst levels is big, by product is many.2000, DuPont company (US 6111135) reported that trifluoroacetic acid ytterbium (or bismuth) is a catalyzer, and catalysis formaldehyde and ethene react 16h under the condition of 130 ℃/6.9MPa, can obtain 62%～66% 1, the ammediol dicarboxylic acid esters can obtain 1 after the hydrolysis, ammediol.This catalyst system severe reaction conditions, selectivity of product are low.Ionic liquid becomes the focus of Green Chemistry research as a kind of novel green solvent or catalyzer, is widely used in some important acetalations.2003, people such as Yadav (Eur.J Org.Chem.) reported first-generation ionic liquid [Bmin] ClAlCl
xApplication in the olefine aldehyde condensation reaction, reaction conversion ratio can reach 95%, but AlCl
3There are defectives such as harsh to the water-content requirement, that hydrothermally stable is poor, catalyst levels is big in the type ionic liquid.Selecting low-corrosiveness and olefine aldehyde condensation catalyst for reaction efficiently, realize effective catalytic cycle, improve selectivity of product, is to solve chemical method to synthesize 1, a key issue of 3-dibasic alcohol technology.
Summary of the invention
The objective of the invention is to overcome defectives such as the catalytic erosion that exists in the prior art is strong, side reaction is many, complex process, under relatively mild condition, a kind of ionic liquid-catalyzed formaldehyde and alkene condensation reaction synthetic 1 is provided, the method of 3-dibasic alcohol or its cyclic acetal (1, the 3-3-dioxane derivatives).
Chemical equation of the present invention is:
R represents H, alkyl or aryl
A kind of 1, the preparation method of 3-dibasic alcohol or its cyclic acetal, it is characterized in that: use formalin and alkene as reactant, with the functionalization acidic ionic liquid body as catalyzer, wherein the cationic moiety of functionalization acidic ionic liquid body is selected from glyoxaline cation or pyridylium, and anionicsite is selected from trifluoromethane sulfonic acid root, bisulfate ion or p-methyl benzenesulfonic acid root; Under inert gas atmosphere, 60～120 ℃ of control reaction temperature, reaction pressure 1.0～8.0MPa, the condensation reaction of 1～10 hour reaction times synthesizes 1,3-dibasic alcohol or its cyclic acetal.
In aforesaid method, alkene is selected from ethene, propylene, 1-butylene, iso-butylene, 1-amylene, 1-hexene, 1-octene, 1-laurylene or vinylbenzene.
In aforesaid method, the massfraction of formalin is 37%～60%.
In aforesaid method, the mol ratio of alkene and formaldehyde is 0.5: 1～5: 1.
In aforesaid method, catalyst consumption is 1～8wt% of total charging capacity.
In aforesaid method, preferable reaction temperature is 80～100 ℃;
In aforesaid method, preferred reaction pressure is 3.0～5.0MPa.
In aforesaid method, the preferred reaction time is 4～8 hours.
In aforesaid method, rare gas element is selected from nitrogen or helium, considers economy, and preferred rare gas element is a nitrogen.
The present invention has the following advantages:
1) catalyst levels is few, the catalytic activity height, and the transformation efficiency of formaldehyde can reach 99.2%.The selectivity of product height, 1, the overall selectivity of 3-dibasic alcohol and its cyclic acetal can reach 99%.
2) catalytic erosion is low, and technology is simple.
3) catalyzer is stable, and reaction can be carried out in the aqueous solution.
4) reaction product and ionic liquid are easily separated, and catalyzer can be recycled.
5) under suitable condition, but single stage method obtains 1, the 3-dibasic alcohol.
6) reaction raw materials there is not particular requirement, cheap and easy to get, the operational condition gentleness.
In a word, reaction raw materials of the present invention is easy to get, and catalytic erosion is low, catalytic activity is high and can be recycled, the selectivity of product height, and easy, the easy operation of reaction process, controllability are strong.
Embodiment
Catalyzer is expressed as follows:
R
1＝CH
3，X＝CF
3SO
3，[MBsIm][CF
3SO
3] R
1＝H， [BsPy][CF
3SO
3]
R
1＝CH
3，X＝HSO
4， [MBsIm][HSO
4] R
1＝CH
3，[MBsPy][CF
3SO
3]
Embodiment 1:
Add 0.42g ionic liquid [MBsIm] [CF in the high-pressure reactor of 30mL
3SO
3] and the formalin of 15.4g 37%, closed reactor, the air with in the nitrogen replacement reactive system of 2.0MPa charges into 5.6g ethene, and inflated with nitrogen is to 3.0MPa.Stir, be warming up to 80 ℃ in the 30min, under the condition of 8.0MPa, react 8h.Reaction is cooled to room temperature, release after finishing.GC analyzes, inner mark method ration.The transformation efficiency of formaldehyde is 99.2%, 1, and the selectivity of 3-dioxane is 83.9%, 1, and the selectivity of ammediol is 12.3%, target product 1, and 3-dioxane and 1, the overall selectivity of ammediol is 96.2%.
Embodiment 2:
With embodiment 1.100 ℃ of reactions down, the transformation efficiency of formaldehyde is 78.4%, 1, and the selectivity of 3-dioxane is 31.5%, 1, and the selectivity of ammediol is 67.5%, target product 1, and 3-dioxane and 1, the overall selectivity of ammediol is 99.0%.
Embodiment 3:
With embodiment 1.With ionic liquid [MBsIm] [HSO
4] be catalyzer, 100 ℃ of reactions down, the transformation efficiency of formaldehyde is 82.5%, 1, and the selectivity of 3-dioxane is 11.9%, 1, and the selectivity of ammediol is 86.1%, target product 1,3-dioxane and 1, the overall selectivity of ammediol is 98.0%.
Embodiment 4:
Add 0.45g ionic liquid [MBsIm] [CF in the high-pressure reactor of 30mL
3SO
3] and the formalin of 15.4g 37%, closed reactor, the air with in the nitrogen replacement reactive system of 2.0MPa charges into the 7.2g propylene, and inflated with nitrogen is to 3.0MPa.Stir, be warming up to 80 ℃ in the 30min, under the condition of 5.0MPa, react 8h.Reaction is cooled to room temperature, release after finishing.GC analyzes, inner mark method ration.The transformation efficiency of formaldehyde is 87.0%, product 1,3 butylene glycol and 4-methyl isophthalic acid, and the overall selectivity of 3-dioxane is 91.2%.
Embodiment 5:
With embodiment 4.With ionic liquid [MBsIm] [HSO
4] be catalyzer.The transformation efficiency of formaldehyde is 53.8%, product 1,3 butylene glycol and 4-methyl isophthalic acid, and the overall selectivity of 3-dioxane is 85.2%.
Embodiment 6:
With embodiment 4.With ionic liquid [BsPy] [CF
3SO
3] be catalyzer.The transformation efficiency of formaldehyde is 56.4%, product 1,3 butylene glycol and 4-methyl isophthalic acid, and the overall selectivity of 3-dioxane is 89.4%.
Embodiment 7:
With embodiment 4.With ionic liquid [MBsPy] [CF
3SO
3] be catalyzer.The transformation efficiency of formaldehyde is 50.7%, product 1,3 butylene glycol and 4-methyl isophthalic acid, and the overall selectivity of 3-dioxane is 91.8%.
Embodiment 8:
With embodiment 4.Ion liquid consumption is 0.2g.The transformation efficiency of formaldehyde is 72.2%, product 1,3 butylene glycol and 4-methyl isophthalic acid, and the overall selectivity of 3-dioxane is 91.5%.
Embodiment 9:
With embodiment 4.Ion liquid consumption is 0.84g.The transformation efficiency of formaldehyde is 87.4%, product 1,3 butylene glycol and 4-methyl isophthalic acid, and the overall selectivity of 3-dioxane is 91.0%.
Embodiment 10:
With embodiment 4.The charging capacity of propylene is 3.6g.The transformation efficiency of formaldehyde is 59.4%, product 1,3 butylene glycol and 4-methyl isophthalic acid, and the overall selectivity of 3-dioxane is 90.3%.
Embodiment 11:
With embodiment 4.The charging capacity of propylene is 14.4g.The transformation efficiency of formaldehyde is 85.1%, product 1,3 butylene glycol and 4-methyl isophthalic acid, and the overall selectivity of 3-dioxane is 91.8%.
Embodiment 12:
With embodiment 4.Temperature of reaction is 120 ℃.The transformation efficiency of formaldehyde is 85.8%, product 1,3 butylene glycol and 4-methyl isophthalic acid, and the overall selectivity of 3-dioxane is 85.6%.
Embodiment 13:
With embodiment 4.With the iso-butylene is reaction raw materials, feeds intake to be 11.2g.The transformation efficiency of formaldehyde is 51.8%, 4,4-dimethyl-1, and the selectivity of 3-dioxane is 45.9%, the 3-methyl isophthalic acid, the overall selectivity of 3-butyleneglycol is 52.3%.
Claims (9)
1, a kind of 1, the preparation method of 3-dibasic alcohol or its cyclic acetal, it is characterized in that: use formalin and alkene as reactant, with the functionalization acidic ionic liquid body as catalyzer, wherein the cationic moiety of functionalization acidic ionic liquid body is selected from glyoxaline cation or pyridylium, and anionicsite is selected from trifluoromethane sulfonic acid root, bisulfate ion or p-methyl benzenesulfonic acid root; Under inert gas atmosphere, 60～120 ℃ of control reaction temperature, reaction pressure 1.0～8.0MPa, the condensation reaction of 1～10 hour reaction times synthesizes 1,3-dibasic alcohol or its cyclic acetal.
2, the method for claim 1 is characterized in that alkene is selected from ethene, propylene, 1-butylene, iso-butylene, 1-amylene, 1-hexene, 1-octene, 1-laurylene or vinylbenzene.
3, the method for claim 1, the massfraction that it is characterized in that formalin is 37%～60%.
4, the method for claim 1, the mol ratio that it is characterized in that alkene and formaldehyde is 0.5: 1～5: 1.
5, the method for claim 1 is characterized in that catalyst consumption is 1～8wt% of total charging capacity.
6, the method for claim 1 is characterized in that temperature of reaction is 80～100 ℃;
7, the method for claim 1 is characterized in that reaction pressure is 3.0～5.0MPa.
8, the method for claim 1 is characterized in that the reaction times is 4～8 hours.
9, the method for claim 1 is characterized in that rare gas element is selected from nitrogen or helium.
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| CN103102246A (en) * | 2011-11-10 | 2013-05-15 | 中国科学院大连化学物理研究所 | Method for preparing 1,3-dihydric alcohol |
| CN103102229A (en) * | 2011-11-10 | 2013-05-15 | 中国科学院大连化学物理研究所 | Method for preparing 1,3-dihydric alcohol directly from olefin |
| CN103958492A (en) * | 2011-11-24 | 2014-07-30 | 提克纳有限公司 | Process for the production of trioxane |
| CN106831358A (en) * | 2017-01-18 | 2017-06-13 | 东营市海科新源化工有限责任公司 | A kind of preparation method of dipropylene glycol |
| CN107032941A (en) * | 2016-02-03 | 2017-08-11 | 中国科学院兰州化学物理研究所 | The method of ionic liquid-catalyzed olefine aldehyde condensation reaction synthesis isoprene |
| CN108017513A (en) * | 2016-11-03 | 2018-05-11 | 中国科学院大连化学物理研究所 | A kind of 3- methyl isophthalic acids, the preparation method of 3- butanediols |
| CN108017512A (en) * | 2016-11-03 | 2018-05-11 | 中国科学院大连化学物理研究所 | One kind prepares 3- methyl isophthalic acids, the method for 3- butanediols |
| CN108586197A (en) * | 2018-05-03 | 2018-09-28 | 浙江新化化工股份有限公司 | A kind of production method of 1,3 butylene glycol |
| CN109776262A (en) * | 2017-11-13 | 2019-05-21 | 中国石油化工股份有限公司 | Olefine aldehyde condensation reaction method |
| CN109776263A (en) * | 2017-11-13 | 2019-05-21 | 中国石油化工股份有限公司 | Method for olefine aldehyde condensation reaction |
| CN109776264A (en) * | 2017-11-13 | 2019-05-21 | 中国石油化工股份有限公司 | The method of olefine aldehyde condensation reaction |
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| US10829467B2 (en) | 2018-03-29 | 2020-11-10 | Celanese Sales Germany Gmbh | Process for producing a cyclic acetal in a heterogeneous reaction system |
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| CN103102229B (en) * | 2011-11-10 | 2015-02-04 | 中国科学院大连化学物理研究所 | Method for preparing 1,3-dihydric alcohol directly from olefin |
| CN103102246A (en) * | 2011-11-10 | 2013-05-15 | 中国科学院大连化学物理研究所 | Method for preparing 1,3-dihydric alcohol |
| CN103958492A (en) * | 2011-11-24 | 2014-07-30 | 提克纳有限公司 | Process for the production of trioxane |
| US9469624B2 (en) | 2011-11-24 | 2016-10-18 | Ticona Gmbh | Integrated process for producing cyclic acetals and oxymethylene polymers |
| US9499512B2 (en) | 2011-11-24 | 2016-11-22 | Ticona Gmbh | Process for producing a cyclic acetal in a heterogeneous reaction system |
| US9546148B2 (en) | 2011-11-24 | 2017-01-17 | Ticona Gmbh | Process for the production of trioxane from aqueous formaldehyde sources |
| US9574061B2 (en) | 2011-11-24 | 2017-02-21 | Celanese Sales Germany Gmbh | Process for producing a cyclic acetal |
| US9604956B2 (en) | 2011-11-24 | 2017-03-28 | Celanese Sales Germany Gmbh | Process for the production of trioxane |
| CN107032941A (en) * | 2016-02-03 | 2017-08-11 | 中国科学院兰州化学物理研究所 | The method of ionic liquid-catalyzed olefine aldehyde condensation reaction synthesis isoprene |
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| CN108017512A (en) * | 2016-11-03 | 2018-05-11 | 中国科学院大连化学物理研究所 | One kind prepares 3- methyl isophthalic acids, the method for 3- butanediols |
| CN108017513B (en) * | 2016-11-03 | 2021-06-01 | 中国科学院大连化学物理研究所 | Preparation method of 3-methyl-1, 3-butanediol |
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| CN109776262A (en) * | 2017-11-13 | 2019-05-21 | 中国石油化工股份有限公司 | Olefine aldehyde condensation reaction method |
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| US10829467B2 (en) | 2018-03-29 | 2020-11-10 | Celanese Sales Germany Gmbh | Process for producing a cyclic acetal in a heterogeneous reaction system |
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| CN114085128B (en) * | 2021-10-28 | 2024-02-20 | 中国科学院过程工程研究所 | Method for separating and purifying 1,2,4-butanetriol based on difunctional ionic liquid |
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Application publication date: 20100310 |