CN109232489A - A kind of preparation method of furans biology base dibutyl ester - Google Patents
A kind of preparation method of furans biology base dibutyl ester Download PDFInfo
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- CN109232489A CN109232489A CN201710555158.9A CN201710555158A CN109232489A CN 109232489 A CN109232489 A CN 109232489A CN 201710555158 A CN201710555158 A CN 201710555158A CN 109232489 A CN109232489 A CN 109232489A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
Abstract
The invention discloses a kind of preparation methods of furans biology base dibutyl ester, include the following steps: in butanol solution, are added 2,5- furandicarboxylic acid is raw material, adds acidic catalyst, is performed under reduced pressure esterification dehydration, 2,5-furandicarboxylic acid dibutyl ester is made.The preparation method reaction condition is mild, yield >=75%, catalyst are cheap and easy to get, high production efficiency, simple process and product purity are high, has huge applications value.
Description
Technical field
The present invention relates to a kind of preparation methods of plasticizer, more particularly, to a kind of preparation of furans biology base dibutyl ester
Method.
Background technique
Plastics since invention, be gradually transitioned into necessary in living usually as people before century more than one
Product develop into globalization industry.And based on its own excellent characteristic, in changeable application environment, plastics are still
Outstanding performance can be showed, still, largely plastics must rely on the use of a variety of materials auxiliary agent.Plasticizer conduct
A kind of important meterial additive accounts for about the one third of global plastic additive market comsupton total value.Wherein phthalic acid ester
Class plasticizer yield highest, use are most extensive.However, in recent years, more and more endangering the mankind about phthalate
The research of health is reported.In animal experiments, phthalic acid ester shows potential endocrine disruption toxicity and cause
It is carcinous, cause experiment body teratogenesis and mutagenesis；There are genotoxicities, such as sperm count and survival rate to be remarkably decreased situation.Mesh
Before, European Union, Japan release one after another the related legal provision with the U.S., are forbidden to use part phthalic ester plasticizer.
2,5-furandicarboxylic acid (FDCA) is used as biology base fragrant monomer, has with petroleum base monomeric phthalic similar
Chemical structure, and phthalic acid ester possesses preferably plasticising performance, and furan near its derivative 2,5-furandicarboxylic acid ester
Class of muttering compound is able to enter internal Krebs circulation, thus 2,5-furandicarboxylic acid ester be expected to replace phthalate at
For a kind of health type plasticizer of novel environmental protection.Synthetic method about 2,5-furandicarboxylic acid ester has very much, such as: Van
Es etc. is using methanesulfonic acid as catalyst, and by FDCA and 2-Ethylhexyl Alcohol, direct esterification is obtained under the conditions of 160 DEG C, nitrogen atmosphere
(acid alcohol ratio 1:3) (Van Es, D.S, Van Haveren, J.et al.Stabilized flexible PVC
compositions and articles made therefrom.WO2015/0183954A1,2015-7-2).However, due to
Higher reaction temperature deepens finally obtained reaction solution color, and usually brown or crocus, not only cause product
Decoloration increased costs, and the product quality decline made.Kenneth etc. is by FDCA and n-butanol in pressure 500psi CO2 atmosphere
It encloses, direct esterification obtains (Kenneth.S.et al.esterification of2,5- under the conditions of 200 DEG C of temperature
Furandicarboxylia acid.WO2015/0315166A1,2015-11-5).Due to higher reaction temperature and high-purity
The CO2 atmosphere requirement of degree, high pressure, not only makes that increased production cost, there are security risk in operating process, and yield
It is low.Therefore, it is difficult to be applied in industry again.So in industrial processes, it is badly in need of a kind of high production efficiency, at low cost, technique letter
Single method.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation methods of furans biology base dibutyl ester.The preparation side
Method reaction condition is mild, yield >=75%, catalyst are cheap and easy to get, high production efficiency, simple process and product purity are high, has
Huge applications value.
To solve the above problems, the present invention adopts the following technical scheme that:
A kind of preparation method of furans biology base dibutyl ester, includes the following steps:
In butanol solution, 2,5-furandicarboxylic acid is added (later referred to as: being FDCA) raw material, add acidic catalyst
Agent is performed under reduced pressure esterification dehydration, and 2,5-furandicarboxylic acid dibutyl ester is made.
Reaction equation of the present invention is as follows:
In above-mentioned preparation method of the invention, since FDCA is solid insoluble in alcohol, therefore it is excessive to need butanol solution to use,
Butanol had not only been used as reactant but also had been used as solvent.FDCA concentration is in 50g/L-150g/L.In this concentration range, FDCA is molten with butanol
Liquid reaction effect is good.
As the further improvement of technical solution, the butanol solution includes n-butanol (CAS:71-36-3), isobutanol
(CAS:78-83-1), one of sec-butyl alcohol (CAS:78-92-2), tert-butyl alcohol (CAS:75-65-0) or a variety of.
As the further improvement of technical solution, the acidic catalyst include B acid, L acid, one of acidic resins or
It is a variety of.
Preferably, the B acid includes but is not limited to sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, fluosulfonic acid, phosphoric acid, amino sulphur
Acid, nitric acid, boric acid, p-methyl benzenesulfonic acid, benzene sulfonic acid, methanesulfonic acid, formic acid, acetic acid, oxalic acid, trifluoroacetic acid, trichloroacetic acid, fluoroform
One of base sulfonic acid, levulic acid are a variety of.
Preferably, the acidic resins include but is not limited to Amberlyst-15, Amberlyst-35, NKC-9,
One of IR120H, HND-32, HND-34, D072, DA345, DA330, D005-T or a variety of.
Preferably, the L acid includes but is not limited to ZSM-5, ZSM-11, ZSM-23, SAPO molecular sieve, HY, USY, β-point
Sub- sieve, aluminium chloride, iron chloride, boron trifluoride, stannous chloride, tin tetrachloride, zinc chloride, boron trifluoride, Boron tribromide, four chlorinations
Zirconium, four chlorinations one of are crowed or a variety of.
As the further improvement of technical solution, concentration of the acid catalyst in reactant is 0.01mol/L-
0.05mol/L, or with FDCA mass ratio be 10:1-1:10.Lower than this range, reaction rate is slack-off, and the time is elongated, is more than this model
It encloses reaction rate not also to be further added by, the increase of yield is also very small, causes the waste of catalyst.
As the further improvement of technical solution, the vacuum degree of the reduced pressure is 0.03Mpa-0.09Mpa.It reacted
Journey is performed under reduced pressure, and facilitates the water generated except dereaction, and reaction is made to be more conducive to positive carry out.Vacuum degree is lower than this model
It encloses, is difficult the water generated except dereaction, be unfavorable for reaction forward progress, vacuum degree is higher than this range, not only can be raw except dereaction
At water can also remove butanol solution, be also unfavorable for the positive of reaction and carry out.
As the further improvement of technical solution, the esterification dehydration temperature is 50 DEG C -150 DEG C, preferably 80 DEG C -90
℃.Temperature makes that reaction rate is slack-off, the reaction time is elongated lower than this range, and temperature is more than this range, the reaction solution that can make
Color burn, yield reduce.
As the further improvement of technical solution, the esterification dehydration time is 0.5h-72h, preferably 3h-6h.Instead
In 3h-6h between seasonable, reaction basically reaches saturation, increases the reaction time, and products collection efficiency increases small.
Any range documented by the present invention includes any numerical value between end value and end value and end value or end value
Between any subrange for being constituted of any number.
Unless otherwise specified, each raw material in the present invention can be obtained by commercially available purchase, equipment used in the present invention
The conventional equipment in fields can be used or carried out referring to the prior art of fields.
The invention has the following beneficial effects:
Preparation method reaction condition of the present invention is mild, yield >=75%, catalyst are cheap and easy to get, high production efficiency, technique
Simple and product purity is high, has huge applications value.
Specific embodiment
In order to illustrate more clearly of the present invention, below with reference to preferred embodiment, the present invention is described further.Ability
Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, this should not be limited with this
The protection scope of invention.
Embodiment 1:
Sulfuric acid catalysis prepares 2,5- furandicarboxylic acid N-butyl
It measures 25ml n-butanol and adds 4g FDCA in two mouth flask, while the 0.75ml concentrated sulfuric acid is added, reaction temperature
Depressor response (0.08MPa) under the conditions of 85 DEG C of degree reacts 5h, yield 99.31%.
Embodiment 2:
Sulfuric acid catalysis prepares 2,5- furandicarboxylic acid isobutyl ester
It measures 25ml isobutanol and adds 3.5g FDCA in two mouth flask, while 1ml sulfuric acid is added, reaction temperature 90
Depressor response (0.07MPa) under the conditions of DEG C reacts 7h, yield 98.11%.
Embodiment 3:
Hydrochloric acid catalysis prepares 2,5- furandicarboxylic acid isobutyl ester
It measures 25ml isobutanol and adds 2.5g FDCA in two mouth flask, while 0.75ml hydrochloric acid is added, reaction temperature
Depressor response (0.07MPa) under the conditions of 90 DEG C of degree reacts 8h, yield 92.31%.
Embodiment 4:
Sulfuric acid catalysis prepares the secondary butyl ester of 2,5- furandicarboxylic acid
It measures 25ml sec-butyl alcohol and adds 2g FDCA in two mouth flask, while 1ml sulfuric acid is added, 85 DEG C of reaction temperature
Under the conditions of Depressor response (0.055MPa), react 10h, yield 93.12%.
Embodiment 5:
Sulfuric acid catalysis prepares the 2,5- furandicarboxylic acid tert-butyl ester
It measures the 25ml tert-butyl alcohol and adds 1.5g FDCA in two mouth flask, while 1.25ml sulfuric acid is added, reaction temperature
Depressor response (0.06MPa) under the conditions of 80 DEG C of degree reacts 12h, yield 91.42%.
Embodiment 6:
Acidic molecular sieve ZSM-5 catalysis preparation 2,5- furandicarboxylic acid N-butyl
It measures 25ml n-butanol and adds 2.5g FDCA in two mouth flask, while ZSM-5 molecular sieve 1.5g is added, instead
Depressor response (0.035MPa) under the conditions of answering 110 DEG C of temperature reacts 23h, yield 83.62%.
Embodiment 7:
Acidic molecular sieve ZSM-5 catalysis preparation 2,5- furandicarboxylic acid isobutyl ester
It measures 25ml isobutanol and adds 2g FDCA in two mouth flask, while ZSM-5 molecular sieve 1g is added, reaction temperature
Depressor response (0.035MPa) under the conditions of 110 DEG C of degree reacts 27h, yield 79.73%.
Embodiment 8:
Acidic resins Amberlyst-15 catalysis preparation 2,5- furandicarboxylic acid N-butyl
It measures 25ml n-butanol and adds 3g FDCA in two mouth flask, while 1.5gAmberlyst-15 is added, instead
Depressor response (0.03MPa) under the conditions of answering 120 DEG C of temperature reacts 32h, yield 82.71%.
Embodiment 9:
Acidic resins Amberlyst-15 catalysis preparation 2,5- furandicarboxylic acid isobutyl ester
It measures 25ml isobutanol and adds 2.5g FDCA in two mouth flask, while 1gAmberlyst-15 is added, instead
Depressor response (0.03MPa) under the conditions of answering 120 DEG C of temperature reacts 36h, yield 80.63%.
Embodiment 10:
Embodiment 9 is repeated, the difference is that only:
The acidic resins select Amberlyst-35, NKC-9, IR120H, HND-32, HND-34, D072, DA345,
DA330 or D005-T.Effect and embodiment 9 are approximate.
Embodiment 11:
Repeat embodiment 1, the difference is that only: the acidic catalyst select hydrobromic acid, hydroiodic acid, fluosulfonic acid,
Phosphoric acid, sulfamic acid, nitric acid, boric acid, p-methyl benzenesulfonic acid, benzene sulfonic acid, methanesulfonic acid, formic acid, acetic acid, oxalic acid, trifluoroacetic acid, trichlorine
Acetic acid, trifluoromethane sulfonic acid or levulic acid.Effect and embodiment 1 are approximate.
Embodiment 12:
Repeat embodiment 1, the difference is that only: the acidic catalyst selects ZSM-11, ZSM-23, SAPO molecule
Sieve, HY, USY, β-molecular sieve, aluminium chloride, iron chloride, boron trifluoride, stannous chloride, tin tetrachloride, zinc chloride, boron trifluoride,
Boron tribromide, zirconium chloride or four chlorinations are crowed.Effect and embodiment 1 are approximate.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention.For those of ordinary skill in the art, may be used also on the basis of the above description
To make other variations or changes in different ways.Here all embodiments can not be exhaustive.It is all to belong to this hair
The obvious changes or variations that bright technical solution is extended out are still in the scope of protection of the present invention.
Claims (10)
1. a kind of preparation method of furans biology base dibutyl ester, which comprises the steps of:
In butanol solution, addition 2,5-furandicarboxylic acid is raw material, adds acidic catalyst, is performed under reduced pressure ester
Change dehydration, 2,5-furandicarboxylic acid dibutyl ester is made.
2. preparation method according to claim 1, it is characterised in that: the butanol solution includes n-butanol, isobutanol, secondary
One of butanol, tert-butyl alcohol are a variety of.
3. preparation method according to claim 1, it is characterised in that: the acidic catalyst includes B acid, L acid, acid tree
One of rouge is a variety of.
4. preparation method according to claim 3, it is characterised in that: the B acid includes but is not limited to sulfuric acid, hydrochloric acid, hydrogen
Bromic acid, hydroiodic acid, fluosulfonic acid, phosphoric acid, sulfamic acid, nitric acid, boric acid, p-methyl benzenesulfonic acid, benzene sulfonic acid, methanesulfonic acid, formic acid, second
One of acid, oxalic acid, trifluoroacetic acid, trichloroacetic acid, trifluoromethane sulfonic acid, levulic acid are a variety of.
5. preparation method according to claim 3, it is characterised in that: the acidic resins include but is not limited to
Amberlyst-15、Amberlyst-35、NKC-9、IR120H、HND-32、HND-34、D072、DA345、DA330、D005-T、
One of acid ZSM-5 molecular sieve is a variety of.
6. preparation method according to claim 3, it is characterised in that: the L acid include but is not limited to ZSM-5, ZSM-11,
ZSM-23, SAPO molecular sieve, HY, USY, β-molecular sieve, aluminium chloride, iron chloride, boron trifluoride, stannous chloride, tin tetrachloride, chlorine
Change zinc, boron trifluoride, Boron tribromide, zirconium chloride, four chlorinations one of are crowed or a variety of.
7. preparation method according to claim 1, it is characterised in that: concentration of the acid catalyst in reactant is
0.01mol/L-0.05mol/L, or with the mass ratio of 2,5-furandicarboxylic acid be 10:1-1:10.
8. preparation method according to claim 1, it is characterised in that: the vacuum degree of the reduced pressure is 0.03Mpa-
0.09Mpa。
9. preparation method according to claim 1, it is characterised in that: the esterification dehydration temperature is 50 DEG C -150
DEG C, preferably 80 DEG C -90 DEG C.
10. preparation method according to claim 1, it is characterised in that: the esterification dehydration time is 0.5h-72h,
It is preferred that 3h-6h.
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Cited By (4)
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| CN110526884A (en) * | 2019-08-05 | 2019-12-03 | 中国科学技术大学 | New bio base furans ester perfume and its synthetic method |
| CN112209906A (en) * | 2019-07-10 | 2021-01-12 | 中国科学院宁波材料技术与工程研究所 | Preparation method of furan didecyl ester |
| CN112724624A (en) * | 2020-12-28 | 2021-04-30 | 生刚 | Full-biodegradable paper-plastic composite material and preparation method thereof |
| CN112745283A (en) * | 2019-10-30 | 2021-05-04 | 中国科学院宁波材料技术与工程研究所 | Method for rapidly improving solubility of 2, 5-furandicarboxylic acid in esterification reaction |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112209906A (en) * | 2019-07-10 | 2021-01-12 | 中国科学院宁波材料技术与工程研究所 | Preparation method of furan didecyl ester |
| CN110526884A (en) * | 2019-08-05 | 2019-12-03 | 中国科学技术大学 | New bio base furans ester perfume and its synthetic method |
| CN112745283A (en) * | 2019-10-30 | 2021-05-04 | 中国科学院宁波材料技术与工程研究所 | Method for rapidly improving solubility of 2, 5-furandicarboxylic acid in esterification reaction |
| CN112745283B (en) * | 2019-10-30 | 2023-01-03 | 中国科学院宁波材料技术与工程研究所 | Method for rapidly improving solubility of 2, 5-furandicarboxylic acid in esterification reaction |
| CN112724624A (en) * | 2020-12-28 | 2021-04-30 | 生刚 | Full-biodegradable paper-plastic composite material and preparation method thereof |
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Application publication date: 20190118 |