CN106631785A - Preparation method of perfluoroheptyl ethyl itaconate - Google Patents
Preparation method of perfluoroheptyl ethyl itaconate Download PDFInfo
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- CN106631785A CN106631785A CN201611114096.XA CN201611114096A CN106631785A CN 106631785 A CN106631785 A CN 106631785A CN 201611114096 A CN201611114096 A CN 201611114096A CN 106631785 A CN106631785 A CN 106631785A
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- itaconate
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- ethanol
- perfluor heptyl
- heptyl ethanol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of perfluoroheptyl ethyl itaconate, and belongs to the field of itaconate. According to the preparation method, perfluoroheptyl ethanol and itaconic acid are subjected to dehydration and esterification reactions in the presence of a solid acid catalyst and a polymerization inhibitor. Specifically, the preparation method comprises the following steps: a, adding an organic solvent into a three-neck flask; b, adding perfluoroheptyl ethanol and itaconic acid; c, adding the polymerization inhibitor; d, adding the solid acid; e, heating the flask to carry out reactions under stirring and protection of nitrogen gas until no water is generated, and stopping esterification reactions; f, cooling and filtering raw reaction products; g, evaporating the organic solvent through rotation; and h, carrying out reduced pressure distillation to obtain perfluoroheptyl ethanol itaconate. The preparation method is environment-friendly and convenient, and has a high yield of perfluoroheptyl ethanol itaconate.
Description
Technical field
The invention belongs to itaconate field, is related to a kind of perfluor heptyl ethanol itaconate, particularly a kind of perfluor heptan
The preparation method of base ethanol itaconate.
Background technology
Itaconate is a kind of important derivatives from itaconic acid and fine chemical material, because its molecule contains one simultaneously
Carbon-to-carbon unsaturated double-bond and two carboxylate active function groups, can carry out various chemistry such as additive reaction and polyreaction anti-
Should, it is the important monomer for producing macromolecular material and fine chemicals, it is widely used in producing synthetic resin, synthetic fibers, knits
Numerous products such as thing finishing agent, surfactant, ion exchange resin, boiler detergent, lubricating additive and binding agent.Except clothing
Health acid mono-methyl, dimethyl itaconate, dibutyl itaconate, diisooctyl itaconate etc. are outer, and important itaconic acid esters are also
There are the fluorine-containing itaconates such as perfluor heptyl ethanol itaconate.
The fluorine-containing itaconates such as perfluor heptyl ethanol itaconate are mainly used in modified amino silicon oil and to prepare fabric whole
Reason agent, using effective shielding of the long chain fluorine-containing alkyl to amino, not only solves the problem of oxidation of amino, while making to change containing fluoroalkyl
Property amido silicon oil show low surface tension, Water-proof and oil-proof, chemical stability, weatherability, corrosion resistance and the antioxidation of brilliance
Property etc. fluorine element premium properties, give full play to the synergism of fluorine element silicon function, make fluorine-containing alkyl modified amido silicone oil and
The advantage of tool silicon fabric finishing agent and fluorine fabric finishing agent, with more perfect textile finishing performance, can be used for senior silks and satins clothes
Wider scope, the more high-grade textile finishings such as dress, room ornament, various families and office appliance.
At present, the synthesis of perfluor heptyl ethanol itaconate, generally with concentrated sulphuric acid as catalyst, catalysis activity is high, inexpensive
It is easy to get.But, reaction selectivity there is also as catalyst with concentrated sulphuric acid low, there is the side reactions such as dehydration, oxidation, carbonization, product
Difficulty is separated with catalyst, the postprocessing working procedures such as needs to neutralize, wash, produce that acid waste liquid is more, by-product is more, and equipment corrosion is tight
The shortcomings of weight, poor product quality.So, for those skilled in the art, needing to be developed one kind can eliminate to ring
The catalyst such as serious sulphuric acid, sulfonic acid, aluminum chloride are endangered in border, replace preparing using the new catalytic material of efficient pollution-free
The method of perfluor heptyl ethanol itaconate.
The content of the invention
The purpose of the present invention is there are the problems referred to above for existing technology, it is proposed that a kind of perfluor heptyl ethanol itaconic acid
The preparation method of ester, the preparation method of this perfluor heptyl ethanol itaconate has environmentally friendly convenient, perfluor heptyl ethanol itaconic acid
The characteristics of pick-up rate of ester is high.
The purpose of the present invention can be realized by following technical proposal：
A kind of preparation method of perfluor heptyl ethanol itaconate, it is characterised in that perfluor heptyl ethanol and itaconic acid exist
Be dehydrated in the presence of solid acid catalyst, polymerization inhibitor, esterification, specifically include following steps：
A, in there-necked flask add organic solvent；
B, addition perfluor heptyl ethanol, itaconic acid；
C, addition polymerization inhibitor；
D, addition solid acid；
E, under nitrogen protection heating, stirring carry out esterification, to there is no longer water generating, stop esterification；
F, cooling, filtration crude product；
G, rotary evaporation organic solvent；
H, decompression, distillation obtain perfluor heptyl ethanol itaconate.
The preparation method of this perfluor heptyl ethanol itaconate is simple and convenient, and unsaturated double-bond is not in esterification reaction process
Can be polymerized and be aoxidized, solid acid is used as catalyst efficiency high, it is ensured that perfluor heptyl ethanol itaconate is had higher
Pick-up rate；Wherein, solid acid catalyst is separated simply, and can directly reclaim reuse, reduces the three wastes, more green ring
Protect.
In the preparation method of above-mentioned perfluor heptyl ethanol itaconate, in described step (1), described organic solvent
For benzene or the double solventss of toluene or dimethylbenzene or toluene and dimethylbenzene.
In the preparation method of above-mentioned perfluor heptyl ethanol itaconate, in described step (d), solid acid is SO4 2-/
TiO2Or SO4 2-/ZrO2, or SO4 2-/TiO2-ZrO2。
In the preparation method of above-mentioned perfluor heptyl ethanol itaconate, in described step (e), reaction temperature 80-110
DEG C, response time 6-10h.
In the preparation method of above-mentioned perfluor heptyl ethanol itaconate, in described step (f), the solid being filtrated to get
Acid can directly be reclaimed and used.
In the preparation method of above-mentioned perfluor heptyl ethanol itaconate, in described step (h), inhibition is continuously added
Agent.
In the preparation method of above-mentioned perfluor heptyl ethanol itaconate, in described step (c) and (h), polymerization inhibitor is
Hydroquinone or p methoxy phenol or benzoquinone.
Compared with prior art, the preparation method of this perfluor heptyl ethanol itaconate is simple and convenient, in esterification mistake
Unsaturated double-bond will not be polymerized and be aoxidized, high catalytic efficiency in journey, and product yield is high, and solid acid separates simple and can be with
Directly reclaim and reuse, reduce the three wastes, more environmental protection.
Specific embodiment
The specific embodiment of the present invention is the following is, technical scheme is further described, but the present invention is simultaneously
It is not limited to these embodiments.
A kind of preparation method of perfluor heptyl ethanol itaconate, perfluor heptyl ethanol and itaconic acid are in solid acid catalysis
Be dehydrated in the presence of agent, polymerization inhibitor, esterification, specifically include following steps：
A, add in there-necked flask organic solvent, organic solvent can be chosen for benzene or toluene or dimethylbenzene or toluene with
The double solventss of dimethylbenzene；
B, addition perfluor heptyl ethanol, itaconic acid；
C, addition polymerization inhibitor, polymerization inhibitor is hydroquinone or p methoxy phenol or benzoquinone；
D, addition solid acid, solid acid is SO4 2-/TiO2Or SO4 2-/ZrO2, or SO4 2-/TiO2-ZrO2；
E, under nitrogen protection heating, stirring carry out esterification, to there is no longer water generating, stop esterification, specifically
For, reaction temperature chooses 80-110 DEG C, response time 6-10h；
F, cooling, filtration crude product, wherein, the solid acid being filtrated to get can directly be reclaimed and used；
G, rotary evaporation organic solvent；
H, decompression, distillation obtain perfluor heptyl ethanol itaconate, and it is hydroquinone or to methoxy to continuously add polymerization inhibitor
Base phenol or benzoquinone.
Summary, this preparation method is simple and convenient, and unsaturated double-bond will not be polymerized and oxygen in esterification reaction process
Change, solid acid is used as catalyst efficiency high, it is ensured that perfluor heptyl ethanol itaconate has higher pick-up rate；Wherein,
Solid acid catalyst is separated simply, and can directly reclaim reuse, reduces the three wastes, more environmental protection.
Embodiment one
Equipped with electromagnetic agitation, water knockout drum, reflux condensing tube, the four-hole boiling flask of thermometer, adding itaconic acid 10g, complete
Fluorine heptyl ethanol 56g, hydroquinone 1.6g, SO4 2-/TiO2Solid acid 0.9g, 250ml benzene；
Stirred under nitrogen atmosphere is heated to 80 DEG C, and reaction 8h is to there is no longer water generating, stopped reaction；
Cool down, filter, obtaining filtrate, rotary evaporation of solvent benzene, obtaining crude product；
1g hydroquinone, vacuum distillation is added to obtain perfluor heptyl ethanol itaconate in crude product；Perfluor heptyl ethanol clothing health
Acid esters yield 93.3%.
Embodiment two
Equipped with electromagnetic agitation, water knockout drum, reflux condensing tube, the four-hole boiling flask of thermometer, adding itaconic acid 10g, complete
Fluorine heptyl ethanol 56g, p methoxy phenol 1.2g, SO4 2-/TiO2-ZrO2Solid acid 0.7g, 250ml benzene；
Stirred under nitrogen atmosphere is heated to 80 DEG C, and reaction 9h is to there is no longer water generating, stopped reaction；Cool down, filter, obtain
Filtrate, rotary evaporation of solvent benzene, obtain crude product；
1g p methoxy phenols, vacuum distillation is added to obtain perfluor heptyl ethanol itaconate in crude product；
Perfluor heptyl ethanol itaconate yield 95.1%.
Embodiment three
Equipped with electromagnetic agitation, water knockout drum, reflux condensing tube, the there-necked flask of thermometer, adding itaconic acid 10g, complete
Fluorine heptyl ethanol 56g, p methoxy phenol 1.6g, embodiment two are recovered by filtration solid acid 0.9g, 250ml toluene；
Stirred under nitrogen atmosphere is heated to 95 DEG C, and reaction 10h is to there is no longer water generating, stopped reaction；
Cool down, filter, obtaining filtrate, rotary evaporation of solvent benzene, obtaining crude product；
1g p methoxy phenols, vacuum distillation is added to obtain perfluor heptyl ethanol itaconate in crude product；
Perfluor heptyl ethanol itaconate yield 94.8%.
Specific embodiment described herein is only explanation for example spiritual to the present invention.Technology neck belonging to of the invention
The technical staff in domain can be made various modifications to described specific embodiment or supplement or replaced using similar mode
Generation, but without departing from the spiritual of the present invention or surmount scope defined in appended claims.
Although more having used term herein, it is not precluded from using the probability of other terms.Using these terms
Just for the sake of more easily describing and explaining the essence of the present invention；Be construed as any additional restriction be all with
Spirit of the invention is contrary.
Claims (7)
1. a kind of preparation method of perfluor heptyl ethanol itaconate, it is characterised in that perfluor heptyl ethanol and itaconic acid are solid
Be dehydrated in the presence of body acid catalyst, polymerization inhibitor, esterification, specifically include following steps：
A, in there-necked flask add organic solvent；
B, addition perfluor heptyl ethanol, itaconic acid；
C, addition polymerization inhibitor；
D, addition solid acid；
E, under nitrogen protection heating, stirring carry out esterification, to there is no longer water generating, stop esterification；
F, cooling, filtration crude product；
G, rotary evaporation organic solvent；
H, decompression, distillation obtain perfluor heptyl ethanol itaconate.
2. the preparation method of perfluor heptyl ethanol itaconate according to claim 1, it is characterised in that described step
(1) in, described organic solvent is the double solventss of benzene or toluene or dimethylbenzene or toluene and dimethylbenzene.
3. the preparation method of perfluor heptyl ethanol itaconate according to claim 1, it is characterised in that described step
D in (), solid acid is SO4 2-/TiO2Or SO4 2-/ZrO2, or SO4 2-/TiO2-ZrO2。
4. the preparation method of perfluor heptyl ethanol itaconate according to claim 1, it is characterised in that described step
In (e), reaction temperature 80-110 DEG C, response time 6-10h.
5. the preparation method of perfluor heptyl ethanol itaconate according to claim 1, it is characterised in that described step
F in (), the solid acid being filtrated to get can directly be reclaimed and used.
6. the preparation method of perfluor heptyl ethanol itaconate according to claim 1, it is characterised in that described step
In (h), polymerization inhibitor is continuously added.
7. the preparation method of perfluor heptyl ethanol itaconate according to claim 6, it is characterised in that described step
C in () and (h), polymerization inhibitor is hydroquinone or p methoxy phenol or benzoquinone.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611114096.XA CN106631785A (en) | 2016-12-07 | 2016-12-07 | Preparation method of perfluoroheptyl ethyl itaconate |
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| CN201611114096.XA CN106631785A (en) | 2016-12-07 | 2016-12-07 | Preparation method of perfluoroheptyl ethyl itaconate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111321176A (en) * | 2020-03-11 | 2020-06-23 | 北京化工大学 | Method for preparing 4-monooctyl itaconate by enzymatic selective catalysis |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3686281A (en) * | 1969-06-02 | 1972-08-22 | Martin Knell | Preparation of polyfluoroalkyl esters of fumaric and related acids |
| CN1613892A (en) * | 2004-08-31 | 2005-05-11 | 复旦大学 | Esterifying method for polyether alcohol and alpha, beta-unsaturated carboxylic acid |
| CN102898308A (en) * | 2011-07-27 | 2013-01-30 | 苏州大学 | Difluoroalkyl itaconate and its preparation method |
-
2016
- 2016-12-07 CN CN201611114096.XA patent/CN106631785A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3686281A (en) * | 1969-06-02 | 1972-08-22 | Martin Knell | Preparation of polyfluoroalkyl esters of fumaric and related acids |
| CN1613892A (en) * | 2004-08-31 | 2005-05-11 | 复旦大学 | Esterifying method for polyether alcohol and alpha, beta-unsaturated carboxylic acid |
| CN102898308A (en) * | 2011-07-27 | 2013-01-30 | 苏州大学 | Difluoroalkyl itaconate and its preparation method |
Non-Patent Citations (2)
| Title |
|---|
| 任剑云 等: "La3+/SO42-/TiO2催化合成衣康酸二丁酯", 《工业催化》 * |
| 侯晓红: "衣康酸酯及衣康酸酐合成新工艺的研究", 《中国优秀硕士学位论文全文数据库-工程科技I辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111321176A (en) * | 2020-03-11 | 2020-06-23 | 北京化工大学 | Method for preparing 4-monooctyl itaconate by enzymatic selective catalysis |
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