CN106045849A - Synthetic method for dicyclopentadiene ethoxy methacrylate - Google Patents
Synthetic method for dicyclopentadiene ethoxy methacrylate Download PDFInfo
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- CN106045849A CN106045849A CN201610384912.2A CN201610384912A CN106045849A CN 106045849 A CN106045849 A CN 106045849A CN 201610384912 A CN201610384912 A CN 201610384912A CN 106045849 A CN106045849 A CN 106045849A
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- acid
- methyl
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- dicyclopentadiene
- acrylic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
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Abstract
The invention relates to a simple synthetic method for dicyclopentadiene ethoxy methacrylate. The synthetic method is characterized in that in the presence of an appropriate catalyst and polymerization inhibitor, addition reaction of hydroxyethyl methacrylate and dicyclopentadiene is used for synthesizing dicyclopentadiene ethoxy methacrylate. The catalyst is strong acid or super acid and includes boron trifluoride diethyl etherate, chlorosulfonic acid, fluorosulfuric acid, trifluoro sulfoacid, polyphosphoric acid, phosphotungstic acid and silicotungstic acid. The polymerization inhibitor is one of or a combination of phenothiazine, hydroquinone, p-benzoquinone, p-hydroxyanisole, 2-tert-butyl-hydroquinone, 2,5-di-tert-butylhydroquinone, dibutyl dithiocarbamic acid and 2,2,6,6-tetramethyl-4-hydroxy-piperidine nitroxide free radical, wherein the combination is formed by two components mentioned above.
Description
Technical field
The present invention relates to the synthetic method of a kind of simple and direct (methyl) acrylic acid bicyclic pentadiene 2-ethoxyethyl acetate, specifically
Say, relate to a kind of electrophilic addition reaction synthesis (methyl) acrylic acid pair utilizing (methyl) 2-(Acryloyloxy)ethanol and dicyclopentadiene
The method of cyclopentadienyl group 2-ethoxyethyl acetate.
Background technology
(methyl) acrylic acid dicyclopentadiene ester molecular structure has two polymerisable groups, i.e. double on acrylic acid
Pi-allyl on key and many alicyclic rings, the former can make monomer carry out radical polymerization, and the latter can make monomer carry out being similar to drying oil
The oxidation polymerization carried out in atmosphere, phase emergencing copolymer has that cure shrinkage is low, adhesive force is high, the characteristic of Heat stability is good,
Therefore it is the high polymer monomer of a class function admirable, has a wide range of applications in industries such as coating, ink, binding agents, but it lacks
Point is to have a kind of special, offensive odour.Research finds, draws between dicyclopentadiene and (methyl) acrylate
Enter ethyoxyl, synthesize (methyl) acrylic acid bicyclic pentadiene 2-ethoxyethyl acetate, this special abnormal smells from the patient can be eliminated, keep simultaneously
The premium properties of (methyl) acrylic acid DCPA.The synthesis of (methyl) acrylic acid bicyclic pentadiene 2-ethoxyethyl acetate is typically adopted
By two-step method, first with dicyclopentadiene and ethylene glycol as raw material, under catalyst action, carry out electrophilic addition reaction synthesis second
Glycol list bicyclic pentadiene ether, then utilizes (methyl) acrylic acid (ester) anti-with the esterification of ethylene glycol list bicyclic pentadiene ether
Target product should be synthesized.Yu Hongyan et al. (petrochemical industry, 2007,36(1): 63～66) use two-step synthesis method, first close
Become intermediate product ethylene glycol double cyclopentenyl ether, then with Dibutyltin oxide as catalyst, hexamethylene and the mixture of toluene
Mixture for water entrainer, hydroquinone and MEHQ is polymerization inhibitor, methacrylic acid and ethylene glycol dicyclo amylene
Base ether is synthesized methacrylic acid bicyclic pentadiene 2-ethoxyethyl acetate, and esterification yield is more than 90%, and product purity reaches 92.12%.
US4097677, first with dicyclopentadiene and ethylene glycol as raw material, synthesizes under catalyst boron trifluoride etherate effect
Ethylene glycol list bicyclic pentadiene ether, then with p-methyl benzenesulfonic acid as catalyst, normal heptane as water entrainer, hydroquinone be inhibition
Agent, methacrylic acid and ethylene glycol double cyclopentenyl ether are synthesized methacrylic acid bicyclic pentadiene 2-ethoxyethyl acetate, from going out
The water yield infers that conversion ratio is 97.8%, containing 3～4% unreacted ethylene glycol list dicyclopentadiene in gas chromatographic detection product
Base ether.
Summary of the invention
It is an object of the invention to provide the synthetic method of a kind of simple and direct (methyl) acrylic acid bicyclic pentadiene 2-ethoxyethyl acetate.
The present invention is achieved in that and it is characterized in that process is: in the presence of suitable catalyst and polymerization inhibitor,
Utilizing the electrophilic addition reaction of (methyl) 2-(Acryloyloxy)ethanol and dicyclopentadiene, single step reaction is directly synthesized (methyl) acrylic acid
Bicyclic pentadiene 2-ethoxyethyl acetate, wherein (methyl) 2-(Acryloyloxy)ethanol is 0.8～2.0:1 with the mol ratio of dicyclopentadiene, if
Being 1.0～1.5:1 more preferably, reaction temperature is 60～120 DEG C, and the response time is 4～10 hours.
According to the present invention, catalyst used in electrophilic addition reaction is strong acid or super acids, such as boron trifluoride diethyl etherate network
Compound, chlorosulfonic acid, fluosulfonic acid, the one in three fluosulfonic acid, trifluoromethayl sulfonic acid, polyphosphoric acids, phosphotungstic acid, silico-tungstic acid etc..Urge
The dosage of agent is 2～8%(relative to the weight ratio of raw material dicyclopentadiene).
According to the present invention, in additive reaction, suitable polymerization inhibitor can be added, to stop in course of reaction it may happen that
Polyreaction.Polymerization inhibitor used includes that phenothiazine, hydroquinone, 1,4-benzoquinone, MEHQ, the 2-tert-butyl group are to benzene two
Phenol, 2,5 di tert butyl hydroquinone, copper dibutyldithiocarbamate, 2,2,6,6-tetramethyl-4-hydroxy piperidine nitrogen oxygen
Free radicals (TEMPO) etc., polymerization inhibitor can be used alone, it is also possible to two kinds of compound uses.The dosage of polymerization inhibitor is 0.1～2%
(relative to the weight ratio of whole reaction raw materials), if 0.5～1.0% more preferable.
Beneficial effects of the present invention: the present invention utilizes the single step reaction of (methyl) 2-(Acryloyloxy)ethanol and dicyclopentadiene,
It is directly synthesized (methyl) acrylic acid bicyclic pentadiene 2-ethoxyethyl acetate.Compared with general two-step method, step is simple, easy and simple to handle.
Greatly reduce the production cost of target product, obtain the purity of acrylic acid bicyclic pentadiene 2-ethoxyethyl acetate product more than 93%.
Detailed description of the invention:
Examples below will be described in further detail the present invention, but the present invention should not be limited only within these concrete enforcements
In example.
Embodiment 1
In 500 milliliters of reaction bulbs equipped with agitator, thermometer, condensing tube and Dropping funnel, (1.3 rub to add 151 grams
You) 2-(Acryloyloxy)ethanol, 3 grams of trifluoromethanesulfonic acid and 0.9 gram of phenothiazine.Stirring makes reactant mix homogeneously.It is heated to 75 DEG C,
Slowly dropping dicyclopentadiene 132 grams (1 mole), during dropping, maintenance temperature is at 75～80 DEG C, after dripping off at this temperature
Continue reaction, utilize gas chromatogram to monitor reaction process.After reacting 6 hours, the content of dicyclopentadiene is down to 1.5%, stops anti-
Should, cooling, wash three times with 80 grams of saturated brines, separate organic facies, then carry out rectification under vacuum, collect 105～113 DEG C/130Pa
Fraction, obtain acrylic acid bicyclic pentadiene 2-ethoxyethyl acetate 162 grams, purity 94.6%.1H NMR (CDCl3) 6.12 is (multiple
Peak, lH, H2C=C, trans), 5.70 (multiplet, lH, H2C=C, cis), 5.50 (multiplet, 2H ,-HC=CH-), 4.80
(multiplet, lH, O-HC=), 3.7～4.4(multiplets, 4H ,-OCH2CH2O-), 1.3～2.7(multiplets, 13H).
Embodiment 2
In 500 milliliters of reaction bulbs equipped with agitator, thermometer, condensing tube and Dropping funnel, (1.3 rub to add 151 grams
You) 2-(Acryloyloxy)ethanol, 3 grams of boron trifluoride etherates, 0.3 gram of phenothiazine and 0.6 gram of hydroquinone.Stirring makes reactant
Mix homogeneously.Be heated to 80 DEG C, slowly dropping dicyclopentadiene 132 grams (1 mole), maintain temperature 80 during dropping～
90 DEG C, after dripping off, continue reaction at this temperature, utilize gas chromatogram to monitor reaction process.After reacting 6 hours, dicyclopentadiene
Content be down to 2.1%, stopped reaction, cooling, wash three times with 80 grams of saturated brines, separate organic facies, then it is smart to carry out decompression
Evaporate, collect the fraction of 105～113 DEG C/130Pa, obtain acrylic acid bicyclic pentadiene 2-ethoxyethyl acetate 149 grams, purity 93.1%.
Embodiment 3
The present embodiment is the industrial amplification test of embodiment 2.2 liter reactors add 755 kilograms of 2-(Acryloyloxy)ethanols, 15
Kilogram boron trifluoride etherate, 4.5 kilograms of composite polymerzation inhibitors (are pressed the weight ratio mixing of 1:2 by phenothiazine and hydroquinone
Form).Open stirring, heat temperature raising, when reactor temperature rises to 77～82 DEG C, be slowly added into 660 kilograms by measuring tank
Dicyclopentadiene (joining day is about 3 hours), maintains reacting liquid temperature at 80～90 DEG C during charging, charging is tieed up after terminating
Hold 80～90 DEG C and continue reaction, and utilize the composition change of gas chromatogram monitoring reactant liquor.After reacting 6 hours, record dicyclo penta
The content of diene is 1.9%.Stop heating, open the cooling of still inner coil pipe.In treating still, reactant liquor is cooled to 25～30 DEG C, adds 400
Kilogram saturated brine, stirs 30 minutes, stands 1 hour, releases water layer from bottom valve.Weigh again with 400 kilograms of saturated brines every time
After backwashing washs reactant liquor twice.Reactant liquor is transferred to 2 liter rectifying stills (the structured packing rectifying columns of about 12 theoretical cam curves),
Carry out rectification under vacuum separation.First, under the conditions of 1～15kPa, remove front-end volatiles, then gradually step up system vacuum, 100
～under the conditions of 130Pa, tower top temperature is stable at 105～110 DEG C, receives tank at product and obtain the purity acrylic acid more than 93.0%
Bicyclic pentadiene 2-ethoxyethyl acetate product 764 kilograms.
Claims (7)
1. the synthetic method of (methyl) acrylic acid bicyclic pentadiene 2-ethoxyethyl acetate, it is characterised in that: at suitable catalyst
In the presence of polymerization inhibitor, utilize the additive reaction synthesis target product of (methyl) 2-(Acryloyloxy)ethanol and dicyclopentadiene, wherein
(methyl) 2-(Acryloyloxy)ethanol is 0.8～2.0:1 with the mol ratio of dicyclopentadiene, and reaction temperature is 60～120 DEG C, during reaction
Between be 4～10 hours.
2. the synthetic method of (methyl) acrylic acid bicyclic pentadiene 2-ethoxyethyl acetate as claimed in claim 1, it is characterised in that:
(methyl) 2-(Acryloyloxy)ethanol is 1.0～1.5:1 with the mol ratio of dicyclopentadiene.
3. the synthetic method of (methyl) acrylic acid bicyclic pentadiene 2-ethoxyethyl acetate as claimed in claim 1, it is characterised in that: institute
The catalyst stated is strong acid or super acids, is boron trifluoride etherate, chlorosulfonic acid, fluosulfonic acid, three fluosulfonic acid, fluoroform
One in sulfonic acid, polyphosphoric acids, phosphotungstic acid, silico-tungstic acid.
4. the synthetic method of (methyl) acrylic acid bicyclic pentadiene 2-ethoxyethyl acetate as claimed in claim 3, it is characterised in that: institute
The dosage of the catalyst stated is 2～8% relative to the weight ratio of raw material dicyclopentadiene.
5. the synthetic method of (methyl) acrylic acid bicyclic pentadiene 2-ethoxyethyl acetate as claimed in claim 1, it is characterised in that: institute
The polymerization inhibitor stated is phenothiazine, hydroquinone, 1,4-benzoquinone, MEHQ, 2-tert-butyl hydroquinone, 2,5-di-t-butyl
One in hydroquinone, copper dibutyldithiocarbamate, 2,2,6,6-tetramethyl-4-hydroxy piperidine NO free radical or
The two or more polymerization inhibitors being composited.
6. the synthetic method of (methyl) acrylic acid bicyclic pentadiene 2-ethoxyethyl acetate as claimed in claim 5, it is characterised in that: institute
The dosage stating polymerization inhibitor is 0.1～2.0% relative to the weight ratio of whole reaction raw materials.
7. the synthetic method of (methyl) acrylic acid bicyclic pentadiene 2-ethoxyethyl acetate as claimed in claim 6, it is characterised in that: institute
The dosage stating polymerization inhibitor is 0.5～1.0% relative to the weight ratio of whole reaction raw materials.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610384912.2A CN106045849A (en) | 2016-06-02 | 2016-06-02 | Synthetic method for dicyclopentadiene ethoxy methacrylate |
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| CN201610384912.2A CN106045849A (en) | 2016-06-02 | 2016-06-02 | Synthetic method for dicyclopentadiene ethoxy methacrylate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113522357A (en) * | 2021-08-20 | 2021-10-22 | 山东瑞博龙化工科技股份有限公司 | Ionic liquid catalyst and preparation method and application thereof |
| CN114394900A (en) * | 2022-01-19 | 2022-04-26 | 山东瑞博龙化工科技股份有限公司 | Preparation method of dicyclopentadiene oxyethyl (meth) acrylate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3705136A (en) * | 1969-11-28 | 1972-12-05 | Eastman Kodak Co | Phosphine or phosphite gold complexes of thioethanol and derivatives thereof |
| JPS57200331A (en) * | 1981-06-03 | 1982-12-08 | Hitachi Chem Co Ltd | Preparation of dicyclopentenyloxyalkyl carboxylate |
| JPH04290847A (en) * | 1991-03-20 | 1992-10-15 | Daicel Chem Ind Ltd | Production of (meth)acrylic acid ester |
| CN105481691A (en) * | 2015-11-30 | 2016-04-13 | 武汉理工大学 | Methacrylic acid dicyclopentenyl oxygen-ethyl ester synthetic method |
-
2016
- 2016-06-02 CN CN201610384912.2A patent/CN106045849A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3705136A (en) * | 1969-11-28 | 1972-12-05 | Eastman Kodak Co | Phosphine or phosphite gold complexes of thioethanol and derivatives thereof |
| JPS57200331A (en) * | 1981-06-03 | 1982-12-08 | Hitachi Chem Co Ltd | Preparation of dicyclopentenyloxyalkyl carboxylate |
| JPH04290847A (en) * | 1991-03-20 | 1992-10-15 | Daicel Chem Ind Ltd | Production of (meth)acrylic acid ester |
| CN105481691A (en) * | 2015-11-30 | 2016-04-13 | 武汉理工大学 | Methacrylic acid dicyclopentenyl oxygen-ethyl ester synthetic method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113522357A (en) * | 2021-08-20 | 2021-10-22 | 山东瑞博龙化工科技股份有限公司 | Ionic liquid catalyst and preparation method and application thereof |
| CN114394900A (en) * | 2022-01-19 | 2022-04-26 | 山东瑞博龙化工科技股份有限公司 | Preparation method of dicyclopentadiene oxyethyl (meth) acrylate |
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Address after: 273300 middle section of Huaxing Road, Linyi County Economic Development Zone, Dezhou, Shandong Applicant after: Shandong Ruibolong Chemical Technology Co., Ltd. Address before: 273300 Pingyi county (Economic Development Zone) of Dezhou, Shandong Province, Hua Xinglu Applicant before: Shandong Ruibolong Chemical Technology Co., Ltd. |
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Application publication date: 20161026 |