CN101993371A - Preparation method of allyl acrylate - Google Patents
Preparation method of allyl acrylate Download PDFInfo
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- CN101993371A CN101993371A CN2010105675912A CN201010567591A CN101993371A CN 101993371 A CN101993371 A CN 101993371A CN 2010105675912 A CN2010105675912 A CN 2010105675912A CN 201010567591 A CN201010567591 A CN 201010567591A CN 101993371 A CN101993371 A CN 101993371A
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Abstract
The invention discloses a preparation method of allyl acrylate. The method comprises the following steps: firstly mixing acrylic acid with phosphorus trichloride; heating the obtained mixture for reflux reaction; after the obtained reaction mixture is cooled, removing supernatant liquid after the reaction mixture is subject to phase separation, and performing reduced pressure distillation to obtain acryloyl chloride; mixing the acryloyl chloride with allyl alcohol, and reacting under the condition of ice-bath cooling in the presence of an acid binding agent and a polymerization inhibitor; and refining the obtained reaction product to obtain the target product of the allyl acrylate with the purity above 98%. In the method, the reaction conversion rate is improved to 80% by synthesizing a high-activity intermediate, namely the acryloyl chloride; and the method has the advantages of high reaction activity of the acryloyl chloride, low reaction temperature, short reaction time, small polymerization probability in reaction, no need of strong acid as a catalyst, and low requirement on reaction equipment.
Description
Technical field
The present invention relates to the substances preparation method of field of fine chemical, particularly a kind of extraordinary acrylate---the preparation method of allyl acrylate with bifunctional.
Technical background
Allyl acrylate is a kind of extraordinary acrylate.Can be used as linking agent and synthesize the PVC properties-correcting agent with nucleocapsid structure---ACR impact modifier, mainly be because: the molecular structure of allyl acrylate has the two keys of two C=C, can provide the effective dual-functional group of subordinate phase crosslinked, makees the nucleation linking agent of ACR.Also can be used for resin modified, modified rubber, modified paint etc., make the material after the modification have fine erosion resistance, shock strength, bounding force, hardness and low-shrinkage water-based etc.
At present, the preparation method of allyl acrylate mainly contains direct esterification method, acrylate and propenyl chloride reaction method, propenal condensation method and ester-interchange method etc.
Nineteen fifty, the synthetic method of disclosed allyl acrylate in patent US2516627 such as George W.Hearne is the direct condensation method of propenal, and selected catalyzer is an aluminum isopropylate, and temperature of reaction is 30 ℃～35 ℃, reaction times is 3h, and the transformation efficiency of propenal is 27.4%.
1961, Harry De V.Finch etc. discloses a kind of synthetic method of allyl acrylate in patent US2998447, this method also is to adopt the method for the direct condensation of propenal, selected catalyzer is tert.-butoxy aluminium or aluminium-sec-butylate, temperature of reaction is 20 ℃～30 ℃, reaction times is 1.5h～3h, and the transformation efficiency of propenal is 20.4%～23.3%.
Above-mentioned two kinds of methods all are to be the synthetic method of raw material with the propenal, equally all do not obtain very high transformation efficiency, and because raw material propylene aldehyde belongs to the hypertoxic type pharmaceutical chemicals, its pungency and toxic are bigger.
Nineteen sixty-five, the synthetic method of Derek Kenneth Vincent Steel disclosed allyl acrylate in patent London 1059875 is an ester-interchange method, and it is to be raw material with allyl acetate and methyl acrylate, and titanium tetraisopropylate is a catalyzer.In synthetic reaction process, should constantly the ritalin that generates in time be steamed, to carry out to positive dirction so that react, thereby obtain higher transformation efficiency, the product yield is 85%.But because the reaction times is longer, temperature of reaction is higher, causes the easy polymerization reaction take place of unsaturated compound in the reaction system, finally influences productive rate and product purity.
1988, disclosed a kind of allyl acrylate synthetic method in patent US 4745213 such as Fritz Schlosser also is an ester-interchange method, it is to be raw material with methyl acrylate or ethyl propenoate and vinyl carbinol, with lithium halide and calcium oxide is catalyzer, reaction 5～20h, should constantly methyl alcohol or the ethanol that generates in time be steamed in the reaction, carry out to positive dirction so that react, thereby obtain higher transformation efficiency.The transformation efficiency of vinyl carbinol reaches 97.7%, and the converted product that obtains is 95%.This reaction is long owing to the reaction times, and the temperature of reaction can make the unsaturated compound generation polymerization in the system equally than higher, the productive rate and the degree of purity of production of final influence reaction.
Wu De and, reported a kind of method of synthesizing propylene allyl propionate in " allyl acrylate synthetic " literary composition of on the chemical industry world (1990:446～448), delivering such as Jin Xuanhan, its reaction raw materials is propenyl chloride and vinylformic acid, the ratio of the amount of substance of reaction mass is 2: 1, with the cuprous chloride is catalyzer, the pH value is controlled between 6.5～7.5, reaction times is 2～3h, and temperature of reaction is 50 ℃, and productive rate reaches 85～90%.
All there is different drawbacks in the method for above-mentioned several synthesizing propylene allyl propionates, or catalyst system can not recycle; Or to equipment requirements height, complicated operation; Or expensive raw material price, thereby increased synthetic cost; Perhaps, cause the various unsaturated compounds in the reaction system that polymerization easily takes place, cause product purity not high because temperature of reaction is too high.
Calendar year 2001, among the patent CN1410412A, a kind of synthetic method of allyl methacrylate(AMA) is disclosed, it is with methacrylic acid and vinyl carbinol reaction, with the tosic acid is catalyzer, and back flow reaction makes in the presence of hydroquinone of polymerization retarder, need constantly remove the water of generation in the reaction process.Productive rate is 90～92%, and purity is 98～99%.
2010, among the patent CN101781205A, a kind of method of synthesizing substitutional crylic acid phenyl ester is disclosed, it is with substitutional crylic acid and one of phosphorus trichloride, phosphorus oxychloride, thionyl chloride or phosphorus pentachloride substitution reaction to take place to generate the replacement acrylate chloride, again with fortified phenol generation nucleophilic addition(Adn)---and eliminate reaction and generate substitutional crylic acid phenyl ester.Product purity is higher than 99%.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of new allyl acrylate, this method is to prepare high reaction activity reaction intermediate---acrylate chloride earlier, be the novel synthesis of feedstock production allyl acrylate with itself and vinyl carbinol again, this method has that temperature of reaction is lower, the reaction times is short, higher, the purity advantages of higher of transformation efficiency.Temperature of reaction is low, product is easy to advantages such as purifying because this method has, and can make target product quickly and easily.
The reaction process of this synthetic method is as follows:
Because vinylformic acid contains the two keys of C=C, autohemagglutination easily takes place in reactant in the reaction, and contain the two keys of two C=C in the molecular structure of product, side reactions such as easier generation polymerization, so, in reaction process, not only to add stopper, but also temperature of reaction will be controlled low as far as possible, and the reaction times shortened as far as possible, this is a raw material with regard to requiring with the higher compound of reactive behavior.For this reason, the allyl acrylate synthetic route that designs among the present invention is carried out in two steps: at first with vinylformic acid and acylation reaction, generate active higher acrylate chloride; Again the acrylate chloride that obtains is mixed with vinyl carbinol, acid binding agent, stopper etc. and react.Like this, not only Fan Ying transformation efficiency height reaches more than 80%, and the target product that obtains---and the purity of allyl acrylate is higher, reaches 98%.
The particular content of synthetic method of the present invention is:
Vinylformic acid is mixed with the ratio of phosphorus trichloride by amount of substance at 4: 1, join in the reactor airtight, that thermometer, mechanical stirring device and reflux are housed, be heated to boiling, react 10min down, cool off 2h then at 60～70 ℃.Be divided into two-layerly after the reaction solution cooling, the liquid on upper strata is shifted out, underpressure distillation is collected pressure at 10kPa, 30 ℃ cut, just obtains acrylate chloride.
Vinyl carbinol after the acrylate chloride that makes and the dehydration is mixed by amount of substance 1: 1.0～1.5, join in the reactor airtight, that thermometer, mechanical stirring device, HCl retrieving arrangement and constant flow pump are housed, add stopper, under the ice bath cooling, drip acid binding agent (amount that splashes into acid binding agent is calculated by acrylate chloride: acrylate chloride press amount of substance than 1: 0.1～0.5 with acid binding agent) after the dehydration with constant flow pump by the speed of 3ml/min, promptly react end after acid binding agent dropwises.With the product washing, after leaving standstill, the upper strata is isolated in layering, is the crude product that contains target product.Add stopper in crude product, carry out underpressure distillation, collect 10kPa, 56～58 ℃ cut, just obtain purity and be the allyl acrylate 98% or more, press acrylate chloride calculating, the transformation efficiency of reaction reaches 80%.
The described stopper of stating is that one or more and air (oxygen) in thiodiphenylamine, para benzoquinone, the MEHQ is composite.
Described acid binding agent is one or more in pyridine, diethylamine, triethylamine or the 2-picoline.
Allyl acrylate new synthetic method of the present invention is compared with additive method, is by the high intermediate of composite reactive---acrylate chloride improves reaction conversion ratio.Because acrylate chloride reactive behavior height, so temperature of reaction is low, the reaction times is very short, and it is little that the polymerization probability takes place in the reaction.And make catalyzer without strong acid, like this, less demanding to conversion unit.
Embodiment
The present invention mainly is by acylation reaction preparation feedback intermediate---acrylate chlorides such as vinylformic acid and phosphorus trichlorides, again with acrylate chloride and vinyl carbinol reaction, generates the allyl acrylate of higher degree at last, and reaction conversion ratio is higher.
Entire synthesis process was divided into for two steps and carries out the first step elder generation synthesizing propylene acyl chlorides, the second step resynthesis allyl acrylate.
Embodiment 1:
The preparation of acrylate chloride: get dry vinylformic acid and the 87ml phosphorus trichloride of 300ml, join after the mixing in the reactor airtight, that thermometer, mechanical stirring device and reflux are housed through anhydrating and handling.The reacting by heating mixture keeps temperature of reaction about 65 ℃, back flow reaction 10min, stopped reaction to boiling under the stirring continuing.Reaction mixture is cooled off 2h, and reaction mixture is divided into two-layer, and lower floor is a solid, and the upper strata is a liquid.Carry out underpressure distillation after supernatant liquid shifted out, collect 10kPa, 30 ℃ cut, promptly obtain intermediate---the acrylate chloride of high reaction activity.
The preparation of allyl acrylate: getting, exsiccant vinyl carbinol 68ml and acrylate chloride 82ml join in the reactor airtight, that thermometer, mechanical stirring device, constant flow pump and HCl retrieving arrangement are housed, add thiodiphenylamine 2g, continuing under the cooling of stirring and ice bath, with the pyridine 17ml that constant flow pump has dewatered by the speed dropping of 3ml/min, i.e. reaction stopped after pyridine dropwised.Product washing back standing demix is isolated the upper strata colourless liquid, promptly gets the crude product that contains target product, adds 5g CuCl then in crude product
2, carry out underpressure distillation, collect 10kPa, 56～58 ℃ cut, just obtain purity and be the allyl acrylate more than 98%.
Embodiment 2:
The preparation of acrylate chloride: with the preparation of acrylate chloride in the example one.
The preparation of allyl acrylate: getting, exsiccant vinyl carbinol 68ml and acrylate chloride 82ml join in the reactor airtight, that thermometer, mechanical stirring device, constant flow pump and HCl retrieving arrangement are housed, add thiodiphenylamine 2g, continuing under the cooling of stirring and ice bath, with the diethylamine 12ml that constant flow pump has dewatered by the speed dropping of 3ml/min, i.e. reaction stopped after diethylamine dropwised.Product washing back standing demix is isolated the upper strata colourless liquid, promptly gets the crude product that contains target product, adds 5g CuCl then in crude product
2, carry out underpressure distillation, collect 10kPa, 56～58 ℃ cut, just obtain purity and be the allyl acrylate more than 98%.
Embodiment 3:
The preparation of acrylate chloride: with the preparation of acrylate chloride among the embodiment 1.
The preparation of allyl acrylate: getting, exsiccant vinyl carbinol 68ml and acrylate chloride 82ml join in the reactor airtight, that thermometer, mechanical stirring device, constant flow pump and HCl retrieving arrangement are housed, add thiodiphenylamine 2g, continuing under the cooling of stirring and ice bath, with the triethylamine 21.6ml that constant flow pump has dewatered by the speed dropping of 3ml/min, i.e. reaction stopped after triethylamine dropwised.Product washing back standing demix is isolated the upper strata colourless liquid, promptly gets the crude product that contains target product, adds 5gCuCl then in crude product
2, carry out underpressure distillation, collect 10kPa, 56～58 ℃ cut, just obtain purity and be the allyl acrylate more than 98%.
Embodiment 4:
The preparation of acrylate chloride: with the preparation of acrylate chloride among the embodiment 1.
The preparation of allyl acrylate: getting, exsiccant vinyl carbinol 68ml and acrylate chloride 82ml join in the reactor airtight, that thermometer, mechanical stirring device, constant flow pump and HCl retrieving arrangement are housed, add thiodiphenylamine 2g, continuing under the cooling of stirring and ice bath, with the 2-picoline 17ml that constant flow pump has dewatered by the speed dropping of 3ml/min, i.e. reaction stopped after the 2-picoline dropwised.Product washing back standing demix is isolated the upper strata colourless liquid, promptly gets the crude product that contains target product, adds 5g CuCl then in crude product
2, carry out underpressure distillation, collect 10kPa, 56～58 ℃ cut, just obtain purity and be the allyl acrylate more than 98%.
Embodiment 5:
The preparation of acrylate chloride: with the preparation of acrylate chloride among the embodiment 1.
The preparation of allyl acrylate: getting, exsiccant vinyl carbinol 102ml and acrylate chloride 82ml join in the reactor airtight, that thermometer, mechanical stirring device, constant flow pump and HCl retrieving arrangement are housed, add thiodiphenylamine 2g, continuing under the cooling of stirring and ice bath, with the pyridine 17ml that constant flow pump has dewatered by the speed dropping of 3ml/min, i.e. reaction stopped after pyridine dropwised.Product washing back standing demix is isolated the upper strata colourless liquid, promptly gets the crude product that contains target product, adds 5g CuCl then in crude product
2, carry out underpressure distillation, collect 10kPa, 56～58 ℃ cut, just obtain purity and be the allyl acrylate more than 98%.
Embodiment 6:
The preparation of acrylate chloride: with the preparation of acrylate chloride among the embodiment 1.
The preparation of allyl acrylate: getting, exsiccant vinyl carbinol 68ml and acrylate chloride 82ml join in the reactor airtight, that thermometer, mechanical stirring device, constant flow pump and HCl retrieving arrangement are housed, add MEHQ 1.5g, continuing under the cooling of stirring and ice bath, with the pyridine 40ml that constant flow pump has dewatered by the speed dropping of 3ml/min, i.e. reaction stopped after pyridine dropwised.Product washing back standing demix is isolated the upper strata colourless liquid, promptly gets the crude product that contains target product, adds 5gCuCl then in crude product
2, carry out underpressure distillation, collect 10kPa, 56～58 ℃ cut, just obtain purity and be the allyl acrylate more than 98%.
Embodiment 7:
The preparation of acrylate chloride: with the preparation of acrylate chloride among the embodiment 1.
The preparation of allyl acrylate: getting, exsiccant vinyl carbinol 68ml and acrylate chloride 82ml join in the reactor airtight, that thermometer, mechanical stirring device, constant flow pump and HCl retrieving arrangement are housed, add MEHQ 1.5g, continuing under the cooling of stirring and ice bath, with the pyridine 17ml that constant flow pump has dewatered by the speed dropping of 3ml/min, i.e. reaction stopped after pyridine dropwised.Product washing back standing demix is isolated the upper strata colourless liquid, promptly gets the crude product that contains target product, adds 5gCuCl then in crude product
2, carry out underpressure distillation, collect 10kPa, 56～58 ℃ cut, just obtain purity and be the allyl acrylate more than 98%.
Embodiment 8:
The preparation of acrylate chloride: with the preparation of acrylate chloride among the embodiment 1.
The preparation of allyl acrylate: getting, exsiccant vinyl carbinol 68ml and acrylate chloride 82ml join in the reactor airtight, that thermometer, mechanical stirring device, constant flow pump and HCl retrieving arrangement are housed, add para benzoquinone 1.5g, continuing under the cooling of stirring and ice bath, with the pyridine 17ml that constant flow pump has dewatered by the speed dropping of 3ml/min, i.e. reaction stopped after pyridine dropwised.Product washing back standing demix is isolated the upper strata colourless liquid, promptly gets the crude product that contains target product, adds 5g CuCl then in crude product
2, carry out underpressure distillation, collect 10kPa, 56～58 ℃ cut, just obtain purity and be the allyl acrylate more than 98%.
Claims (4)
1. the preparation method of an allyl acrylate, allyl acrylate is the extraordinary acrylate that contains bifunctional, this preparation method comprises in regular turn and may further comprise the steps:
(1), vinylformic acid is mixed with phosphorus trichloride, mixture heating up refluxed react, after the reaction, the reaction mixture cooling after the phase-splitting of question response mixture, is shifted out supernatant liquid, and underpressure distillation promptly obtains acrylate chloride;
(2), acrylate chloride is mixed with vinyl carbinol, in the presence of acid binding agent and stopper, react under ice bath refrigerative condition, reaction after finishing is made with extra care product, promptly obtains the target product allyl acrylate.
2. the preparation method of allyl acrylate according to claim 1, this method is that vinylformic acid is mixed with phosphorus trichloride ratio by weight at 4: 1, join in the reactor airtight, that thermometer, mechanical stirring device and reflux are housed, be heated to boiling, react 10min down at 60～70 ℃, cool off 2h then; Be divided into two-layerly after the reaction solution cooling, the liquid on upper strata is shifted out, underpressure distillation is collected pressure at 10kPa, 30 ℃ cut, just obtains acrylate chloride;
The acrylate chloride that makes is mixed with vinyl carbinol ratio 1.0: 1.0～1.5 by weight after the dehydration, join in the reactor airtight, that thermometer, mechanical stirring device, HCl retrieving arrangement and constant flow pump are housed, add stopper, under the ice bath cooling, the speed of pressing 3ml/min with constant flow pump drips the acid binding agent after the dehydration, the amount that splashes into acid binding agent is calculated by acrylate chloride, and acrylate chloride is 1.0: 0.1～0.5 with acid binding agent ratio by weight, and i.e. reaction finished after acid binding agent dropwised; With the product washing, after leaving standstill, the upper strata is isolated in layering, is the crude product that contains target product; Add stopper in crude product, the consumption of stopper is 1%～10%wt of crude product, carries out underpressure distillation, collects 10kPa, 56～58 ℃ cut, just obtains purity and be the allyl acrylate more than 98%.
3. the preparation method of allyl acrylate according to claim 1 and 2, it is characterized in that: described acid binding agent is selected from one or more in pyridine, diethylamine, triethylamine and the 2-picoline.
4. the preparation method of allyl acrylate according to claim 1 and 2 is characterized in that: one or more and air that described stopper is selected from thiodiphenylamine, Resorcinol, para benzoquinone and the MEHQ carry out composite.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106542994A (en) * | 2016-10-09 | 2017-03-29 | 烟台德邦先进硅材料有限公司 | A kind of synthetic method of allyl acrylate |
| CN106905362A (en) * | 2017-03-02 | 2017-06-30 | 太原理工大学 | A kind of end alkenyl unsaturation phosphonate monomers and preparation method thereof |
| CN108698972A (en) * | 2016-02-25 | 2018-10-23 | 3M创新有限公司 | The method that (alkyl) acrylate is prepared in flow reactor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781205A (en) * | 2010-03-30 | 2010-07-21 | 丽水市南明化工有限公司 | Method for synthesizing substitutional crylic acid phenyl ester |
-
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781205A (en) * | 2010-03-30 | 2010-07-21 | 丽水市南明化工有限公司 | Method for synthesizing substitutional crylic acid phenyl ester |
Non-Patent Citations (3)
| Title |
|---|
| 《合成化学》 19960930 张洪敏 等 alpha-甲基丙烯酸烯丙酯的合成及其自由基、阴离子聚合的研究 第4卷, 第3期 * |
| 傅相锴: "《高等有机化学》", 30 April 2003, 高等教育出版社 * |
| 张洪敏 等: "α-甲基丙烯酸烯丙酯的合成及其自由基、阴离子聚合的研究", 《合成化学》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108698972A (en) * | 2016-02-25 | 2018-10-23 | 3M创新有限公司 | The method that (alkyl) acrylate is prepared in flow reactor |
| CN108698972B (en) * | 2016-02-25 | 2021-06-29 | 3M创新有限公司 | Method for producing (alkyl) acrylates in a flow reactor |
| CN106542994A (en) * | 2016-10-09 | 2017-03-29 | 烟台德邦先进硅材料有限公司 | A kind of synthetic method of allyl acrylate |
| CN106542994B (en) * | 2016-10-09 | 2018-11-09 | 烟台德邦先进硅材料有限公司 | A kind of synthetic method of allyl acrylate |
| CN106905362A (en) * | 2017-03-02 | 2017-06-30 | 太原理工大学 | A kind of end alkenyl unsaturation phosphonate monomers and preparation method thereof |
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