CN101250087B - Method for preparing allyl chloride by using byproduct of polyol allyl ether production - Google Patents
Method for preparing allyl chloride by using byproduct of polyol allyl ether production Download PDFInfo
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- CN101250087B CN101250087B CN2008100650803A CN200810065080A CN101250087B CN 101250087 B CN101250087 B CN 101250087B CN 2008100650803 A CN2008100650803 A CN 2008100650803A CN 200810065080 A CN200810065080 A CN 200810065080A CN 101250087 B CN101250087 B CN 101250087B
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Abstract
The invention provides a method for preparing allyl chloride from the byproduct of polyol allyl ether production, belonging to the technical field of organic synthesis, which comprises adding the byproduct and lewis acid catalyst into a reactor, adding hydrochloric acid or hydrogen chloride gas, heating the reactor slowly until the reaction solution refluxes, keeping reflux state and lasting the reflux state for some time when the hydrochloric acid or hydrogen chloride gas is fed completely, distilling the reaction mixture to obtain product, wherein the mol ratio of the hydrogen chloride in the hydrochloric acid and the byproduct is 1.1-2 or the mol ratio of the hydrogen chloride gas and the byproduct is 1.1-1.4, and the mol ratio of the catalyst and the byproduct is 0.005-0.2. The inventive prepration method of allyl chloride can utilize harmful waste and the purity of prepared allyl chloride can reach 96%, therefore, the allyl chloride can be used as the reaction material of polyol allyl ether. And the invention has mild reaction conditions, high reaction speed and high reaction yield.
Description
Technical field
The present invention relates to the preparation method of propenyl chloride, relate in particular to the method for preparing propenyl chloride with the by product of producing polylol allyl ether.
Background technology
Polyvalent alcohol (as glycerine, TriMethylolPropane(TMP), tetramethylolmethane etc.) allyl ethers is the important chemical intermediate raw material, can be used for solvent and unsaturated polyester coating, ion exchange resin, High hydrophilous resin field.Trimethylolpropane allyl ether is the important modification agent of unsaturated polyester coating, can make polyester rapid film forming in air; And can be used for doing in the ion exchange resin linking agent.Allylin can be as the raw material of the cocuring agent of urethanes, antitartar agents, vibrin quick dry agent.Pentaerythrite allyl ether is a kind of linking agent that is widely used in high molecular polymerization, is usually used in the High hydrophilous resin.The method of this type of allyl ethers of preparation also only limits to the William Mu Xunfa of traditional chloro-alkenes at present, and this kind method has obtained numerous investigators' concern.The clear 48-22198 of open special permission of known William Mu Xunfa such as Japan speciallys permit clear 54-32598, U.S. Pat 312460 and German patent DE 1021346 etc.This method adopts propenyl chloride and sodium alkoxide reaction.
Because sodium alkoxide is a highly basic, reaction system alkalescence is strong excessively, and side reaction takes place in reaction process propenyl chloride easily, generates the mixture of vinyl carbinol and diallyl ether, and diallyl ether is 50～70% in the shared weight ratio of mixture usually, and vinyl carbinol is 30～50%.And vinyl carbinol and diallyl ether strong toxicity, smell stimulates, and high volatility is inflammable and explosive, causes safety in production hidden danger easily.
Because the diallyl ether stable in properties is difficult to carry out chemical reaction, generally be burning disposal in the by product, cause the significant wastage of resource, can not realize effective utilization of atom economy.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide a kind of by product to prepare the method for propenyl chloride, realize the cyclic utilization of waste with the production polylol allyl ether.
The technical scheme of finishing the foregoing invention task is:
A kind of method for preparing propenyl chloride with the by product of producing polylol allyl ether, it is characterized in that: in reactor, add described by product and lewis acid catalyst, dripping hydrochloric acid or feed hydrogen chloride gas then, slowly reactor heating to reaction solution refluxes simultaneously, keep reflux state, treat to reflux for some time again after hydrochloric acid dropwises or the hydrogenchloride feeding finishes, last distillation reaction mixture promptly gets product, wherein the mol ratio of hydrogenchloride and described by product is 1.1～2 in the hydrochloric acid, perhaps the mol ratio of hydrogen chloride gas and described by product is 1.1～1.4, and the mol ratio of catalyzer and described by product is 0.005～0.2.
In a kind of optimized technical scheme, described catalyzer is a zinc chloride, cupric chloride, in tin chloride or the iron(ic) chloride any one.
In a kind of optimized technical scheme, the functional quality percentage concentration is 31～37% technical hydrochloric acid.
In a kind of optimized technical scheme, the hydrochloric acid dropping time is 4～8h, and return time is 1～2h.
In a kind of optimized technical scheme,, treat that reflux temperature reduces to about 50 ℃ the beginning reflux water-dividing if hydrogen chloride gas is reactant.
In a kind of optimized technical scheme, if hydrogen chloride gas is a reactant, the reaction times is 10～16h.
Following reaction all takes place as reactant in hydrochloric acid or hydrogen chloride gas:
CH2CHCH2——O——CH2CHCH2+HCL→CH2＝CH——CH2——CL+
CH2＝CH——CH2——OH
CH2＝CH——CH2——OH+HCL→CH2＝CH——CH2——CL+H2O
At hydrogen chloride gas is that initial reaction stage is regardless of water under the reactant situation, and reason is dissociating into ionic condition with the easier hydrogenchloride that makes, and forms H+, ether is combined with proton earlier form salt, will impel ether bond rupture.Reaction mechanism is as follows:
It is in order to promote molecular balance to move, to impel ether bond rupture that the reaction later stage is divided water.
Hydrochloric acid liquid phase method and hydrogenchloride gas phase method respectively have quality: the required technical hydrochloric acid of liquid phase method is easy to get, wide material sources, but by with the technical hydrochloric acid moisture content be 63～67%, bring big water gaging to reaction system, balance is moved to the left, ether bond rupture is not thorough, and reaction conversion ratio has only 55～80%, and produces the waste water of a large amount of contaminate environment; Vapor phase process reaction conversion ratio height can reach 85～95%, and does not produce waste water, but commercial hydrogenchloride is because transportation is inconvenient, cost an arm and a leg, have only oneself produce hydrogenchloride or cooperate with other manufacturers to be stablized, inexpensive hydrogenchloride, this technology just has industrialized value.
Beneficial effect of the present invention: utilized harmful danger wastes fully, the propenyl chloride purity that makes can reach 96%, can be as the reaction raw materials of polylol allyl ether, and the reaction conditions gentleness, speed of response is fast, the reaction yield height.
Embodiment
For better explanation the present invention, our following examples of giving an example, but the present invention is not limited in following examples.
Embodiment 1
Mechanical stirring is being housed, thermometer, in the four-hole boiling flask of the 1000ml of condensing works, add catalyzer zinc chloride 11.34g, the mixture 144.35g of diallyl ether and vinyl carbinol, wherein the vinyl carbinol mass ratio is 31%, diallyl ether is 68%, begins to drip 31% hydrochloric acid, and reactor begins slowly to be heated to reaction solution and refluxes, initial reflux temperature is 72 ℃, dripping hydrochloric acid 6h slowly, the salt acid consumption is 461.65g (3.92mol), reflux temperature is reduced to 50 ℃, hydrochloric acid dropwises, keep backflow 1h, beginning distillation reaction mixture, the control gas phase temperature is 45～60 ℃, obtain purity and be 93% propenyl chloride cut 156g, reaction conversion ratio is 68%.
Embodiment 2
In the four-hole boiling flask of the 1000ml that mechanical stirring, thermometer, condensing works are housed, add catalyzer zinc chloride 11.34g, the mixture 144.35g of diallyl ether and vinyl carbinol, wherein the vinyl carbinol mass ratio is 31%, diallyl ether is 68%, begin to feed hydrogen chloride gas, reactor begins slowly to be heated to reaction solution and refluxes, initial reflux temperature is 72 ℃, slowly feed hydrogenchloride 10h, hydrogenchloride consumption 122.67g (3.36mol), reflux temperature reduce to 50 ℃, sampling is formed with gas-chromatography measured reaction liquid: propenyl chloride 72.4%, diallyl ether 23.6%.Continue to keep the hydrogenchloride flow constant, logical hydrogen chloride gas is to 143.11g (3.92mol), and reflux temperature remains unchanged, and still is 50 ℃, and reaction solution is formed constant: propenyl chloride 72.4%, allyl ether 23.6%.Stop logical hydrogen chloride gas, beginning distillation reaction mixture, the control gas phase temperature is 45～60 ℃, obtains purity and be 93% propenyl chloride cut 153.7g, reaction conversion ratio is 67%.
Embodiment 3
Embodiment and example 2 are basic identical, introduce the later stage and divide the water measure.Feeding intake finishes, and feeds hydrogen chloride gas 122.67g (3.36mol), when reflux temperature is reduced to 50 ℃, continues to keep the hydrogenchloride flow constant, logical hydrogen chloride gas, and later stage reflux water-dividing when opening.During to hydrogen chloride gas feeding 143.11g (3.92mol), reflux temperature is reduced to 45～46 ℃, and sampling is formed with gas-chromatography measured reaction liquid: propenyl chloride 92.5%, diallyl ether 3.0%.Stop logical hydrogen chloride gas, beginning distillation reaction mixture, the control gas phase temperature is 45～60 ℃, obtains purity and be 96% propenyl chloride cut 206g, reaction conversion ratio is 93%.
Embodiment 4
Basic identical with example 1 embodiment, change the hydrochloric acid add-on.Feed intake and finish, dripping hydrochloric acid 7h slowly, the salt acid consumption is 659.35g (5.6mol), reflux temperature is reduced to 47 ℃, and hydrochloric acid dropwises, and keeps backflow 1h, beginning distillation reaction mixture, the control gas phase temperature is 45～60 ℃, obtains purity and be 94% propenyl chloride cut 182.3g, and reaction conversion ratio is 80%.
Embodiment 5
Mechanical stirring is being housed, thermometer, in the four-hole boiling flask of the 1000ml of condensing works, add catalyzer iron(ic) chloride 7.53g, the mixture 144.35g of diallyl ether and vinyl carbinol, wherein the vinyl carbinol mass ratio is 40%, diallyl ether is 60%, begins to drip 31% hydrochloric acid, and reactor begins slowly to be heated to reaction solution and refluxes, initial reflux temperature is 72 ℃, dripping hydrochloric acid 6h slowly, the salt acid consumption is 455.46g (3.87mol), reflux temperature is reduced to 54 ℃, hydrochloric acid dropwises, keep backflow 1h, beginning distillation reaction mixture, the control gas phase temperature is 45～60 ℃, obtain purity and be 90% propenyl chloride cut 129g, reaction conversion ratio is 55%.
Claims (5)
1. method for preparing propenyl chloride with the by product of producing polylol allyl ether, it is characterized in that: in reactor, add described by product and lewis acid catalyst, dripping hydrochloric acid or feed hydrogen chloride gas then, slowly reactor heating to reaction solution refluxes simultaneously, keep reflux state, treat to reflux for some time again after hydrochloric acid dropwises or the hydrogenchloride feeding finishes, last distillation reaction mixture promptly gets product, wherein the mol ratio of hydrogenchloride and described by product is 1.1～2 in the hydrochloric acid, perhaps the mol ratio of hydrogen chloride gas and described by product is 1.1～1.4, and the mol ratio of catalyzer and described by product is 0.005～0.2; Described catalyzer is a zinc chloride, cupric chloride, in tin chloride or the iron(ic) chloride any one.
2. the by product with the production polylol allyl ether according to claim 1 prepares the method for propenyl chloride, and it is characterized in that: the functional quality percentage concentration is 31～37% technical hydrochloric acid.
3. the by product with the production polylol allyl ether according to claim 1 prepares the method for propenyl chloride, it is characterized in that: hydrochloric acid drips time 4～8h, return time 1～2h.
4. according to claim 1ly prepare the method for propenyl chloride, it is characterized in that:, treat that reflux temperature reduces to 50 ℃, the beginning reflux water-dividing if hydrogen chloride gas is a reactant with the by product of producing polylol allyl ether.
5. the by product with the production polylol allyl ether according to claim 1 prepares the method for propenyl chloride, it is characterized in that: if hydrogen chloride gas is a reactant, the reaction times is 10～16h.
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| CN2008100650803A CN101250087B (en) | 2008-01-18 | 2008-01-18 | Method for preparing allyl chloride by using byproduct of polyol allyl ether production |
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| CN101250087B true CN101250087B (en) | 2010-07-21 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1362942A (en) * | 2000-02-15 | 2002-08-07 | 昭和电工株式会社 | Process for production of allyl chloride |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1362942A (en) * | 2000-02-15 | 2002-08-07 | 昭和电工株式会社 | Process for production of allyl chloride |
Non-Patent Citations (3)
| Title |
|---|
| JP特开昭62-286936A 1987.12.12 |
| 石玉千 等.氯丙烯的衍生物及其应用.化工生产与技术11 6.2004,11(6),23-25. |
| 石玉千等.氯丙烯的衍生物及其应用.化工生产与技术11 6.2004,11(6),23-25. * |
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