CN101815699A - Process for preparing dialkyl amino alkyl (meth) acrylate quaternary salt - Google Patents
Process for preparing dialkyl amino alkyl (meth) acrylate quaternary salt Download PDFInfo
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Abstract
The object of the present invention is to provide a process for continuously producing a dialkylaminoalkyl (meth) acrylate quaternary salt by reacting a dialkylaminoalkyl (meth) acrylate with a gaseous quaternizing agent in an aqueous dialkylaminoalkyl (meth) acrylate quaternary salt solution to produce a dialkylaminoalkyl (meth) acrylate quaternary salt, wherein the efficiency of the reaction of the gaseous quaternizing agent is increased and the production of acrylic acid as a by-product is suppressed. According to the present invention, a dialkylaminoalkyl (meth) acrylate, a gaseous quaternizing agent and water are supplied to a dialkylaminoalkyl (meth) acrylate quaternary salt aqueous solution contained in a reactor (11), and the quaternizing agent is continuously supplied as a bubble-like material (2) having an average diameter of 100 [ mu ] m or less when the dialkylaminoalkyl (meth) acrylate and the quaternizing agent are reacted.
Description
Technical field
The present invention relates to the continuous preparation method of good (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt of productivity.
Background technology
(methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt prepares by quaternizing agents such as (methyl) propenoic acid dialkyl aminoalkyl ester and methyl chloride are reacted.As its preparation method, known following patent documentation 1～5 disclosed method.
In preparation method in the past, someone has proposed the using method of the raw materials such as supply method of raw material, for example, in patent documentation 1 disclosed method, to the solution that only contains (methyl) propenoic acid dialkyl aminoalkyl ester or, contain in the mixing solutions of (methyl) propenoic acid dialkyl aminoalkyl ester, glass ingress pipe by an internal diameter 6mm directly imports haloalkane, follows the carrying out of reaction to import water from ingress pipe.According to this method, might make the bubble of the haloalkane of importing become big, thereby cause these bubbles not react and be discharged in the gas phase.
Patent documentation 3 discloses a kind of preparation method, it is characterized in that, in the reactor that contains (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt aqueous solution, supply with (methyl) propenoic acid dialkyl aminoalkyl ester, boiling point is at quaternizing agent below 25 ℃ and water, prepare (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt thus, at this moment, feed speed according to 0.06～1.1 quality % that is equivalent to the reaction solution quality in the reactor, supply with (methyl) propenoic acid dialkyl aminoalkyl ester to reactor, and, under being condition more than 10 (1/h), the mass transfer capacity coefficient with aquametry reacts.
According to these methods, in order not allow the hold-up of quaternizing agent reduce and in reactor, to pressurize, but in order to prevent that unreacted quaternizing agent is from aqueous solution release, rear treating groove (flnishing tank) is set after reactive tank, thus, unreacted quaternizing agent is reacted, thereby reduce the loss of quaternizing agent.
Patent documentation 4 discloses the technology of a kind of preparation (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt, and this technology as certain conditions, and reclaims, removes unreacted quaternizing agent with the usage quantity of the quaternizing agent supplied with and feed speed.
In addition, patent documentation 5 discloses a kind of method, this method is when adding vinyl monomer such as (methyl) propenoic acid dialkyl aminoalkyl ester and water respectively prepare (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt in quaternizing agent, limits the adding conditional of water.
Patent documentation 1: the spy opens the 2005-220111 communique
Patent documentation 2: the spy opens the 2003-342244 communique
Patent documentation 3; The spy opens the 2004-10508 communique
Patent documentation 4: the spy opens clear 63-5064 communique
Patent documentation 5: the spy opens flat 3-135945 communique
Summary of the invention
The problem that invention will solve
When preparation (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt, in order not allow its yield reduce, usually, the usage quantity of quaternizing agent is excessive with respect to (methyl) propenoic acid dialkyl aminoalkyl ester.But, as quaternizing agent, normally used methyl chloride is the object material of PRTR method (about particular chemicals to the assurance of environment output etc. and the law that promotes the improvement of management), this material of a large amount of releases in gas phase, viewpoints such as security in environmental pollution, operation are considered, are not preferred.In addition, when for the purpose of utilizing again the operation that reclaims quaternizing agent being set, existence must be carried out the problem of extra operations such as concentration control.And then, as patent documentation 2 and 3 disclosed preparation methods, when preparation (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt in the aqueous solution, quaternizing agent shifts in gas phase, on the other hand, the hydrolysis in the aqueous solution of (methyl) propenoic acid dialkyl aminoalkyl ester generates a large amount of vinylformic acid, and these all are the problems that exists.
The objective of the invention is to, the method of continuous preparation (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt is provided, this method is by in (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt aqueous solution, make (methyl) propenoic acid dialkyl aminoalkyl ester with as the reaction of the gas quaternizing agents such as methyl chloride of PRTR method object chemical substance, during preparation (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt, improve the reaction efficiency of quaternizing agent, suppress the acrylic acid generation of by product, productivity is good.
Be used to solve the means of problem
The present invention is as follows.
1. the preparation method of (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt, this method comprises supplies with (methyl) propenoic acid dialkyl aminoalkyl ester, gas quaternizing agent and water in (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt aqueous solution that accommodates in reactor, make the reaction of (methyl) propenoic acid dialkyl aminoalkyl ester and quaternizing agent, it is characterized in that
Above-mentioned quaternizing agent is supplied with continuously as the air bubble-shaped thing of mean diameter below 100 μ m, and the mol ratio of the usage quantity of the usage quantity of above-mentioned quaternizing agent and above-mentioned (methyl) propenoic acid dialkyl aminoalkyl ester is 1～1.2.
2. the preparation method of above-mentioned 1 described (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt, the concentration of (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt in above-mentioned (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt aqueous solution that wherein, accommodates in the above-mentioned reactor is 30～90 quality %.
3. the preparation method of above-mentioned 1 or 2 described (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt, wherein, the pressure in the above-mentioned reactor is in the scope of normal atmosphere～1MPaG.
4. the preparation method of above-mentioned 1～3 each described (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt, wherein, as acrylic acid content of by product less than 1000 quality ppm.
5. the preparation method of above-mentioned 1 described (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt, wherein, above-mentioned quaternizing agent is a methyl chloride, above-mentioned (methyl) propenoic acid dialkyl aminoalkyl ester is (methyl) dimethylaminoethyl acrylate, and, (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt in above-mentioned (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt aqueous solution that accommodates in the above-mentioned reactor is a muriate, this muriatic concentration is 60～85 quality %, and the mol ratio of the usage quantity of the usage quantity of above-mentioned quaternizing agent and above-mentioned (methyl) propenoic acid dialkyl aminoalkyl ester is 1～1.1.
6. the preparation method of above-mentioned 1 described (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt, wherein, above-mentioned quaternizing agent is a methyl chloride, above-mentioned (methyl) propenoic acid dialkyl aminoalkyl ester is (methyl) dimethylaminoethyl acrylate, and, the mean diameter of above-mentioned air bubble-shaped thing is below the 80 μ m, and, (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt in above-mentioned (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt aqueous solution that accommodates in the above-mentioned reactor is a muriate, this muriatic concentration is 70～85 quality %, and, the mol ratio of the usage quantity of the usage quantity of above-mentioned quaternizing agent and above-mentioned (methyl) propenoic acid dialkyl aminoalkyl ester is 1～1.05, and, the concentration of prepared (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt is lower than the concentration of (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt that accommodates before the reaction, is 50～82 quality %.
The invention effect
According to the present invention, can suppress to prepare (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt under the acrylic acid condition of by-product continuously.Especially, owing to can make the acrylic acid content of by product less than 1000 quality ppm, and improve the reaction efficiency of gas quaternizing agent, therefore, the productivity of (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt is good.In addition, gas quaternizing agents such as normally used methyl chloride though be the object material of PRTR method, adopt preparation method of the present invention, can reduce and then suppress its burst size in gas phase significantly, the aspects such as security in environmental pollution, operation are useful.
When the concentration of (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt in above-mentioned (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt aqueous solution that accommodates in the above-mentioned reactor is 30～90 quality %, can improve the reaction efficiency of gas quaternizing agent, be applicable to continuous preparation (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt.
When the pressure in the above-mentioned reactor is in the pressurized state of normal atmosphere～1MPaG (more than the normal atmosphere to 1MPaG), can increase the meltage of quaternizing agent in above-mentioned (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt aqueous solution, simultaneously, can make it be trapped in the solution more chronically, and suppress it and be discharged in the gas phase, promote the reaction of (methyl) propenoic acid dialkyl aminoalkyl ester and quaternizing agent, thus can quaternizing agent in (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt aqueous solution almost all be used for and the reaction of (methyl) propenoic acid dialkyl aminoalkyl ester with supplying to.
In the following cases, promptly, above-mentioned quaternizing agent is a methyl chloride, above-mentioned (methyl) propenoic acid dialkyl aminoalkyl ester is (methyl) dimethylaminoethyl acrylate, and, (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt in above-mentioned (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt aqueous solution that accommodates in the above-mentioned reactor is a muriate, this muriatic concentration is 60～85 quality %, and, when the ratio of the usage quantity of the usage quantity of above-mentioned quaternizing agent and above-mentioned (methyl) propenoic acid dialkyl aminoalkyl ester is 1～1.1 times (mol ratio), can improve the reaction efficiency of quaternizing agent like this, suppress the acrylic acid generation of by product, productivity prepares (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt goodly continuously.
In the following cases, promptly, above-mentioned quaternizing agent is a methyl chloride, above-mentioned (methyl) propenoic acid dialkyl aminoalkyl ester is (methyl) dimethylaminoethyl acrylate, and, the mean diameter of above-mentioned air bubble-shaped thing is below the 80 μ m, and, (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt in above-mentioned (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt aqueous solution that accommodates in the above-mentioned reactor is a muriate, this muriatic concentration is 70～85 quality %, and, the ratio of the usage quantity of the usage quantity of above-mentioned quaternizing agent and above-mentioned (methyl) propenoic acid dialkyl aminoalkyl ester is 1～1.05 times (mol ratio), and, the concentration of prepared (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt is lower than the concentration of (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt that accommodates before the reaction, be 50～82 quality %, can improve the reaction efficiency of quaternizing agent like this, suppress the acrylic acid generation of by product, productivity prepares (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt goodly continuously.
Description of drawings
Fig. 1 is the mode chart that a routine preparation facilities of method produced according to the present invention is shown.
Nomenclature
1: preparation facilities
11: reactor
12: the micro bubble generator
13: the quaternizing agent reservoir
The 15:(methyl) propenoic acid dialkyl aminoalkyl ester supply-pipe
16: water supplying pipe
17: stirrer
19:DAM aqueous solution transfer lime
2: air bubble-shaped thing (quaternizing agent)
Embodiment
The preparation method (hereinafter referred to as " preparation method of the present invention ") of (methyl) of the present invention propenoic acid dialkyl aminoalkyl ester quaternary salt (below be also referred to as " DAM ") comprises in (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt aqueous solution of accommodating in reactor (below be also referred to as " the DAM aqueous solution ") and supplies with (methyl) propenoic acid dialkyl aminoalkyl ester, gas quaternizing agent and water, make the reaction of (methyl) propenoic acid dialkyl aminoalkyl ester and quaternizing agent, it is characterized in that, above-mentioned quaternizing agent is supplied with continuously as the air bubble-shaped thing of mean diameter below 100 μ m, and the mol ratio of the usage quantity of the usage quantity of above-mentioned quaternizing agent and above-mentioned (methyl) propenoic acid dialkyl aminoalkyl ester is 1～1.2.
Illustrated that in this manual, " (methyl) vinylformic acid " is meant vinylformic acid and methacrylic acid, " (methyl) acrylate " is meant acrylate and methacrylic ester.
In preparation method of the present invention, preferably continuous supply gas quaternizing agent in the DAM aqueous solution in reactor is supplied with (methyl) propenoic acid dialkyl aminoalkyl ester and water continuously or in batches.
As above-mentioned (methyl) propenoic acid dialkyl aminoalkyl ester, can enumerate (methyl) dimethylaminoethyl acrylate, (methyl) vinylformic acid lignocaine ethyl ester, (methyl) vinylformic acid two n-propylamine base ethyl esters, (methyl) vinylformic acid diisopropylaminoethyl ethyl ester etc.They can use a kind separately, perhaps will be used in combination more than 2 kinds.In the present invention, preferred (methyl) dimethylaminoethyl acrylate.
As above-mentioned quaternizing agent, be compound below 50 ℃ preferably at the boiling point under 1 air pressure, more preferably-30 ℃～30 ℃ compound.As boiling point is compound below 50 ℃, can enumerate methyl chloride (boiling point-24.2 ℃), monochloroethane (12.3 ℃ of boiling points), chloro n-propane (46.6 ℃ of boiling points), chloroisopropane (38.8 ℃ of boiling points) etc.They can use a kind separately, perhaps will be used in combination more than 2 kinds.In the present invention, preferred normal temperature is the methyl chloride of gas down.
In addition,, preferably use the content water seldom of metal ingredient, use distilled water, ion exchanged water etc. usually as above-mentioned water.
The kind of contained DAM does not have particular determination in the above-mentioned DAM aqueous solution, uses the DAM identical with the DAM that wants to prepare usually.That is, when the DAM that wants to prepare was the methyl chloride quaternary ammonium salt of dimethylaminoethyl acrylate, contained DAM also was identical compound (that is the methyl chloride quaternary ammonium salt of dimethylaminoethyl acrylate) in the above-mentioned DAM aqueous solution.Preparation raw material under this situation as above-mentioned (methyl) propenoic acid dialkyl aminoalkyl ester, uses (methyl) dimethylaminoethyl acrylate, as above-mentioned quaternizing agent, uses methyl chloride.
In addition, the concentration of the DAM in the above-mentioned DAM aqueous solution does not have particular determination, is preferably 30～90 quality %, more preferably 60～85 quality %, 70～85 quality % more preferably.If above-mentioned DAM concentration is in this scope, then can prepare DAM with high reaction efficiency.
In preparation method of the present invention, the above-mentioned DAM aqueous solution is housed within the reactor in advance.After the reaction beginning, that is, after beginning to supply with (methyl) propenoic acid dialkyl aminoalkyl ester, gas quaternizing agent and water, in addition, can on one side the DAM concentration in the reactor be maintained in the above-mentioned preferable range, Yi Bian add the DAM aqueous solution continuously or in batches.The DAM aqueous solution that use this moment is preferably the aqueous solution (contain the aqueous solution with a kind of DAM) identical with the DAM aqueous solution that accommodates in advance or the high aqueous solution (containing the aqueous solution with a kind of DAM) of this DAM concentration of aqueous solution that accommodates in advance of concentration ratio.
Illustrated; when not accommodating under the state of the DAM aqueous solution in advance; when supply (methyl) propenoic acid dialkyl aminoalkyl ester, gas quaternizing agent and water react in above-mentioned reactor; because (methyl) vinylformic acid dimethylamino acryl ester generation hydrolysis; generate (methyl) vinylformic acid, might make the purity drop of the DAM in the reaction solution of acquisition like this.
As above-mentioned reactor, as long as have thermotolerance, erosion resistance, just there is not particular determination, its material, structure and size there are not particular determination yet.Preferred reactor for its inner face coating and/or in be lined with the reactor of glass etc.In addition, because the using gas quaternizing agent, but the therefore preferred reactor that has the good structure of resistance to air loss, more preferably has pressure structure that uses for example can be enumerated autoclave etc.
As described below, in above-mentioned reactor, can dispose the stirrer that is used to stir material composition etc., be used for the micro bubble generator of supply gas quaternizing agent etc.
In preparation method of the present invention, preferably with above-mentioned quaternizing agent as mean diameter be below the 100 μ m, be preferably below the 95 μ m, more preferably below the 90 μ m, the air bubble-shaped thing below the 80 μ m more preferably, supply to continuously in the above-mentioned DAM aqueous solution, the lower value of the mean diameter of this air bubble-shaped thing is generally 1 μ m.If have the quaternizing agent of above-mentioned mean diameter, then can make the lift velocity of the air bubble-shaped thing in the DAM aqueous solution slack-off, thereby make above-mentioned quaternizing agent be difficult for being discharged in the gas phase.As a result, can further prolong the residence time of quaternizing agent in the above-mentioned DAM aqueous solution, thereby can prepare DAM with high reaction efficiency.Illustrated that above-mentioned mean diameter can adopt is visual, use the light scattering method of laser etc. to wait measures.
The method of above-mentioned quaternizing agent being made the air bubble-shaped thing does not have particular determination, can only use this quaternizing agent, can use this quaternizing agent and water to make the air bubble-shaped thing yet.As the bubble generation mode of above-mentioned micro bubble generator, can enumerate gas liquid two-phase whirl mode, spray regime etc.
The supply of above-mentioned air bubble-shaped thing can in any direction be carried out.That is, any one direction in top, side and the below of the DAM aqueous solution that can accommodate from above-mentioned reactor is supplied with.Therefore, above-mentioned micro bubble generator can be configured in any position of reactor.
The feed speed of above-mentioned quaternizing agent, can wait suitable the selection according to the volume of the concentration of the DAM aqueous solution that accommodates in the reactor and usage quantity thereof, reactor, with respect to 1 liter of the above-mentioned DAM aqueous solution or prepared reaction solution, be generally 25～400g/ hour, be preferably 100～200g/ hour.If be in this scope, then above-mentioned quaternizing agent is difficult for being discharged in the gas phase, thereby can prepare DAM with high reaction efficiency.
For the composition of inhibited reaction system through the time become unstable, for the supply of above-mentioned (methyl) propenoic acid dialkyl aminoalkyl ester and water, compare with supplying with by disposable mode, preferably supply with according to successive or batch-wise mode.
The feed speed of above-mentioned (methyl) propenoic acid dialkyl aminoalkyl ester and water does not have particular determination.The feed speed of above-mentioned (methyl) propenoic acid dialkyl aminoalkyl ester with respect to 1 liter of the above-mentioned DAM aqueous solution or prepared reaction solution, is generally 50～1200g/ hour, is preferably 200～600g/ hour.Illustrated, be used to prepare (methyl) propenoic acid dialkyl aminoalkyl ester of DAM and the reaction of quaternizing agent is a reaction with same mole.But, can carry out with higher reaction efficiency in order to make these reactions, and, even a part of quaternizing agent is discharged into the gas phase from reaction solution, still have the quaternizing agent of higher concentration to be present in the reaction solution, should make that the usage quantity (accumulative total feed rate) of above-mentioned quaternizing agent is identical with the mole number of the usage quantity (accumulative total feed rate) of (methyl) propenoic acid dialkyl aminoalkyl ester, perhaps the mole number than the usage quantity of (methyl) propenoic acid dialkyl aminoalkyl ester (accumulative total feed rate) is higher, and the mol ratio that can make them is 1～1.2, be preferably 1～1.1, more preferably 1～1.05.By mol ratio is in this scope, can make productivity, quality and security good.
In addition, the feed speed of water is generally 25～400g/ hour, is preferably 100～200g/ hour with respect to 1 liter of the above-mentioned DAM aqueous solution or prepared reaction solution.When reacting, along with the generation of DAM, the DAM concentration in the reaction solution changes, and by the supply of water, can wait according to purpose, purposes and regulate DAM concentration.
In preparation method of the present invention, preferably according to the DAM concentration in the reaction solution that can make acquisition, identical with the DAM concentration in the DAM aqueous solution that accommodates in advance before the reaction, perhaps preferably than its low 1～5 quality %, more preferably the condition of low 2～4 quality % is supplied with above-mentioned (methyl) propenoic acid dialkyl aminoalkyl ester, quaternizing agent and water.Thus, can prepare the DAM aqueous solution that has suppressed the acrylic acid content of by product.
In preparation method of the present invention, temperature of reaction can wait suitable the selection according to the kind of (methyl) propenoic acid dialkyl aminoalkyl ester that is used to prepare DAM, the kind of quaternizing agent, is generally 30 ℃～60 ℃, is preferably 40 ℃～60 ℃.Illustrated, be housed within advance in the reactor the DAM aqueous solution and as (methyl) propenoic acid dialkyl aminoalkyl ester and the water of material composition, in use, also can be heated to said temperature.
In addition, the pressure in the above-mentioned reactor preferably is in the scope of normal atmosphere～1MPaG.Thus, quaternizing agent is trapped in the above-mentioned DAM aqueous solution for more time, and, can suppress it and be discharged in the gas phase.Above-mentioned pressure is 0.05～0.7MPaG, 0.1～0.5MPaG more preferably more preferably.
Adopt preparation method of the present invention, can suppress the acrylic acid generation of by product, therefore, in the DAM aqueous solution that obtains, acrylic acid content usually less than 1000 quality ppm, preferably less than 900 quality ppm, be more preferably less than 700 quality ppm.Illustrated,, therefore,, can be obtained the DAM aqueous solution that content is few, purity is high of the composition beyond the DAM according to preparation method of the present invention owing to almost do not have residually as the quaternizing agent of material composition.DAM concentration in the DAM aqueous solution that obtains is generally 50～85 quality %, is preferably 50～82 quality %.
In preparation method of the present invention, preferably in the process of preparation DAM, the DAM aqueous solution (reaction solution) in the reactor is discharged.The discharge of this DAM aqueous solution, can with beginning base feed composition in begin, also can begin again at the base feed composition and through behind the certain hour.Under these situations, discharge method and condition thereof do not have particular determination, and discharging operation can carry out continuously, can carry out off and on yet.By the output of regulating the DAM aqueous solution, can carry out the preparation of DAM and the discharge of the aqueous solution thereof by certain speed according to the feed rate of material composition.Under this situation, in above-mentioned reactor, DAM concentration is stable all the time, can prepare the DAM aqueous solution that by-products content has reduced continuously.
The DAM aqueous solution of being discharged is received in storagetank etc., as required, carries out the oxygen dissolution process with oxygen-containing gas.Handle by this, can prevent the polymerization of DAM.In addition, when residual when unreacted quaternizing agent is arranged in the DAM aqueous solution, quaternizing agent can be removed.This oxygen-containing gas can be imported to the gas phase portion in the storagetank, also can be with its bubbling in the DAM aqueous solution.In addition, also can or alternately carry out these two kinds of methods whiles.In order to remove quaternizing agent residual in the DAM aqueous solution efficiently, preferably with oxygen-containing gas bubbling in the DAM aqueous solution.
Illustrated, as above-mentioned oxygen-containing gas, the mixed gas that uses oxygen or air and rare gas element (nitrogen, argon gas etc.) to form usually.The importing condition of above-mentioned oxygen-containing gas (temperature of import volume, importing time, the DAM aqueous solution etc.) does not have particular determination.
The internal pressure of above-mentioned storagetank etc. preferably is in the scope of normal atmosphere～0.7MPaG (normal atmosphere is above to 0.7MPaG).Can prevent the polymerization of DAM thus.
In the present invention, preferred manufacturing procedure possesses following condition, promptly, above-mentioned quaternizing agent is a methyl chloride, above-mentioned (methyl) propenoic acid dialkyl aminoalkyl ester is (methyl) dimethylaminoethyl acrylate, and, (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt that is housed within above-mentioned (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt aqueous solution in the above-mentioned reactor is a muriate, this muriatic concentration is 60～85 quality %, and the mol ratio of the usage quantity of the usage quantity of above-mentioned quaternizing agent and above-mentioned (methyl) propenoic acid dialkyl aminoalkyl ester is 1～1.1.According to this method, need not to supply with the above quaternizing agent (methyl chloride) of necessary amount, also can improve its reaction efficiency, and, can be continuously and stably prepare the DAM aqueous solution that acrylic acid content is lower than 1000 quality ppm.Under the situation of the DAM aqueous solution (reaction solution) in discharging reactor, can further improve above-mentioned effect.Therefore, this preparation method can suppress quaternizing agent (methyl chloride) and be discharged in the gas phase, security, best in quality, and productivity is also good simultaneously.
In addition, in the present invention, preferred manufacturing procedure possesses following condition, promptly, above-mentioned quaternizing agent is a methyl chloride, above-mentioned (methyl) propenoic acid dialkyl aminoalkyl ester is (methyl) dimethylaminoethyl acrylate, and, the mean diameter of above-mentioned air bubble-shaped thing is below the 80 μ m, be preferably 10～70 μ m, and, (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt in above-mentioned (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt aqueous solution that accommodates in the above-mentioned reactor is a muriate, this muriatic concentration is 70～85 quality %, and the mol ratio of the usage quantity of the usage quantity of above-mentioned quaternizing agent and above-mentioned (methyl) propenoic acid dialkyl aminoalkyl ester is 1～1.05, and, the concentration of prepared (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt is lower than the concentration of (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt that accommodates before the reaction, is 50～82 quality %.According to this method, need not to supply with the above quaternizing agent (methyl chloride) of necessary amount, also can improve its reaction efficiency.And, can be continuously and stably prepare the DAM aqueous solution that acrylic acid content is lower than 1000 quality ppm.Under the situation of the DAM aqueous solution (reaction solution) in discharging reactor, can further improve above-mentioned effect.Therefore, this preparation method can suppress the release of quaternizing agent (methyl chloride) in gas phase, security, best in quality, and productivity is also good simultaneously.
Fig. 1 illustrates an example of the preparation facilities that uses among the preparation method of the present invention.Micro bubble generator 12, (methyl) propenoic acid dialkyl aminoalkyl ester supply-pipe 15, water supplying pipe 16, stirrer 17 that the preparation facilities 1 of Fig. 1 possesses reactor 11, disposes near the inner bottom surface of reactor 11.And then, can also possess and be used for supplying with DAM aqueous solution transfer lime 19 that the quaternizing agent reservoir 13 of quaternizing agents, the DAM aqueous solution that is used for that reaction is obtained discharge etc. to bubble generation machine 12.
Embodiment
Below enumerate embodiment, specifically describe the present invention, but the present invention is not subjected to any restriction of these embodiment.
Embodiment 1
Employed reactor is vertical autoclave, is used to make micro bubble generator, stirrer, thermometer, pressure warning unit and the temperature regulation chuck of methyl chloride gas with fine bubble state generation according to the bottom side in reactor to the order equipment of liquid level direction.
At first, in autoclave, add concentration and be the aqueous solution 517g of methyl chloride quaternary ammonium salt of the dimethylaminoethyl acrylate of 82 quality %, under air-tight state, heat.
Then, on one side the above-mentioned aqueous solution is remained on 50 ℃ and stir, confirm that the pressure in the autoclave maintains normal atmosphere, on one side methyl chloride gas, dimethylaminoethyl acrylate and water are supplied with the feed speed of 72.8g/ hour, 206.2g/ hour and 69.8g/ hour respectively.In addition, simultaneously, the aqueous solution in the autoclave is extracted out with 348.8g/ hour the velocity of discharge, be delivered to storagetank.Illustrated, will contain the aqueous solution sampling of the methyl chloride gas that is in the bubble state, with the mean diameter of laser type nanometer particle size measure of spread device mensuration bubble, the mean diameter of the bubble that records is 39 μ m.In reaction process, confirming does not almost have methyl chloride gas to be discharged in the gas phase.
From beginning to supply with above-mentioned each composition meter through 6 hours time point, the accumulative total feed rate of methyl chloride gas, dimethylaminoethyl acrylate and water is respectively 437g (8.66 moles), 1237g (8.64 moles) and 419g (mol ratio of methyl chloride and dimethylaminoethyl acrylate is 1.002).
In addition, from beginning to supply with above-mentioned each composition meter through after 6 hours, analyze the aqueous solution in the autoclave, result, the concentration of the methyl chloride quaternary ammonium salt of dimethylaminoethyl acrylate are 80.1 quality %.In addition, the acrylic acid concentration of by product is 676 quality ppm.
Except the pressure in the autoclave being maintained 0.5MPaG, all the other are operated similarly to Example 1, spend the methyl chloride quaternary ammonium salt of 6 hours preparation dimethylaminoethyl acrylates.The concentration of this resultant is 80.4 quality %.In addition, the acrylic acid concentration of by product is 426 quality ppm.
Embodiment 3
Except the mean diameter that makes the bubble of methyl chloride gas in reaction solution was 90 μ m, all the other were operated similarly to Example 1, spent the methyl chloride quaternary ammonium salt of 6 hours preparation dimethylaminoethyl acrylates.The concentration of this resultant is 80.2 quality %.In addition, the acrylic acid concentration of by product is 933 quality ppm.
Comparative example 1
Use the preparation facilities identical with embodiment 1, adding concentration is the aqueous solution 517g of methyl chloride quaternary ammonium salt of the dimethylaminoethyl acrylate of 82 quality % in autoclave, heats under air-tight state.
Then, on one side the above-mentioned aqueous solution is remained on 50 ℃ and stir, confirm that the pressure in the autoclave maintains normal atmosphere, on one side methyl chloride gas (the mean diameter 39 μ m of bubble), dimethylaminoethyl acrylate and water are supplied with the feed speed of 43.3g/ hour, 128.4g/ hour and 40.3g/ hour respectively.In addition, simultaneously, the aqueous solution in the autoclave is extracted out with 212.0g/ hour the velocity of discharge, be delivered to storagetank.In reaction process, confirming does not almost have methyl chloride gas to be discharged in the gas phase.
From beginning to supply with above-mentioned each composition meter through 6 hours time point, the accumulative total feed rate of methyl chloride gas, dimethylaminoethyl acrylate and water is respectively 260g (5.15 moles), 770.2g (5.38 moles) and 241.7g (mol ratio of methyl chloride and dimethylaminoethyl acrylate is 0.957).
In addition, from beginning to supply with above-mentioned each composition meter through after 6 hours, analyze the aqueous solution in the autoclave, result, the concentration of the methyl chloride quaternary ammonium salt of dimethylaminoethyl acrylate are 81.0 quality %.In addition, the acrylic acid concentration of by product is 4489 quality ppm.
Comparative example 2
Use the preparation facilities identical with embodiment 1, adding concentration is the aqueous solution 517g of methyl chloride quaternary ammonium salt of the dimethylaminoethyl acrylate of 82 quality % in autoclave, heats under air-tight state.
Then, on one side the above-mentioned aqueous solution is remained on 50 ℃ and stir, confirm that the pressure in the autoclave maintains 0.5MPaG, on one side methyl chloride gas (the mean diameter 39 μ m of bubble), dimethylaminoethyl acrylate and water are supplied with the feed speed of 80g/ hour, 128.4g/ hour and 43.4g/ hour respectively.In addition, simultaneously, the aqueous solution in the autoclave is extracted out with 251.8g/ hour the velocity of discharge, be delivered to storagetank.In reaction process, confirming has methyl chloride gas to be discharged in the gas phase.
From beginning to supply with above-mentioned each composition meter through 6 hours time point, the accumulative total feed rate of methyl chloride gas, dimethylaminoethyl acrylate and water is respectively 480g (9.51 moles), 770.2g (5.38 moles) and 260.5g (mol ratio of methyl chloride and dimethylaminoethyl acrylate is 1.768).
In addition, from beginning to supply with above-mentioned each composition meter through after 6 hours, analyze the aqueous solution in the autoclave, result, the concentration of the methyl chloride quaternary ammonium salt of dimethylaminoethyl acrylate are 79.8 quality %.In addition, the acrylic acid concentration of by product is 430 quality ppm.
Comparative example 3
Use possesses the autoclave of being used chuck by gas supply device, stirrer, thermometer, pressure warning unit, the temperature regulation of the nozzle supply methyl chloride gas of the about 2mm of internal diameter, to wherein adding the aqueous solution 517g of methyl chloride quaternary ammonium salt that concentration is the dimethylaminoethyl acrylate of 82 quality %, under air-tight state, heat.
Then, on one side the above-mentioned aqueous solution is remained on 50 ℃ and stir, confirm that the pressure in the autoclave maintains 0.5MPaG, on one side methyl chloride gas, dimethylaminoethyl acrylate and water are supplied with the feed speed of 80g/ hour, 206.2g/ hour and 69.7g/ hour respectively.In addition, simultaneously, the aqueous solution in the autoclave is extracted out with 355.9g/ hour the velocity of discharge, be delivered to storagetank.Illustrated, estimated the external diameter of supplying with methyl chloride gas by nozzle, the result, external diameter is about 1mm.In reaction process, confirming has methyl chloride gas to be discharged in the gas phase.
From beginning to supply with above-mentioned each composition meter through 6 hours time point, the accumulative total feed rate of methyl chloride gas, dimethylaminoethyl acrylate and water is respectively 480g (9.51 moles), 1237g (8.64 moles) and 418.3g (mol ratio of methyl chloride and dimethylaminoethyl acrylate is 1.101).
In addition, from beginning to supply with above-mentioned each composition meter through after 6 hours, analyze the aqueous solution in the autoclave, result, the concentration of the methyl chloride quaternary ammonium salt of dimethylaminoethyl acrylate are 80.1 quality %.In addition, the acrylic acid concentration of by product is 2205 quality ppm.
Comparative example 4
Use the preparation facilities identical with embodiment 1, adding dimethylaminoethyl acrylate 614.2g (4.29mol) is heated to 50 ℃ under air-tight state in autoclave.
Then, aforesaid liquid is remained on 50 ℃ and stir,, make the pressure in the enclosed autoclave reach 0.5MPaG the methyl chloride pressurization.
Methyl chloride is supplied with 3 hours according to 1.32g/ minute feed speed is continuous, on one side the pressure in the autoclave is maintained 0.5MPaG, supply with the amount of used up methyl chloride on one side owing to reaction.
Beginning to supply with methyl chloride after 30 minutes, beginning water is supplied with 2.5 hours continuously with 1.38g/ minute feed speed.
Begin to supply with methyl chloride after 3 hours, the methyl chloride in the autoclave is discharged from venting port.The accumulative total feed rate of methyl chloride heretofore is 238.3g (4.72mol).
Then, in autoclave, be blown into air 3 hours,, obtain the aqueous solution of the methyl chloride quaternary ammonium salt of dimethylaminoethyl acrylate to remove the methyl chloride of molten surplus of depositing in the reaction solution.In this aqueous solution, the concentration of the methyl chloride quaternary ammonium salt of dimethylaminoethyl acrylate is 79.9 quality %.In addition, the acrylic acid concentration of by product is 3140 quality ppm.
Industrial applicability
Adopt (methyl) propenoic acid dialkyl aminoalkyl ester quaternary salt of the inventive method preparation, can be widely used in the raw material monomers such as the pigment dispersing agent of antistatic additive, coating of those dyeability modifying agents that are used for preparing fiber, plastics or ultraviolet curing auxiliary agent, fibre finish, resin for toner, coating, lube oil additive, paper power reinforcing agent, adhesive, ion exchange resin, cationic high-molecular flocculating agent etc.
Claims (6)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008-008470 | 2008-01-17 | ||
| JP2008008470 | 2008-01-17 | ||
| PCT/JP2008/070429 WO2009090791A1 (en) | 2008-01-17 | 2008-11-10 | Process for producing quaternary salt of dialkylaminoalkyl (meth)acrylate |
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| Publication Number | Publication Date |
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| CN101815699A true CN101815699A (en) | 2010-08-25 |
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| CN200880109792A Pending CN101815699A (en) | 2008-01-17 | 2008-11-10 | Process for preparing dialkyl amino alkyl (meth) acrylate quaternary salt |
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| Country | Link |
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| JP (1) | JPWO2009090791A1 (en) |
| CN (1) | CN101815699A (en) |
| WO (1) | WO2009090791A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153484A (en) * | 2011-01-07 | 2011-08-17 | 烟台开发区星火化工有限公司 | Quaternarization method of (dialkyl) aminoethyl methacrylate |
| CN104744275A (en) * | 2015-03-23 | 2015-07-01 | 浙江友联化学工业有限公司 | Preparation method of quaternary ammonium cationic monomer aqueous solution |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US8247597B2 (en) * | 2010-01-21 | 2012-08-21 | Nalco Company | Continuous production of DMAEA quaternary salts |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01249749A (en) * | 1988-03-30 | 1989-10-05 | Sanyo Chem Ind Ltd | Production of unsaturated quaternary ammonium salt |
| JPH0495053A (en) * | 1990-08-08 | 1992-03-27 | Mitsubishi Gas Chem Co Inc | Production of aqueous solution of unsaturated quaternary ammonium salt |
| FR2750697B1 (en) * | 1996-07-08 | 1998-10-30 | Atochem Elf Sa | PROCESS FOR THE MANUFACTURE OF AQUEOUS SOLUTIONS OF UNSATURATED AMATONIUM SALTS |
| JPH1180058A (en) * | 1997-09-08 | 1999-03-23 | Nippon Steel Chem Co Ltd | Method for producing phenols |
| JP3895065B2 (en) * | 1998-12-28 | 2007-03-22 | ライオン株式会社 | Method and apparatus for producing α-sulfo fatty acid alkyl ester salt |
| FR2812874B1 (en) * | 2000-08-11 | 2002-10-18 | Atofina | PROCESS FOR MANUFACTURING AQUEOUS SOLUTIONS OF (METH) ACRYLOYLOXYBENZYLDIMETHYLAMMONIUM CHLORIDES |
| FR2824062B1 (en) * | 2001-04-27 | 2004-10-15 | Atofina | PROCESS FOR PRODUCING AQUEOUS SOLUTIONS OF QUATERNARY AMMONIUM UNSATURATED SALTS |
| JP2003286235A (en) * | 2002-03-26 | 2003-10-10 | Mitsubishi Rayon Co Ltd | Method for producing unsaturated quaternary ammonium salt |
| JP4426164B2 (en) * | 2002-09-27 | 2010-03-03 | ダイヤニトリックス株式会社 | Method for producing unsaturated quaternary ammonium salt |
| JP2004168676A (en) * | 2002-11-18 | 2004-06-17 | Mitsubishi Rayon Co Ltd | Method for producing unsaturated quaternary ammonium salt |
| JP2006087876A (en) * | 2004-09-27 | 2006-04-06 | Saburo Ishiguro | Decomposition method of organochlorine compound |
| JP2008081443A (en) * | 2006-09-27 | 2008-04-10 | Toagosei Co Ltd | Manufacturing method of dialkylaminoalkyl (meth)acrylate quaternary salt and manufacturing apparatus therefor |
-
2008
- 2008-11-10 WO PCT/JP2008/070429 patent/WO2009090791A1/en not_active Ceased
- 2008-11-10 JP JP2009549959A patent/JPWO2009090791A1/en active Pending
- 2008-11-10 CN CN200880109792A patent/CN101815699A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153484A (en) * | 2011-01-07 | 2011-08-17 | 烟台开发区星火化工有限公司 | Quaternarization method of (dialkyl) aminoethyl methacrylate |
| CN104744275A (en) * | 2015-03-23 | 2015-07-01 | 浙江友联化学工业有限公司 | Preparation method of quaternary ammonium cationic monomer aqueous solution |
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| WO2009090791A1 (en) | 2009-07-23 |
| JPWO2009090791A1 (en) | 2011-05-26 |
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