CN103193923A - Preparation method and application of pervaporation separation material based on polyacrylate resin - Google Patents

Preparation method and application of pervaporation separation material based on polyacrylate resin Download PDF

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CN103193923A
CN103193923A CN2012100061788A CN201210006178A CN103193923A CN 103193923 A CN103193923 A CN 103193923A CN 2012100061788 A CN2012100061788 A CN 2012100061788A CN 201210006178 A CN201210006178 A CN 201210006178A CN 103193923 A CN103193923 A CN 103193923A
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monomer
preparation
infiltration evaporation
polyacrylate resin
solution
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CN103193923B (en
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夏雪伟
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Suzhou National Environmental New & Hi-Tech Industrial Park Development Co Ltd
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Suzhou National Environmental New & Hi-Tech Industrial Park Development Co Ltd
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Abstract

A preparation method of a pervaporation separation material based on polyacrylate resin. The method comprises the following steps: step one, preparing water, a dispersing agent and a surface active agent into an aqueous solution under the conditions of heating and stirring; step two, preparing monomers, an initiator and a crosslinking agent into a monomer solution; and step three, adding the aqueous solution into a reaction vessel, heating while stirring, then adding monomer solution into the reaction vessel, maintaining the temperature, stirring for reaction, curing, cooling to the room temperature, filtering, washing and drying to a constant weight, and crushing into particles to obtain the separation material based on pervaporation polyacrylate resin. In addition, the invention also provides application of the material prepared by the preparation method provided by the invention to a pervaporation separation device.

Description

Preparation method and application based on the infiltration evaporation parting material of polyacrylate resin
[technical field]
The present invention relates to a kind of preparation method and application of the infiltration evaporation parting material based on polyacrylate resin.
[background technology]
The infiltration evaporation technology is that nearly twenty or thirty develops a kind of new separation technology rapidly over year.Therefore the infiltration evaporation sepn process gentle restriction of liquid phase of not being bullied can be used for traditional liquid liquid and separate as the reluctant system of rectifying, as removing of minor amount of water in azeotrope separation, the organism etc.Infiltration evaporation often needs to rely on separatory membrane to realize, comprises multiple polymers film and inorganic material film, and its principle optionally holds certain nothing more than the regular micropore that relies on film inside or certain class material is realized separating substances by film.Infiltrating and vaporizing membrane is divided into water and preferentially preferentially passes through film by film and organism.Yet, no matter be that organism preferentially preferentially passes through film by film or water, the preparation technology of film itself is loaded down with trivial details, and cost is higher.On the other hand, the pressure drop when material passes through film is bigger, needs the film both sides to have pressure reduction, and therefore need pressurization or at opposite side certain vacuum tightness is arranged, its process complexity, running cost is higher, and especially energy consumption is higher.
[summary of the invention]
Based on this, be necessary to provide a kind of preparation method relatively simply based on the preparation method and application of the infiltration evaporation parting material of polyacrylate resin.
A kind of preparation method of the infiltration evaporation parting material based on polyacrylate resin comprises the steps:
Step 1, Jiang Shui, dispersion agent and tensio-active agent are mixed with aqueous phase solution under the condition of heated and stirred, wherein, the mass percent of described dispersion agent is 0.5%～1%, and the adding quality of described tensio-active agent is 0.1%～0.2% of described water;
Step 2, monomer, initiator and linking agent are mixed with monomer solution, wherein, described monomer is that 30%～50% methyl methacrylate, 10%～20% ethyl propenoate and 30%～60% butyl acrylate constitute by mass percent, the adding quality of described initiator is 0.3%～0.5% of described monomer, and the adding quality of described linking agent is 0.1%～0.2% of described monomer; And
Step 3, described aqueous phase solution is joined in the reaction vessel, under agitation condition, be heated to 75 ℃～85 ℃, be that 1: 2～1: 5 ratio joins described monomer solution in the described reaction vessel according to the volume ratio of described monomer solution and described aqueous phase solution then, holding temperature is at 80 ℃～85 ℃, with the speed stirring reaction of 150～250rpm 3～4 hours, temperature is risen to 90 ℃ of slakings 1 hour, be down to the room temperature after-filtration, washing, dry to constant weight, be ground into the particle that particle diameter is 0.5mm～2mm, obtain described infiltration evaporation parting material based on polyacrylate resin.
In a preferred embodiment, in the step 1, described dispersion agent is gelatin.
In a preferred embodiment, in the step 1, described tensio-active agent is Sodium dodecylbenzene sulfonate or sodium lauryl sulphate.
In a preferred embodiment, in the step 2, described initiator is dibenzoyl peroxide and N, the N-Diisopropyl azodicarboxylate.
In a preferred embodiment, in the step 2, described linking agent is Vinylstyrene or ethylene glycol diacrylate.
The application of material in the infiltration evaporation tripping device that obtains according to the preparation method of above-mentioned infiltration evaporation parting material based on polyacrylate resin.
A kind of preparation method of the infiltration evaporation parting material based on polyacrylate resin comprises the steps:
Step 1, dispersion agent is dissolved into is mixed with dispersant solution in the solvent, wherein, the adding quality of described dispersion agent is 1%～3% of described solvent;
Step 2, Jiang Shui, monomer, initiator and linking agent are mixed with monomer solution, wherein, described monomer is that 20%～40% Hydroxyethyl acrylate and 60%～80% vinylformic acid constitute by mass percent, the volume ratio of described monomer and water is 1: 1, the adding quality of described initiator is 0.5%～1% of described monomer, and the adding quality of described linking agent is 0.2%～0.5% of described monomer; And
Step 3, dispersant solution is joined in the reaction vessel, under agitation condition, be heated to 55 ℃～60 ℃, be that 1: 3～1: 5 ratio joins described monomer solution in the described reaction vessel according to the volume ratio of described monomer solution and described dispersant solution then, holding temperature is at 65 ℃, with the speed stirring reaction of 150～200rpm 3～4 hours, temperature is risen to 70 ℃ of slakings 1 hour, be down to the room temperature after-filtration, washing, dry to constant weight, be ground into the particle that particle diameter is 0.4mm～1mm, obtain described infiltration evaporation parting material based on polyacrylate resin.
In a preferred embodiment, in the step 1, described solvent is normal heptane or whiteruss.
In a preferred embodiment, in the step 1, described dispersion agent is calcium phosphate or calcium phosphate powder.
In a preferred embodiment, in the step 2, described initiator is Potassium Persulphate-sodium bisulfite.
In a preferred embodiment, in the step 2, described linking agent is N,N methylene bis acrylamide.
The application of material in the infiltration evaporation tripping device that obtains according to the preparation method of above-mentioned infiltration evaporation parting material based on polyacrylate resin.
A kind of preparation method of the infiltration evaporation parting material based on polyacrylate resin comprises the steps:
Step 1, monomer and water are mixed with monomer solution according to 1: 1 volume ratio, wherein said monomer is that 20%～40% Hydroxyethyl acrylate and 60%～80% vinylformic acid constitute by mass percent;
Step 2, be 1% initiator solution with the water-soluble formation mass concentration of initiator;
Step 3, described monomer solution is joined in the reaction vessel, under agitation condition, be heated to 60 ℃, 2%～5% ratio according to described monomer solution quality adds described initiator solution then, question response liquid becomes sticky to can't continue to stir the time, reaction solution is moved in the baking oven, 70 ℃ of following slakings 1 hour, be down to room temperature after-filtration, washing, dry to constant weight, be ground into the particle that particle diameter is 3mm～5mm, obtain described infiltration evaporation parting material based on polyacrylate resin.
In a preferred embodiment, in the step 2, described initiator is Potassium Persulphate-sodium bisulfite.
The application of material in the infiltration evaporation tripping device that obtains according to the preparation method of above-mentioned infiltration evaporation parting material based on polyacrylate resin.
Above-mentioned infiltration evaporation parting material is based on the infiltration evaporation parting material of polyacrylate resin, it can be realized in the water or mix and optionally to absorb certain or certain type organic in the organism, thereby and limit organic vaporization rate by the cross-linked network structure of polyacrylate resin inside and change water and organic gas-liquid phase equilibrium, realize a small amount of organic separation and purifying in the water with the rectifying coupling.In addition, with respect to traditional infiltrating and vaporizing membrane, above-mentioned infiltration evaporation parting material technical maturity based on polyacrylate resin, simple.
[description of drawings]
By the more specifically explanation of the preferred embodiments of the present invention shown in the accompanying drawing, above-mentioned and other purpose, feature and advantage of the present invention will become more clear.Reference numeral identical in whole accompanying drawings is indicated identical part, and painstakingly draws accompanying drawing by physical size equal proportion convergent-divergent, focuses on illustrating purport of the present invention.
Fig. 1 is the structural representation of the infiltration evaporation separating device of an embodiment.
[embodiment]
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing the specific embodiment of the present invention is described in detail.A lot of details have been set forth in the following description so that fully understand the present invention.But the present invention can implement much to be different from alternate manner described here, and those skilled in the art can do similar improvement under the situation of intension of the present invention, so the present invention is not subjected to the restriction of following public concrete enforcement.
See also Fig. 1, the infiltration evaporation separating device 100 of an embodiment comprises electric heater 1, container for storing liquid 2, knockout tower 3, condenser 4, return line 5 and discharge nozzle 6.
Electric heater 1 is used for the stoste to be separated in the heating container for storing liquid 2.Knockout tower 3 is made by glass, and its inside is filled with infiltration evaporation parting material 31.In the present embodiment, the internal diameter of knockout tower 3 is 50mm, and length is 1m.The infiltration evaporation parting material 31 of filling is divided into three sections, and every section about 20mm supports with Stainless Steel Cloth between section and the section, and keeps the distance between the section section to be about 100mm, is used for gas and distributes.The top of knockout tower 3 is provided with discharge port and refluxing opening (not indicating).Condenser 4 links to each other with refluxing opening with discharge port respectively with return line 5 by discharging pipeline 41, and discharge nozzle 6 links to each other with return line 5.Also be provided with under meter and valve on return line 5 and the discharge nozzle 6.
During use, electric heater 1 is heated into steam with the stoste to be separated in the container for storing liquid 2, mixing steam is by knockout tower 3, and the infiltration evaporation of the infiltration evaporation parting material through filling separates can realize that the organism that usual way is difficult to separate effectively separates the removal that maybe can realize less water in the organism.
Above-mentioned infiltration evaporation parting material is based on the infiltration evaporation parting material of polyacrylate resin, it can be realized in the water or mix and optionally to absorb certain or certain type organic in the organism, as optionally absorbing the water-soluble or materials such as the sl. sol. ketone of water, ester class of trace, thereby and limit organic vaporization rate by the cross-linked network structure of polyacrylate resin inside and change water and organic gas-liquid phase equilibrium, realize a small amount of organic separation and purifying in the water with the rectifying coupling; Also can absorb separation and the purifying of certain type organic in the realization organism mixing solutions by polyacrylate resin to the selectivity of certain type organic.
Above-mentioned infiltration evaporation parting material is based on the infiltration evaporation parting material of polyacrylate resin, and wherein polyacrylic ester can be selected methyl acrylate, ethyl propenoate, butyl acrylate etc. for use.Can select different polyacrylic ester monomers to generate corresponding polyacrylate polymers according to different separation systems.Its preparation process can be selected suspend poly-, inverse suspension polymerization and solution polymerization for use, and can make material to certain organism or glassware for drinking water absorptive character selectively by the adjusting of monomer component.Describe below by concrete preparation method.
The preparation method based on the infiltration evaporation parting material of polyacrylate resin of embodiment one comprises the steps:
Step 1, Jiang Shui, dispersion agent and tensio-active agent are mixed with aqueous phase solution under the condition of heated and stirred, wherein, the mass percent of described dispersion agent is 0.5%～1%, and the adding quality of described tensio-active agent is 0.1%～0.2% of described water.
Wherein, described dispersion agent is gelatin.Described tensio-active agent can be selected the anionic surfactant for use, for example can be Sodium dodecylbenzene sulfonate or sodium lauryl sulphate.
Step 2, monomer, initiator and linking agent are mixed with monomer solution, wherein, described monomer is that 30%～50% methyl methacrylate, 10%～20% ethyl propenoate and 30%～60% butyl acrylate constitute by mass percent, the adding quality of described initiator is 0.3%～0.5% of described monomer, and the adding quality of described linking agent is 0.1%～0.2% of described monomer.
Wherein, described initiator is dibenzoyl peroxide (BPO) and N, N-Diisopropyl azodicarboxylate (AIBN).Described linking agent is Vinylstyrene or ethylene glycol diacrylate.
Step 3, described aqueous phase solution is joined in the reaction vessel (reaction flask that for example has stirring and reflux), under agitation condition, be heated to 75 ℃～85 ℃, be that 1: 2～1: 5 ratio joins described monomer solution in the described reaction vessel according to the volume ratio of described monomer solution and described aqueous phase solution then, holding temperature is at 80 ℃～85 ℃, with the speed stirring reaction of 150～250rpm 3～4 hours, temperature is risen to 90 ℃ of slakings 1 hour, be down to the room temperature after-filtration, wash with water three times, with washing with alcohol once after, dry to constant weight, be ground into the particle that particle diameter is 0.5mm～2mm, obtain the infiltration evaporation parting material based on polyacrylate resin.
Can realize separating of the close pure and mild aromatic hydrocarbons of boiling point (for example methyl alcohol and benzene, methyl alcohol and tetrahydrofuran (THF)) by the infiltration evaporation parting material that above-mentioned preparation method obtains.
The preparation method based on the infiltration evaporation parting material of polyacrylate resin of embodiment two comprises the steps:
Step 1, dispersion agent is dissolved into is mixed with dispersant solution in the solvent, wherein, the adding quality of described dispersion agent is 1%～3% of described solvent.
Described dispersion agent is calcium phosphate or calcium phosphate powder.Described solvent is normal heptane or whiteruss.
Step 2, Jiang Shui, monomer, initiator and linking agent are mixed with monomer solution, wherein, described monomer is that 20%～40% Hydroxyethyl acrylate and 60%～80% vinylformic acid constitute by mass percent, the volume ratio of described monomer and water is 1: 1, the adding quality of described initiator is 0.5%～1% of described monomer, and the adding quality of described linking agent is 0.2%～0.5% of described monomer.
Described initiator is oxidation-reduction quality initiator, for example Potassium Persulphate-sodium bisulfite.Described linking agent is N,N methylene bis acrylamide.
Step 3, dispersant solution is joined in the reaction vessel (reaction flask that for example has stirring and reflux), under agitation condition, be heated to 55 ℃～60 ℃, be that 1: 3～1: 5 ratio joins described monomer solution in the described reaction vessel according to the volume ratio of described monomer solution and described dispersant solution then, holding temperature is at 65 ℃, with the speed stirring reaction of 150～200rpm 3～4 hours, temperature is risen to 70 ℃ of slakings 1 hour, be down to the room temperature after-filtration, behind water and the ethanol repetitive scrubbing three times, dry to constant weight, be ground into the particle that particle diameter is 0.4mm～1mm, obtain the infiltration evaporation parting material based on polyacrylate resin.
The infiltration evaporation parting material that obtains by above-mentioned preparation method can realize that some can form the dewatering of organism (for example ethyl acetate) of azeotropic point with water, can also realize the removing of minor amount of water in some organism (for example tetrahydrofuran (THF)) that can infinitely dissolve each other with water.
The preparation method based on the infiltration evaporation parting material of polyacrylate resin of embodiment three comprises the steps:
Step 1, monomer and water are mixed with monomer solution according to 1: 1 volume ratio, wherein said monomer is that 20%～40% Hydroxyethyl acrylate and 60%～80% vinylformic acid constitute by mass percent.
Step 2, be 1% initiator solution with the water-soluble formation mass concentration of initiator.
Described initiator is Potassium Persulphate-sodium bisulfite.
Step 3, described monomer solution is joined in the reaction vessel, under agitation condition, be heated to 60 ℃, 2%～5% ratio according to described monomer solution quality adds described initiator solution then, question response liquid becomes sticky to can't continue to stir the time, reaction solution is moved in the baking oven, 70 ℃ of following slakings 1 hour, be down to the room temperature after-filtration, behind water and the ethanol repetitive scrubbing three times, dry to constant weight, be ground into the particle that particle diameter is 3mm～5mm, obtain the infiltration evaporation parting material based on polyacrylate resin.
The infiltration evaporation parting material that obtains by above-mentioned preparation method can realize that some can form the dewatering of organism (for example ethyl acetate) of azeotropic point with water, can also realize the removing of minor amount of water in some organism (for example tetrahydrofuran (THF)) that can infinitely dissolve each other with water.
The present invention selects for use based on the infiltration evaporation parting material of the polyacrylate resin packing material as knockout tower, and its preparation method is comparatively convenient.Utilize polyacrylate resin, especially the resin that has certain degree of crosslinking (0.05～0.2%) is swelling and absorb the characteristics of specific solvent in its specific good solvent optionally, and the cross-linked network result by polymkeric substance inside changes balancing each other between organism and water and organism and the organism to the restriction that organism freely spreads.For example in containing the methyl alcohol of a small amount of benzene, because of benzene (good solvent of polyacrylic ester) can be preferential, optionally impel polymers swell to enter in the polymkeric substance internal network structure, and when vaporization, be restricted because of its speed that diffuses to the gas-solid two-phase interface, thereby itself and balancing each other of methyl alcohol are affected, and (namely with respect to the solution phase) more a spot of benzene is vaporized and is transferred steam to.And methyl alcohol is the poor solvent of polyacrylate resin, can't enter in the polymeric system, so less being affected of gas-liquid phase equilibrium of methyl alcohol, thereby be in the knockout tower of filler device with the infiltration evaporation parting material based on polyacrylate resin, can obtain benzene concentration at cat head and be lower than 1% methanol product.Because polyacrylate resin is realized by the selectivity swelling of organism to polymkeric substance organic separation, and the swelling of polymkeric substance in some organism or organic solvent is the characteristic property of polymeric system, therefore less demanding to the preparation of acrylate resin, spherical, the particulate state of this infiltration evaporation sepn process even pulverous resin all can use.
In addition, the separation factor of polyacrylate resin itself is low than infiltrating and vaporizing membrane, therefore polyacrylate resin is prepared into particulate state, state such as spherical after, it can be loaded into fixed bed as filler, can realize separating effect preferably equally.And the fixed-bed process maturation, gas percent of pass height, pressure drop are little.Need not to exert pressure and to realize in the fixed bed both sides.In addition, because above-mentioned parting material device becomes the fixed bed form of comparative maturity, its technical maturity, equipment are simple, and running cost is lower, is convenient to maximize and the commercialization popularization.
Below illustrate with specific embodiment.
Embodiment 1
Preparation aqueous phase solution: water, dispersion agent, tensio-active agent wiring solution-forming under condition of heating and stirring.Wherein dispersion agent is gelatin, and content is 0.5%; Tensio-active agent is Sodium dodecylbenzene sulfonate, and consumption is 0.1% of quality.
The preparation monomer solution wherein contains monomer, initiator, linking agent.Wherein monomer is methyl methacrylate, ethyl propenoate and butyl acrylate.Concrete ratio is methyl methacrylate 30%; Ethyl propenoate 10%; Butyl acrylate 60%.Linking agent is selected dibenzoyl peroxide (BPO) and N for use, and N-Diisopropyl azodicarboxylate (AIBN), consumption are 0.3% of monomer mass.Linking agent is selected Vinylstyrene for use, and consumption is 0.1% of monomer.
The volume ratio control of monomer solution and aqueous phase solution was at 1: 2.
Aqueous phase solution is added in the reaction flask that has backflow and whipping appts, is heated to 75 ℃ under agitation condition, keeps stirring velocity, and the monomer solution for preparing is once added.Be warming up to 80 ℃ of temperature of reaction, keep stirring (150rpm) and thermotonus after 3 hours, temperature is risen to 90 ℃ of slakings one hour.To react resulting resin filter after being cooled to normal temperature, wash with water three times, dry to constant weight after once with washing with alcohol, be ground into the particle that particle diameter is 0.5mm～2mm, obtain described infiltration evaporation parting material based on polyacrylate resin.
Embodiment 2
Preparation aqueous phase solution: water, dispersion agent, tensio-active agent wiring solution-forming under condition of heating and stirring.Wherein dispersion agent is gelatin, and content is 1%; Tensio-active agent is sodium lauryl sulphate, and consumption is 0.2% of quality.
The preparation monomer solution wherein contains monomer, initiator, linking agent.Wherein monomer is methyl methacrylate, ethyl propenoate and butyl acrylate.Concrete ratio is methyl methacrylate 50%; Ethyl propenoate 20%; Butyl acrylate 30%.Linking agent is selected dibenzoyl peroxide (BPO) and N for use, and N-Diisopropyl azodicarboxylate (AIBN), consumption are 0.5% of monomer mass.Linking agent is selected ethylene glycol diacrylate for use, and consumption is 0.2% of monomer.
The volume ratio control of monomer solution and aqueous phase solution was at 1: 5.
Aqueous phase solution is added in the reaction flask that has backflow and whipping appts, is heated to 85 ℃ under agitation condition, keeps stirring velocity, and the monomer solution for preparing is once added.Be warming up to 85 ℃ of temperature of reaction, keep stirring (250rpm) and thermotonus after 4 hours, temperature is risen to 90 ℃ of slakings one hour.To react resulting resin filter after being cooled to normal temperature, wash with water three times, dry to constant weight after once with washing with alcohol, be ground into the particle that particle diameter is 0.5mm～2mm, obtain described infiltration evaporation parting material based on polyacrylate resin.
Embodiment 3
Preparation dispersant solution: wherein contain normal heptane and dispersion agent.Dispersion agent is selected calcium phosphate for use, and consumption is 1% of dispersant solution.
Preparation water-soluble mono liquid solution: water, monomer, initiator and linking agent are mixed with homogeneous phase solution.Wherein monomer and water volume ratio are 1: 1, and monomer is Hydroxyethyl acrylate 20% and vinylformic acid 80%; Initiator adopts the oxidation-reduction type initiator, i.e. Potassium Persulphate-sodium bisulfite, and consumption is 0.5% of amount of monomer; Linking agent is N,N methylene bis acrylamide, and its consumption is 0.2% of amount of monomer.
The volume ratio control of monomer solution and dispersant solution is between 1: 3.
Dispersant solution is added in the reaction flask that has stirring and reflux, under agitation condition, be heated to 55 ℃, keep stirring velocity, the monomer solution for preparing is once added.Be warming up to 65 ℃ of temperature of reaction, keep stirring and thermotonus after 3 hours, temperature is risen to 70 ℃ of slakings one hour.To react resulting resin filter after being cooled to normal temperature, with after the washing with alcohol three times, dry to constant weight after washing three times with massive laundering standby.Control stir speed (S.S.) (150rpm-200rpm) can obtain the different rosin products of particle diameter with dispersant dosage, and the ultimate size of the resin that present embodiment synthesized is 0.4-1mm.
Embodiment 4
Preparation dispersant solution: wherein contain whiteruss and dispersion agent.Dispersion agent is selected calcium phosphate powder for use, and consumption is 2% of dispersant solution.
Preparation water-soluble mono liquid solution: water, monomer, initiator and linking agent are mixed with homogeneous phase solution.Wherein monomer and water volume ratio are 1: 1, and monomer is Hydroxyethyl acrylate 30% and vinylformic acid 70%; Initiator adopts the oxidation-reduction type initiator, i.e. Potassium Persulphate-sodium bisulfite, and consumption is 0.6% of amount of monomer; Linking agent is N,N methylene bis acrylamide, and its consumption is 0.3% of amount of monomer.
The volume ratio control of monomer solution and dispersant solution is between 1: 4.
Dispersant solution is added in the reaction flask that has stirring and reflux, under agitation condition, be heated to 56 ℃, keep stirring velocity, the monomer solution for preparing is once added.Be warming up to 65 ℃ of temperature of reaction, keep stirring and thermotonus after 3 hours, temperature is risen to 70 ℃ of slakings one hour.To react resulting resin filter after being cooled to normal temperature, with after the washing with alcohol three times, dry to constant weight after washing three times with massive laundering standby.Control stir speed (S.S.) (150rpm-200rpm) can obtain the different rosin products of particle diameter with dispersant dosage, and the ultimate size of the resin that present embodiment synthesized is 0.4-1mm.
Embodiment 5
Preparation dispersant solution: wherein contain normal heptane and dispersion agent.Dispersion agent is selected calcium phosphate for use, and consumption is 3% of dispersant solution.
Preparation water-soluble mono liquid solution: water, monomer, initiator and linking agent are mixed with homogeneous phase solution.Wherein monomer and water volume ratio are 1: 1, and monomer is Hydroxyethyl acrylate 40% and vinylformic acid 80%; Initiator adopts the oxidation-reduction type initiator, i.e. Potassium Persulphate-sodium bisulfite, and consumption is 0.8% of amount of monomer; Linking agent is N,N methylene bis acrylamide, and its consumption is 0.4% of amount of monomer.
The volume ratio control of monomer solution and dispersant solution is between 1: 5.
Dispersant solution is added in the reaction flask that has stirring and reflux, under agitation condition, be heated to 58 ℃, keep stirring velocity, the monomer solution for preparing is once added.Be warming up to 65 ℃ of temperature of reaction, keep stirring and thermotonus after 4 hours, temperature is risen to 70 ℃ of slakings one hour.To react resulting resin filter after being cooled to normal temperature, with after the washing with alcohol three times, dry to constant weight after washing three times with massive laundering standby.Control stir speed (S.S.) (150rpm-200rpm) can obtain the different rosin products of particle diameter with dispersant dosage, and the ultimate size of the resin that present embodiment synthesized is 0.4-1mm.
Embodiment 6
Preparation dispersant solution: wherein contain liquid paraffin and dispersion agent.Dispersion agent is selected calcium phosphate powder for use, and consumption is 2.5% of dispersant solution.
Preparation water-soluble mono liquid solution: water, monomer, initiator and linking agent are mixed with homogeneous phase solution.Wherein monomer and water volume ratio are 1: 1, and monomer is Hydroxyethyl acrylate 30% and vinylformic acid 70%; Initiator adopts the oxidation-reduction type initiator, i.e. Potassium Persulphate-sodium bisulfite, and consumption is 1% of amount of monomer; Linking agent is N,N methylene bis acrylamide, and its consumption is 0.5% of amount of monomer.
The volume ratio control of monomer solution and dispersant solution is between 1: 5.
Dispersant solution is added in the reaction flask that has stirring and reflux, under agitation condition, be heated to 60 ℃, keep stirring velocity, the monomer solution for preparing is once added.Be warming up to 65 ℃ of temperature of reaction, keep stirring and thermotonus after 4 hours, temperature is risen to 70 ℃ of slakings one hour.To react resulting resin filter after being cooled to normal temperature, with after the washing with alcohol three times, dry to constant weight after washing three times with massive laundering standby.Control stir speed (S.S.) (150rpm-200rpm) can obtain the different rosin products of particle diameter with dispersant dosage, and the ultimate size of the resin that present embodiment synthesized is 0.4-1mm.
Embodiment 7
Monomer and water are mixed with monomer solution, and monomer and water volume ratio are 1: 1.Monomer is Hydroxyethyl acrylate 20% and vinylformic acid 80%.Monomer solution is added in the reaction beaker, is heated to 60 ℃ in water bath with thermostatic control, add initiator solution (initiator be Potassium Persulphate and sodium bisulfite 1%) under agitation condition, add-on is 2% of monomer solution.Becoming sticky to the aqueous solution moves into baking oven with reaction solution can't stir the time, and oven temperature is kept 70 degree, and slaking was taken out after one hour.Behind the block rosin products water of gained and ethanol repetitive scrubbing three times, resin is inserted oven for drying to constant weight.It is that the particulate state of 3-5mm is standby that rosin products is crushed to yardstick.
Embodiment 8
Monomer and water are mixed with monomer solution, and monomer and water volume ratio are 1: 1.Monomer is Hydroxyethyl acrylate 30% and vinylformic acid 70%.Monomer solution is added in the reaction beaker, is heated to 60 ℃ in water bath with thermostatic control, add initiator solution (initiator is Potassium Persulphate and sodium bisulfite, and mass concentration is 1%) under agitation condition, add-on is 3% of monomer solution.Becoming sticky to the aqueous solution moves into baking oven with reaction solution can't stir the time, and oven temperature is kept 70 degree, and slaking was taken out after one hour.Behind the block rosin products water of gained and ethanol repetitive scrubbing three times, resin is inserted oven for drying to constant weight.It is that the particulate state of 3-5mm is standby that rosin products is crushed to yardstick.
Embodiment 9
Monomer and water are mixed with monomer solution, and monomer and water volume ratio are 1: 1.Monomer is Hydroxyethyl acrylate 40% and vinylformic acid 60%.Monomer solution is added in the reaction beaker, is heated to 60 ℃ in water bath with thermostatic control, add initiator solution (initiator is Potassium Persulphate and sodium bisulfite, and mass concentration is 1%) under agitation condition, add-on is 4% of monomer solution.Becoming sticky to the aqueous solution moves into baking oven with reaction solution can't stir the time, and oven temperature is kept 70 degree, and slaking was taken out after one hour.Behind the block rosin products water of gained and ethanol repetitive scrubbing three times, resin is inserted oven for drying to constant weight.It is that the particulate state of 3-5mm is standby that rosin products is crushed to yardstick.
Embodiment 10
Monomer and water are mixed with monomer solution, and monomer and water volume ratio are 1: 1.Monomer is Hydroxyethyl acrylate 30% and vinylformic acid 70%.Monomer solution is added in the reaction beaker, is heated to 60 ℃ in water bath with thermostatic control, add initiator solution (initiator is Potassium Persulphate and sodium bisulfite, and mass concentration is 1%) under agitation condition, add-on is 5% of monomer solution.Becoming sticky to the aqueous solution moves into baking oven with reaction solution can't stir the time, and oven temperature is kept 70 degree, and slaking was taken out after one hour.Behind the block rosin products water of gained and ethanol repetitive scrubbing three times, resin is inserted oven for drying to constant weight.It is that the particulate state of 3-5mm is standby that rosin products is crushed to yardstick.
Embodiment 1～10 prepared infiltration evaporation parting material based on polyacrylate resin is respectively charged in the separation tower body as filler, makes the infiltration evaporation knockout tower and be respectively applied to separation of methanol-benzene, ethyl acetate-water and tetrahydrofuran (THF)-aqueous systems.During separation, setting the temperature that heats in the electric heater is 70 ℃, and the maintenance mixture is boiling state, and opens the water of condensation in the overhead condenser.Keeping under certain reflux ratio or the full discharging situation from cat head extraction sample, with fixed benzene content or the water content wherein of chromatography of gases mensuration.Test result such as following table.
Table 1
Figure BDA0000129907190000121
Figure BDA0000129907190000131
Can be drawn by table 1, by with based on the infiltration evaporation parting material of the polyacrylate resin fixed bed device as the filler filling, and by its separately the vaporization of system and the process of osmosis in the fixed bed ORGANIC SOLVENT MIXTURES that the conventional distillation process can be difficult to separate boiling point close (methyl alcohol and benzene) realize separating; Can realize certain and water are formed organic the dewatering (ethyl acetate and water form azeotrope) of azeotropic, and its removal process can finish once, technology is simple.Its result also is better than azeotropic distillation; The removing of less water or minor amount of water (tetrahydrofuran (THF) can infinitely dissolve each other with water, and conventional distillation also is difficult to remove wherein contained less water or minor amount of water) in the organism that also can realize infinitely dissolving each other with water.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.

Claims (7)

1. the preparation method based on the infiltration evaporation parting material of polyacrylate resin is characterized in that, comprises the steps:
Step 1, Jiang Shui, dispersion agent and tensio-active agent are mixed with aqueous phase solution under the condition of heated and stirred, wherein, the mass percent of described dispersion agent is 0.5%～1%, and the adding quality of described tensio-active agent is 0.1%～0.2% of described water;
Step 2, monomer, initiator and linking agent are mixed with monomer solution, wherein, described monomer is that 30%～50% methyl methacrylate, 10%～20% ethyl propenoate and 30%～60% butyl acrylate constitute by mass percent, the adding quality of described initiator is 0.3%～0.5% of described monomer, and the adding quality of described linking agent is 0.1%～0.2% of described monomer; And
Step 3, described aqueous phase solution is joined in the reaction vessel, under agitation condition, be heated to 75 ℃～85 ℃, be that 1: 2～1: 5 ratio joins described monomer solution in the described reaction vessel according to the volume ratio of described monomer solution and described aqueous phase solution then, holding temperature is at 80 ℃～85 ℃, with the speed stirring reaction of 150～250rpm 3～4 hours, temperature is risen to 90 ℃ of slakings 1 hour, be down to the room temperature after-filtration, washing, dry to constant weight, be ground into the particle that particle diameter is 0.5mm～2mm, obtain described infiltration evaporation parting material based on polyacrylate resin.
2. the preparation method of the infiltration evaporation parting material based on polyacrylate resin according to claim 1, it is characterized in that: in the step 1, described dispersion agent is gelatin.
3. the preparation method of the infiltration evaporation parting material based on polyacrylate resin according to claim 1, it is characterized in that: in the step 1, described tensio-active agent is Sodium dodecylbenzene sulfonate or sodium lauryl sulphate.
4. the preparation method of the infiltration evaporation parting material based on polyacrylate resin according to claim 1, it is characterized in that: in the step 2, described initiator is dibenzoyl peroxide and N, the N-Diisopropyl azodicarboxylate.
5. the preparation method of the infiltration evaporation parting material based on polyacrylate resin according to claim 1, it is characterized in that: in the step 2, described linking agent is Vinylstyrene or ethylene glycol diacrylate.
6. the application of material in the infiltration evaporation tripping device that obtains according to the preparation method of any described infiltration evaporation parting material based on polyacrylate resin of claim 1～5.
7. an infiltration evaporation tripping device comprises knockout tower, it is characterized in that, is filled with the material that the preparation method according to the described infiltration evaporation parting material based on polyacrylate resin of claim 1 obtains in the described knockout tower.
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