CN101974122A - Method for preparing solid acrylic acid copolymer - Google Patents
Method for preparing solid acrylic acid copolymer Download PDFInfo
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Abstract
The invention discloses a method for preparing a solid acrylic acid copolymer, which comprises the following steps of: adding acrylic acid, acrylic acid long-chain ester and copolymerization monomer into a reaction kettle in a molar ratio of 0.5-99.5: 0.5-20: 0.5-99.5, adding an initiator in an amount which is 0.1 to 4.0 weight percent of the total weight of the reactants into the reaction kettle, introducing carbon dioxide of 9 to 16MPa into the reaction kettle, stirring the mixture, heating the mixture to between 45 and 90 DEG C, reacting the mixture under the pressure of 14 to 19MPa for 10 to 120 minutes, releasing the carbon dioxide to obtain a white powdery product after the pressure in the reaction kettle is constant, and finally performing in-situ extraction at the temperature of between 30 and 60 DEG C under the pressure of 8 to 16MPa by using the carbon dioxide till the product has constant weight so as to obtain the solid acrylic acid copolymer. The conversion rate of the polymer is over 95 percent, and the solid acrylic acid copolymer is applied in the fields of daily necessities, food, cosmetics, medicaments and the like with high material purity requirements.
Description
Technical field
The present invention relates to a kind of preparation method of solid propenoic acid multipolymer, be meant a kind of method that in supercritical co, prepares hydrophobic association type solid propenoic acid multipolymer fast especially.
Background technology
Existing hydrophobic association type acrylic copolymer mainly is the liquid product with solution polymerization and letex polymerization, and preparation solid propenoic acid multipolymer then is the important development direction of acrylic copolymer.Compare with the propylene liquid acid copolymer, the solid propenoic acid multipolymer has the storage convenient transportation, transportation cost is low, the transporting procedures security is good, the effective constituent advantages of higher.Therefore, the research to water-soluble solid acrylic copolymers synthetic method and performance thereof has important practical significance.
The hydrophobic association type water-soluble polymers is meant introduces the prepared polymkeric substance of a spot of hydrophobic grouping in water-soluble polymer.The preparation of hydrophobic association type acrylic copolymer is carried out at organic (water) solvent usually, and polymerization reaction time needs more than 12 hours usually, and the reaction products therefrom need be with last handling processes such as other organic solvent deposits, filtration, dryings.Be one and not only consumed energy but also time-consuming process, but also cause environmental pollution easily; Publication number is that CN101096394 discloses the patent of invention of " a kind of siloxanes reunion acryhic material and synthetic technology thereof of containing ", and the employing supercritical co is a medium, has prepared a kind of siloxanes reunion acryhic material that contains.Carry out normal Raolical polymerizable in reactor, the preparation silyl acrylate copolymer reaction time needs 4 hours, and the polymkeric substance transformation efficiency is about 90%.
The organism monomer carries out high molecular polymerization, all is strong exothermal reaction, and particularly the organism monomer need add the chain reaction of a small amount of initiator with initiated polymerization.If the heat in the polymerization process can not be derived rapidly, local in reactor, temperature of reaction sharply rises, and speed of reaction also sharply rises, and the speed of chain reaction reaches out of control and explodes, and implode takes place.The result of implode generates hard blocks of solid, product forfeiture use value, and implode must be avoided and be prevented in polymerization process.
Along with improving constantly that the greenization of chemosynthesis process requires, people replace the work of conventional organic solvents to give more concern to seeking environmentally friendly solvent, and wherein free of contamination supercutical fluid is an ideal surrogate comparatively.
When material was in the above state of its critical temperature and emergent pressure, to this state gas pressurization, gas can not liquefy, and just density increases, and both had similar liquid character this moment, and gas performance is arranged again, and the fluid of this state is called supercutical fluid.Because supercritical co density is big, dissolving power is strong, the rate of mass transfer height.The critical temperature of carbonic acid gas (Tc=31.06 ℃) be the supercritical medium stagnation point introduced on the document near room temperature, its emergent pressure (Pc=7.39MPa) is also more moderate, sepn process can be near carrying out under the room temperature condition; Cheaply be easy to get, nontoxic, inertia and series of advantages such as very easily separate from product becomes the focus of current people's research.
Supercritical co has series of advantages as polymerization reaction medium, and the density of supercritical co is bigger hundreds of times than gas, and concrete numerical value and liquid phase are worked as.Its viscosity is still near gas, but than little 2 orders of magnitude of liquid.Spread coefficient approximately is 1/100 of a gas between gas and liquid, and is bigger hundreds of times than liquid.Thereby supercritical co both had liquid solute had the characteristics of bigger solubleness, had gas again and was easy to the characteristic that spreads and move, conducted heat, rate of mass transfer is much higher than liquid phase cracking process.And adjustable pressure is controlled the speed of reacting in the supercritical co.Make implode be reflected in the supercritical co and carry out, not only can prepare premium quality product, and speed of response is fast, the reaction times short, polymkeric substance transformation efficiency height.
Summary of the invention
The objective of the invention is with easy and also with eco-friendly supercritical co as the quick synthetizing hydrophobic associated type solid propenoic acid multipolymer of solvent, a kind of preparation method of solid propenoic acid multipolymer promptly is provided.
Based on above-mentioned purpose, the preparation method of a kind of solid propenoic acid multipolymer that the present invention proposes comprises the steps:
At first, be to add vinylformic acid, acrylate long-chain ester and comonomer at 0.5～99.5: 0.5～20: 0.5～99.5 in molar ratio in reactor, after add the initiator of azo-compound, superoxide or the persulphate of reactant gross weight 0.1～4.0wt% again;
Secondly, feed carbonic acid gas in reactor, pressure is 9～16Mpa, stirs, and is warming up to 45～90 ℃, and reaction pressure is 14～19Mpa, and in 10～120 minutes reaction times, behind the constant pressure in the reactor, release of carbon dioxide obtains the white powder product;
At last, obtain the white powder product in reactor, again by the extracting of carbonic acid gas original position, temperature is 30～60 ℃, and pressure is 8～16MPa, and extracting makes the solid propenoic acid multipolymer up to the product constant weight.
In above-mentioned method, described comonomer is one or more in vinylbenzene, vinyl pyrrolidone, the acrylamide; The described reactant gross weight that it adds reactor is further elected 0.2～0.5kg/L as; Temperature of reaction in described its reactor is further elected 55～70 ℃, reaction pressure as and is further elected 15～18Mpa as, and the reaction times is further elected 40～100 minutes as; Described its azo-compound is Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile); Described its superoxide is dibenzoyl peroxide or peroxidation two acyls; Described its persulphate is Potassium Persulphate or ammonium persulphate.
In the preparation method of above-mentioned a kind of solid propenoic acid multipolymer, its innovation part is to react synthetizing hydrophobic associated type solid propenoic acid multipolymer by implode in supercritical co.Used solvent is a supercritical co, and it is cheap, and nontoxic pollution-free is nonflammable explosive, is convenient to reclaim.
In the prepared polymer architecture, each monomeric amount can reach arbitrary proportion in the polymkeric substance in aforesaid method, and as the implode polymerization reaction medium, polyreaction is easy to control with supercritical co; The acrylic copolymer pressed powder that reaction obtains need not dewatered drying, does not have any pollution, saves the energy, is convenient to transportation; Product yield is up to more than 95%.
Prepared solid propenoic acid multipolymer in aforesaid method, can be applicable to tertiary oil recovery, solar energy converting, soil improvement, friction drag reduction, water-borne coatings, caking agent, printing ink, papermaking, textile printing and dyeing, food-drink, brewage, field such as medicine, makeup, civil engineering and water treatment, be particularly suitable for the higher daily necessities of the purity requirement of material, food, makeup, field such as medical, and method is easy, saves energy and reduce the cost, have broad application prospects.
Compared with prior art, the characteristics that the present invention gives prominence to are: the comonomer that implode is reacted can take place by adding in (1) in free of contamination supercritical co, prepare hydrophobic association type solid propenoic acid multipolymer fast by free radical implode reaction, reaction times is shortened greatly, energy-saving and cost-reducing, the simple environmental protection of synthetic method, polyreaction are easy to control; (2) prepared hydrophobic associated polymer transformation efficiency is higher than the polymkeric substance transformation efficiency of other prior art for preparing, and yield is up to more than 95%; (3) each monomeric amount can reach arbitrary proportion in the hydrophobic association type acrylic copolymer, and product is highly purified loose white powder.
Description of drawings
Fig. 1 is the sem photograph of the hydrophobic association type acrylic copolymer of embodiment of the present invention 1 preparation.
Embodiment
The professional and technical personnel is further detailed by the preparation method of embodiment below, so that can realize being as the criterion to a kind of solid propenoic acid multipolymer of the present invention's proposition.
A kind of preparation method of solid propenoic acid multipolymer, its described method prepare hydrophobic association type solid propenoic acid multipolymer fast in supercritical co, its reaction medium is a supercritical co.Used polymer monomer is in supercritical co the implode reactive polymeric to take place, or can with another kind of or several monomer generation implode reactive polymerics.Be in vinylformic acid, acrylate long-chain ester and vinyl pyrrolidone, vinylbenzene, the acrylamide one or more.Prepared polymkeric substance can be two membered copolymers or terpolymer among the present invention.Concrete steps and processing condition are as follows:
In autoclave, add vinylformic acid, acrylate long-chain ester, and one of vinylbenzene, vinyl pyrrolidone, acrylamide.Wherein vinylformic acid, acrylate long-chain ester, comonomer are 0.5～99.5: 0.5～20 according to mol ratio: 0.5～99.5, add the initiator of total monomer weight 0.1～4.0wt% then.Put into magnetic stir bar, sealing.
Slowly charge into carbonic acid gas and discharge the interior air of reactor.By high-pressure metering pump carbonic acid gas is fed in the autoclave, pressure is 9～16Mpa, closes intake valve; Start magnetic stirring apparatus, progressively be warming up to 45～90 ℃ simultaneously.When reaction was carried out about 10～40 minutes, tangible implode took place in reaction, and pressure is fast rise 8～20Mpa in tens seconds.It is excessive for fear of implode reaction reactor pressure to be raise, and reactor can be adopted water-cooled or air naturally cooling, continues reaction again after making reacting kettle inner pressure reduce in the best polymerization pressure scope.Amount to reaction 40～120 minutes, no longer rise until system pressure.Reaction finishes the postcooling reactor, slowly emits carbonic acid gas again, collects the white powder product that obtains loosening.
With the extracting of carbonic acid gas original position, temperature is 30～60 ℃ to the synthetic product in autoclave, and pressure is 8～16MPa, and repeatedly extracting is up to the product constant weight, and the white powder that is obtained is the high-purity propylene acid copolymer.
Described best polymeric reaction temperature is that 55～70 ℃, best polymerization pressure are 15-18Mpa, best polymerization reaction time 40～100 minutes.
Described initiator is meant azo-compound, superoxide or persulphate, or oxidation～reduction system class initiator; Can be preferably from Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, peroxidation two acyls, Potassium Persulphate or ammonium persulphate, optimum amount is 0.4%～0.6wt% of total monomer weight.
The total monomer weight of described adding reactor is 0.2～0.5kg/L.
Embodiment 1
What the present invention proposed is the method for preparing hydrophobic association type solid propenoic acid multipolymer in supercritical co fast.
Weighing vinylformic acid 2.0g, initiator Diisopropyl azodicarboxylate 0.021g, octadecyl acrylate 0.12g, vinyl pyrrolidone 0.1g join in the 20mL stainless steel autoclave, put into magnetic stir bar, sealing; Slowly charge into carbonic acid gas to 4Mpa, close inlet mouth, discharge air in the still.With high-pressure metering pump carbonic acid gas is fed in the autoclave, add pressure carbon dioxide, fasten terminal valve, heating in water bath then to 9Mpa.Start magnetic agitation, heating in water bath to 60 ℃, when treating that temperature is raised to 60 ℃ of preset values, if pressure does not reach preset value 16Mpa, restock or emit carbonic acid gas and make its pressure reach required pressure.React system generation implode reaction after 30 minutes.Be that the interior pressure of reactor rose to 25Mpa rapidly in 35 seconds.No longer rise until system pressure, reaction finishes, and amounts to reaction 60 minutes.
With the extracting of carbonic acid gas original position, repeatedly extracting is up to the product constant weight in autoclave for the product of preparation, removes in the system unreacted monomer etc. simultaneously.Reactor naturally cools to room temperature, opens the valve of giving vent to anger and slowly emits atmospheric carbon dioxide, opens reactor at last and takes out polymkeric substance, the white powder product that obtains loosening.Collect final product, polymkeric substance transformation efficiency 97%.Adopting determination of ubbelohde viscometer polymkeric substance viscosity-average molecular weight is 6.2 * 10
5Through rotary viscosity design determining concentration is that the polymers soln apparent viscosity of 0.1g/dL is 1680mPas.
Embodiment 2
Weighing vinylformic acid 1.5g, initiator Diisopropyl azodicarboxylate 0.021g, octadecyl acrylate 0.1g; Vinyl pyrrolidone 0.5g joins in the 20mL stainless steel autoclave, puts into magnetic stir bar, sealing; Slowly charge into carbonic acid gas to 2Mpa, close inlet mouth, discharge air in the still.With high-pressure metering pump carbonic acid gas is fed in the autoclave, add pressure carbon dioxide, fasten terminal valve, heating in water bath then to 10Mpa.Start magnetic agitation, heating in water bath to 60 ℃, when treating that temperature is raised to 60 ℃ of preset values, if pressure does not reach preset value 18Mpa, restock or emit carbonic acid gas and make its pressure reach required pressure.React system generation implode reaction after 15 minutes.It is excessive for fear of implode reaction reactor pressure to be raise, and reactor is adopted water-cooled, make reacting kettle inner pressure reduce to 18Mpa after, continue that again reactor is put into 60 ℃ of water-baths and react.No longer rise until system pressure, reaction finishes, and amounts to reaction 40 minutes.Reactor naturally cools to room temperature, opens the valve of giving vent to anger and slowly emits atmospheric carbon dioxide, opens reactor at last and takes out polymkeric substance.The white powder product that obtains loosening is collected final product.
With the extracting of carbonic acid gas original position, repeatedly extracting is up to the product constant weight in autoclave for the product of preparation, removes in the system unreacted monomer etc. simultaneously.Operational condition: 45 ℃, 7MPa, CO
2Flow 5L/min, extracting time 3min.The cooling reactor is to room temperature, and final product is collected in slowly venting.The white powder that is obtained is the hydrophobic association type acrylic copolymer.Polymkeric substance transformation efficiency 99%.Adopting determination of ubbelohde viscometer polymkeric substance viscosity-average molecular weight is 8.5 * 10
5, be that the polymers soln apparent viscosity of 0.1g/dL is 2460mPas through rotary viscosity design determining concentration.
Embodiment 3
Weighing vinylformic acid 1.8g, initiator Diisopropyl azodicarboxylate 0.021g, vinylformic acid heptyl ester 0.3g; Vinyl pyrrolidone 0.2g joins in the 20mL stainless steel autoclave, puts into magnetic stir bar, sealing; Slowly charge into carbonic acid gas to 3Mpa, close inlet mouth, discharge air in the still.With high-pressure metering pump carbonic acid gas is fed in the autoclave, add pressure carbon dioxide, fasten terminal valve, heating in water bath then to 9.5Mpa.Start magnetic agitation, heating in water bath to 55 ℃, when treating that temperature is raised to 55 ℃ of preset values, if pressure does not reach preset value 15Mpa, restock or emit carbonic acid gas and make its pressure reach required pressure.React system generation implode reaction after 20 minutes.Be that the interior pressure of reactor rose to 27Mpa rapidly in 45 seconds.No longer rise until system pressure, reaction finishes, and amounts to reaction 50 minutes.
With the extracting of carbonic acid gas original position, repeatedly extracting is up to the product constant weight in autoclave for the product of preparation, removes in the system unreacted monomer etc. simultaneously.Reactor naturally cools to room temperature, opens the valve of giving vent to anger and slowly emits atmospheric carbon dioxide, opens reactor at last and takes out polymkeric substance.Collect final product.The white powder that is obtained is the hydrophobic association type acrylic copolymer, polymkeric substance transformation efficiency 98%.Adopting determination of ubbelohde viscometer polymkeric substance viscosity-average molecular weight is 4.3 * 10
5, be that the polymers soln apparent viscosity of 0.1g/dL is 1480mPas through rotary viscosity design determining concentration.
Embodiment 4
Weighing vinylformic acid 1.0g, initiator Diisopropyl azodicarboxylate 0.021g, octadecyl acrylate 0.2g; Vinyl pyrrolidone 1.0g joins in the 20mL stainless steel autoclave, puts into magnetic stir bar, sealing; Slowly charge into carbonic acid gas to 1Mpa, close inlet mouth, discharge air in the still.With high-pressure metering pump carbonic acid gas is fed in the autoclave, add pressure carbon dioxide, fasten terminal valve, heating in water bath then to 10.5Mpa.Start magnetic agitation, heating in water bath to 65 ℃, when treating that temperature is raised to 65 ℃ of preset values, if pressure does not reach preset value 14Mpa, restock or emit carbonic acid gas and make its pressure reach required pressure.React system generation implode reaction after 10 minutes.Be that the interior pressure of reactor rose to 31Mpa rapidly in 25 seconds.No longer rise until system pressure, reaction finishes, and amounts to reaction 30 minutes.Reactor naturally cools to room temperature, opens the valve of giving vent to anger and slowly emits atmospheric carbon dioxide, opens reactor at last and takes out polymkeric substance.The white powder product collection final product that obtains loosening.
With the extracting of carbonic acid gas original position, repeatedly extracting is up to the product constant weight in autoclave for the product of preparation, removes in the system unreacted monomer etc. simultaneously.Operational condition: 35 ℃, 8MPa, CO
2Flow 3L/min, extracting time 2min.The cooling reactor is to room temperature, and final product is collected in slowly venting.The white powder that is obtained is the hydrophobic association type acrylic copolymer, polymkeric substance transformation efficiency 99%.Adopting determination of ubbelohde viscometer polymkeric substance viscosity-average molecular weight is 6.7 * 10
5, be that the polymers soln apparent viscosity of 0.1g/dL is 2130mPas through rotary viscosity design determining concentration.
Embodiment 5
Weighing vinylformic acid 1.8g, initiator peroxidation two acyl 0.011g, Process Conditions of Cetane Acrylate 0.12g; Vinyl pyrrolidone 0.2g joins in the 20mL stainless steel autoclave, puts into magnetic stir bar, sealing; Slowly charge into carbonic acid gas to 3Mpa, close inlet mouth, discharge air in the still.With high-pressure metering pump carbonic acid gas is fed in the autoclave, add pressure carbon dioxide, fasten terminal valve, heating in water bath then to 9Mpa.Start magnetic agitation, heating in water bath to 55 ℃, when treating that temperature is raised to 55 ℃ of preset values, if pressure does not reach preset value 20Mpa, restock or emit carbonic acid gas and make its pressure reach required pressure.React system generation implode reaction after 30 minutes.Be that the interior pressure of reactor rose to 33Mpa rapidly in 40 seconds.No longer rise until system pressure, reaction finishes, and amounts to reaction 55 minutes.
With the extracting of carbonic acid gas original position, repeatedly extracting is up to the product constant weight in autoclave for the product of preparation, removes in the system unreacted monomer etc. simultaneously.Reactor naturally cools to room temperature, opens the valve of giving vent to anger and slowly emits atmospheric carbon dioxide, opens reactor at last and takes out polymkeric substance.Collect final product.The white powder that is obtained is the hydrophobic association type acrylic copolymer, polymkeric substance transformation efficiency 98%.Adopting determination of ubbelohde viscometer polymkeric substance viscosity-average molecular weight is 6.4 * 10
5, be that the polymers soln apparent viscosity of 0.1g/dL is 1260mPas through rotary viscosity design determining concentration.
Embodiment 6
Weighing vinylformic acid 1.3g, initiator peroxidation two acyl 0.011g, butyl acrylate 0.6g; Vinyl pyrrolidone 0.2g joins in the reactor and seals; Join in the 20mL stainless steel autoclave, put into magnetic stir bar, sealing; Slowly charge into carbonic acid gas to 4Mpa, close inlet mouth, discharge air in the still.With high-pressure metering pump carbonic acid gas is fed in the autoclave, add pressure carbon dioxide, fasten terminal valve, heating in water bath then to 9.5Mpa.Start magnetic agitation, heating in water bath to 65 ℃, when treating that temperature is raised to 65 ℃ of preset values, if pressure does not reach preset value 15Mpa, restock or emit carbonic acid gas and make its pressure reach required pressure.React system generation implode reaction after 25 minutes.It is excessive for fear of implode reaction reactor pressure to be raise, and reactor is adopted the air naturally cooling, make reacting kettle inner pressure reduce to 16Mpa after, continue that again reactor is put into 65 ℃ of water-baths and react.No longer rise until system pressure, reaction finishes, and amounts to reaction 60 minutes.Reactor naturally cools to room temperature, opens the valve of giving vent to anger and slowly emits atmospheric carbon dioxide, opens reactor at last and takes out polymkeric substance, collects final product.The white powder that is obtained is the hydrophobic association type acrylic copolymer, polymkeric substance transformation efficiency 98%.Adopting determination of ubbelohde viscometer polymkeric substance viscosity-average molecular weight is 1.5 * 10
5, be that the polymers soln apparent viscosity of 0.1g/dL is 960mPas through rotary viscosity design determining concentration.
Embodiment 7
Weighing vinylformic acid 1.1g, Diisopropyl azodicarboxylate 0.021g, vinylbenzene 1.0g, octadecyl acrylate 0.1g join in the 20mL stainless steel autoclave, put into magnetic stir bar, sealing; Slowly charge into carbonic acid gas to 4Mpa, close inlet mouth, discharge air in the still.With high-pressure metering pump carbonic acid gas is fed in the autoclave, add pressure carbon dioxide, fasten terminal valve, heating in water bath then to 10Mpa.Start magnetic agitation, heating in water bath to 65 ℃, when treating that temperature is raised to 65 ℃ of preset values, if pressure does not reach preset value 17Mpa, restock or emit carbonic acid gas and make its pressure reach required pressure.Question response is system generation implode reaction after 40 minutes.Be that the interior pressure of reactor rose to 26Mpa rapidly in 50 seconds.No longer rise until system pressure, reaction finishes, and amounts to reaction 120 minutes.Reactor naturally cools to room temperature, opens the valve of giving vent to anger and slowly emits atmospheric carbon dioxide, opens reactor at last and takes out polymkeric substance.The white powder product that obtains loosening is collected final product.The white powder that is obtained is the hydrophobic association type acrylic copolymer, polymkeric substance transformation efficiency 95%.Adopting determination of ubbelohde viscometer polymkeric substance viscosity-average molecular weight is 1.2 * 10
5, be that the polymers soln apparent viscosity of 0.1g/dL is 870mPas through rotary viscosity design determining concentration.
Embodiment 8
Weighing vinylformic acid 1.0g, acrylamide 1.1g, dodecyl acrylate 0.18g, Diisopropyl azodicarboxylate 0.021g join in the 20mL stainless steel autoclave, put into magnetic stir bar, sealing; Slowly charge into carbonic acid gas to 4Mpa, close inlet mouth, discharge air in the still.With high-pressure metering pump carbonic acid gas is fed in the autoclave, add pressure carbon dioxide, fasten terminal valve, heating in water bath then to 11Mpa.Start magnetic agitation, heating in water bath to 60 ℃, when treating that temperature is raised to 60 ℃ of preset values, if pressure does not reach preset value 19Mpa, restock or emit carbonic acid gas and make its pressure reach required pressure.React system generation implode reaction after 35 minutes.Be that the interior pressure of reactor rose to 29Mpa rapidly in 50 seconds.No longer rise until system pressure, reaction finishes, and amounts to reaction 90 minutes.With the extracting of carbonic acid gas original position, repeatedly extracting is up to the product constant weight in autoclave for the synthetic product, removes in the system unreacted monomer etc. simultaneously.Reactor naturally cools to room temperature, opens the valve of giving vent to anger and slowly emits atmospheric carbon dioxide, opens reactor at last and takes out polymkeric substance.The white powder product that obtains loosening is collected final product.The white powder that is obtained is the hydrophobic association type acrylic copolymer, polymkeric substance transformation efficiency 96%.Adopting determination of ubbelohde viscometer polymkeric substance viscosity-average molecular weight is 2.1 * 10
5, be that the polymers soln apparent viscosity of 0.1g/dL is 1050mPas through rotary viscosity design determining concentration.
Embodiment 9
Weighing vinylformic acid 0.7g, acrylamide 1.3g, butyl acrylate 0.28g, Diisopropyl azodicarboxylate 0.021g join in the 20mL stainless steel autoclave, put into magnetic stir bar, sealing; Slowly charge into carbonic acid gas to 3Mpa, close inlet mouth, discharge air in the still.With high-pressure metering pump carbonic acid gas is fed in the autoclave, add pressure carbon dioxide, fasten terminal valve, heating in water bath then to 12Mpa.Start magnetic agitation, heating in water bath to 60 ℃, when treating that temperature is raised to 60 ℃ of preset values, if pressure does not reach preset value 17Mpa, restock or emit carbonic acid gas and make its pressure reach required pressure.React system generation implode reaction after 40 minutes.It is excessive for fear of implode reaction reactor pressure to be raise, and reactor is adopted the air naturally cooling, make reacting kettle inner pressure reduce to 20Mpa after, continue that again reactor is put into 60 ℃ of water-baths and react.No longer rise until system pressure, reaction finishes, and amounts to reaction 80 minutes.Reactor naturally cools to room temperature, opens the valve of giving vent to anger and slowly emits atmospheric carbon dioxide, opens reactor at last and takes out polymkeric substance.The white powder product that obtains loosening is collected final product.The white powder that is obtained is the hydrophobic association type acrylic copolymer.Polymkeric substance transformation efficiency 97%.Adopting determination of ubbelohde viscometer polymkeric substance viscosity-average molecular weight is 7.5 * 10
5, be that the polymers soln apparent viscosity of 0.1g/dL is 1450mPas through rotary viscosity design determining concentration.
Claims (7)
1. the preparation method of a solid propenoic acid multipolymer, this method comprises the steps:
At first, be to add vinylformic acid, acrylate long-chain ester and comonomer at 0.5～99.5: 0.5～20: 0.5～99.5 in molar ratio in reactor, after add the initiator of azo-compound, superoxide or the persulphate of reactant gross weight 0.1～4.0wt% again;
Secondly, feed carbonic acid gas in reactor, pressure is 9～16Mpa, stirs, and is warming up to 45～90 ℃, and reaction pressure is 14～19Mpa, and in 10～120 minutes reaction times, behind the constant pressure in the reactor, release of carbon dioxide obtains the white powder product;
At last, obtain the white powder product in reactor, again by the extracting of carbonic acid gas original position, temperature is 30～60 ℃, and pressure is 8～16MPa, and extracting makes the solid propenoic acid multipolymer up to the product constant weight.
2. the method for claim 1, its comonomer is one or more in vinylbenzene, vinyl pyrrolidone, the acrylamide.
3. the method for claim 1, its reactant gross weight that adds reactor is further elected 0.2～0.5kg/L as.
4. the method for claim 1, the temperature of reaction in its reactor are further elected 55～70 ℃, reaction pressure as and are further elected 15～18Mpa as, and the reaction times is further elected 40～100 minutes as.
5. the method for claim 1, its azo-compound is Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile).
6. the method for claim 1, its superoxide is dibenzoyl peroxide or peroxidation two acyls.
7. the method for claim 1, its persulphate is Potassium Persulphate or ammonium persulphate.
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| CN102701353A (en) * | 2012-05-25 | 2012-10-03 | 中科院广州化学有限公司 | Long-branched-chain water-soluble polymer water treatment agent, and preparation method and application thereof |
| CN105542067A (en) * | 2016-02-19 | 2016-05-04 | 山东省计量科学研究院 | Method for preparing N-vinylformamide and acrylonitrile copolymer based on supercritical CO2 |
| CN105585650A (en) * | 2014-10-21 | 2016-05-18 | 中国石油化工股份有限公司 | Preparation method of high-molecular-weight polyacrylamide |
| CN108250346A (en) * | 2018-01-18 | 2018-07-06 | 嘉兴学院 | A kind of synthetic method of Diacetone Acrylamide and acrylic copolymer |
| CN114057920A (en) * | 2022-01-17 | 2022-02-18 | 中海油天津化工研究设计院有限公司 | Oil-based self-suspension polymer thickener and preparation method thereof |
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| US20020053413A1 (en) * | 1999-12-06 | 2002-05-09 | Zhang Huashi T. | Method for using hydrophobically associative polymers in preparing cellulosic fiber compositions, and cellulosic fiber compositions incorporating the hydrophobically associative polymers |
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Patent Citations (1)
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| US20020053413A1 (en) * | 1999-12-06 | 2002-05-09 | Zhang Huashi T. | Method for using hydrophobically associative polymers in preparing cellulosic fiber compositions, and cellulosic fiber compositions incorporating the hydrophobically associative polymers |
Non-Patent Citations (2)
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| 《化工学报》 20081015 张怀平 超临界二氧化碳中乙烯基三乙氧基硅烷改性丙烯酸的合成及溶液性质 第2263-2267页 1-7 第59卷, 第10期 2 * |
| 《石油化工》 20080115 张怀平 超临界CO2中疏水改性聚丙烯酸的合成及其溶液性质 第44-48页 1-7 第37卷, 第1期 2 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701353A (en) * | 2012-05-25 | 2012-10-03 | 中科院广州化学有限公司 | Long-branched-chain water-soluble polymer water treatment agent, and preparation method and application thereof |
| CN105585650A (en) * | 2014-10-21 | 2016-05-18 | 中国石油化工股份有限公司 | Preparation method of high-molecular-weight polyacrylamide |
| CN105542067A (en) * | 2016-02-19 | 2016-05-04 | 山东省计量科学研究院 | Method for preparing N-vinylformamide and acrylonitrile copolymer based on supercritical CO2 |
| CN105542067B (en) * | 2016-02-19 | 2017-10-31 | 山东省计量科学研究院 | One kind is based on supercritical CO2The method for preparing N vinyl formamides and acrylonitrile copolymer |
| CN108250346A (en) * | 2018-01-18 | 2018-07-06 | 嘉兴学院 | A kind of synthetic method of Diacetone Acrylamide and acrylic copolymer |
| CN114057920A (en) * | 2022-01-17 | 2022-02-18 | 中海油天津化工研究设计院有限公司 | Oil-based self-suspension polymer thickener and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN101974122B (en) | 2012-07-04 |
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