CN1914236B - Method for producing polymer - Google Patents

Method for producing polymer Download PDF

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Publication number
CN1914236B
CN1914236B CN2005800035368A CN200580003536A CN1914236B CN 1914236 B CN1914236 B CN 1914236B CN 2005800035368 A CN2005800035368 A CN 2005800035368A CN 200580003536 A CN200580003536 A CN 200580003536A CN 1914236 B CN1914236 B CN 1914236B
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acrylate
methyl
acid
solution
described method
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CN1914236A (en
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T·丹尼尔
U·里格尔
M·埃利奥特
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BASF SE
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BASF SE
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Priority claimed from DE102004057280A external-priority patent/DE102004057280A1/en
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Priority claimed from PCT/EP2005/000421 external-priority patent/WO2005073260A1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention relates to a method for producing polymers which contain (meth)acrylate salt units by radical polymerization of (meth)acrylate salt and optionally other monomers in an aqueous medium, using a supersaturated aqueous solution of (meth)acrylate salt. The highly concentrated reaction mixtures so obtained are characterized by a high solid content and increased space-time yield.

Description

Method for producing polymer
The present invention relates to a kind of method of in aqueous medium, producing (methyl) acrylate polymer.
The production of sodium acrylate has been known.For example, by GB-C-1,073,856 instruction mixes under the solution of sodium hydroxide in methyl alcohol and the temperature of the solution of vinylformic acid in methyl alcohol in 5-50 ℃ scope.Preferably the solution of sodium hydroxide in methyl alcohol is added in the acrylic acid solution.The sodium acrylate that forms precipitates from solution, can centrifugation or leach.Can be with solid propenoic acid sodium drying, preferably be lower than under 40 ℃ the temperature.
EP-B-0372706 discloses a kind of method of producing acrylate in aqueous medium by the neutralization reaction of vinylformic acid and basic cpd, wherein vinylformic acid and basic cpd are added in the water, at first acrylic acid degree of neutralization is adjusted to 75-100mol%, and then the interpolation alkaline mixt is increased to 100.0-110mol% with this degree of neutralization, reaction mixture was worn out 1 minute-120 minutes down with degree hereinto, add enough vinylformic acid subsequently acrylic acid degree of neutralization is in the scope of 20-100mol%.The part or all of neutral acrylic acid aqueous solution that so obtains is used to produce crosslinked polypropylene in the presence of linking agent, with the polymer phase ratio of handling without excessive neutralizing agent that polyreaction by acrylate obtains, this crosslinked polypropylene has lower residual monomer content.
DE10234772 has described a kind of method for preparing super-absorbent.It relates to from the preparation of solid propenoic acid sodium not by oversaturated solution.The slurries of sodium acrylate in water have also been described.
Commercial grade vinylformic acid contains at least a stablizer usually controls premature polymerization.When making, when for example producing superabsorbent polymer, obtain coloured product by disclosed method in the document of above citation through stable acroleic acid polymerization.For producing colourless super-absorbent, must perhaps from vinylformic acid, remove destabilizing agent earlier with through stable vinylformic acid distillation by absorption, for example be adsorbed onto on the gac; And do not make acroleic acid polymerization with not stopping over ideally.Produce the unsaturated sodium acrylate solution of the special use of existing method of crosslinked super-absorbent polyacrylic ester, but this does not make the space-time yield maximization.
Target of the present invention provides a kind of polymerization process, and it improves space-time yield by using highly spissated monomer solution, and provides high-quality polymkeric substance in the mode of economy thus.
Be surprisingly found out that now the polymkeric substance that the polyreaction by supersaturation (methyl) acrylate solution obtains has very good quality production quality and high space-time yield concurrently.
For all (methyl) acrylate of the present invention, now be that example is described the present invention in detail with the sodium acrylate.According to the present invention, use the mixture of other (methyl) acrylate or (methyl) acrylate to come instead of propylene acid sodium also to be fine similarly.Correspondingly available methacrylic acid or methacrylic acid and acrylic acid mixture come instead of propylene acid.
Can be particularly useful as flocculation agent and super-absorbent by the polymkeric substance that the inventive method is produced.Preferred super-absorbent.Super-absorbent is meant at 5g/cm 3Pressure under every g polymkeric substance can absorb the polymkeric substance of 10g water at least.
We have found that target of the present invention realizes by the following method: the radical polymerization preparation comprises the unitary polymkeric substance of sodium acrylate under another monomeric situation existing or do not exist in aqueous medium by sodium acrylate, this method comprises the supersaturated aqueous solution that uses sodium acrylate, this aqueous solution can be by being dissolved in solid propenoic acid sodium in the aqueous medium with postcooling, perhaps by will be in the abundant spissated acrylic acid solution before the polymerization with obtain.If desired, can also be with this supersaturated solution stabilization, for example by adding suitable polymer blend.And, can also make sodium acrylate part redeposition from this supersaturated solution.
Supersaturated solution is meant metastable state, compares with the complete saturated salt solution under being in the Thermodynamically stable balance, and more acrylate is in solution under this metastable state.Supersaturated solution preferably refers to compare with Thermodynamically stable solution, comprise more than 1.01 times, preferably more than 1.03 times, more preferably more than 1.05 times, more preferably more than 1.07 times, especially preferably more than 1.1 times, especially more than the solution of 1.2 times salt.
The sodium acrylate of solid form is described by document, but also is not used to produce polymkeric substance so far.The sodium acrylate polymkeric substance up to now always from the sodium acrylate aqueous solution that generates by with the aqueous sodium hydroxide solution with pure acrylic acid or contain that the vinylformic acid of stablizer produces---be normally just at before the polymerization.Because the pure acrylic acid instability must neutralize it with aqueous sodium hydroxide solution after distillation or after the fractional crystallization immediately.For storing and transport the long time, solid propenoic acid sodium is enough stablized and be need not is opposing polymerization stabilization.Sodium acrylate should be no more than 40 ℃ of storage and transportations down.Store and transportation stable usually in 5-35 ℃ of scope for example, particularly 10-20 ℃.
Solid propenoic acid sodium can have the median size of 45 μ m-2000 μ m, preferred 45 μ m-500 μ m.The monomeric aqueous solution is preferably from the production of anhydrous sodium acrylate.Yet hygroscopic pressed powder sodium acrylate also can contain for example 0.1 weight %-10 weight %, the particularly water of 0.5 weight %-2 weight %.When the heat solid sodium acrylate, this solid salt is all constant in fact under 250 ℃; On the contrary, can not decompose before being higher than this temperature reaching during the fusion.
Solid propenoic acid sodium is very easily water-soluble.Solid propenoic acid sodium can be used for preparing monomer solution or aqueous liquid dispersion, contains for example sodium acrylate of 5 weight %-75 weight %, preferred 20 weight %-45 weight % under every kind of situation.When the concentration of sodium acrylate surpassed 45 weight %, this system was the dispersion liquid of sodium acrylate.These solution and dispersion liquid can direct polymerization.In the polyreaction of sodium acrylate aqueous liquid dispersion, the sodium acrylate that is dissolved in the water at first reacts, and the dispersive sodium acrylate will dissolve between polymerization period.Yet, if suitable, also vinylformic acid can be added in these solution, provide to have for example part neutral vinylformic acid of 10-95mol%, preferred 40-90mol%, particularly 60-80mol% degree of neutralization.
Method of the present invention preferably neutralizes vinylformic acid with aqueous sodium hydroxide solution, sodium hydroxide, yellow soda ash or sodium bicarbonate, forms sodium acrylate and acrylic acid supersaturated aqueous solution, wherein sodium acrylate partly precipitated.When using other salt or salt mixture, use to have the cationic alkali of corresponding difference.
In particularly preferred embodiments, initial aqueous vinylformic acid is mixed with aqueous sodium hydroxide solution, form the 100% neutral sodium acrylate solution that is not less than 30 weight % and is not higher than 45 weight %.Preferred especially the sodium acrylate aqueous solution that is no more than 40 weight % of producing with 100% saturation ratio.In order to remove all or some neutralization heat, during neutralizing or afterwards, these sodium acrylate aqueous solution are cooled off with interchanger.Neutralization and partially or completely removing after the reaction heat, the temperature of this sodium acrylate solution especially preferably is no more than 50 ℃, more preferably no more than 40 ℃, more preferably is no more than 20 ℃ and usually greater than 0 ℃.
Add excessive sodium hydrate solution to the solution that so obtains then, form greater than 100mol% neutral sodium acrylate solution, this solution does not generate any precipitation in the method for the invention.
In another preferred implementation of the present invention, this excessive sodium hydroxide solution also can be from beginning just with in the method for the invention, and the solution that is guided through interchanger is just excessively neutralized from beginning.
Can also part add this excessive sodium hydrate in the downstream of interchanger in addition in upstream, the part of interchanger.
In another modification, only acrylic acid solution is neutralized to and is not less than 80mol%, preferably be not less than 90mol%, most preferably surpass 95mol%, then after partly or entirely removing neutralization heat, interpolation is according to excessive sodium hydrate solution required for the present invention, and described heat is removed and for example can be used tube bank or flat plate heat exchanger or realize with some alternate manners.
In all embodiments, add enough sodium hydroxide solutions, to form 100% above neutral sodium acrylate solution all the time, plussage depends on due solid content and the degree of neutralization for the treatment of the polymeric monomer solution.Solid content is meant treats neutralization and unneutralized monomeric gross weight mark in the polymeric monomer solution.
The sodium hydroxide that uses exists with the aqueous solution that is no less than 25 weight % usually, but the preferred aqueous solution that uses 50 weight %.
Yet, also can use to have the sodium hydroxide that surpasses 50 weight % concentration, for example with about 70 weight % wax shapes or with 100% pure solid form.
But it is in all continuous treatment steps, reduce, but preferably use the pumping and the unusual sodium hydroxide of height conc forms, if suitable then can mix with potassium hydroxide or other material in order to make fusing point.
Add acid monomer, preferred vinylformic acid to the solution that so obtains then, if suit then excessive interpolation, the degree of neutralization of gained solution is adjusted to 10-100mol%, preferred-95mol%, more preferably 40-90mol%, is more preferably 60-80mol%, most preferably 65-78mol%.In a particularly preferred embodiment of the present, the heat that neutralization generates and the heat of crystallization of slow sedimentary sodium acrylate are removed to very little degree, if remove.In another embodiment, for example can dry ice is all or part of removes this heat by adding.
When acid monomer is acrylic or methacrylic when acid, it with the aqueous solution that is no less than 70 weight %, preferably be no less than the aqueous solution of 85 weight %, more preferably be no less than the aqueous solution of 95 weight %, most preferably be no less than the aqueous solution of 99.3 weight %, use with the pure substance of 100 weight % at the most usually.
When acid monomer was acrylic or methacrylic acid, the dimer composition in the inventive method was no more than 2000ppm, preferably is less than 1200ppm, more preferably less than 900ppm, most preferably is less than 600ppm, and all are all based on used total acid monomer.
In addition, in the method for the invention, acid monomer was stablized with inhibitor before neutralization.Used inhibitor is preferably the monomethyl ether of quinhydrones, the monomethyl ether and the tocopherol of preferred especially quinhydrones.The amount of used stablizer is no more than 150ppm, preferably is no more than 100ppm, more preferably no more than 60ppm, is more preferably and is no more than 40ppm, is most preferably not exceeding 20ppm, and all are all based on used total acid monomer.
In the monomer solution that so obtains, add linking agent and essential initiator then.Yet linking agent also in the end adds to produce supersaturated solution, as long as it is chemically enough stable with vinylformic acid in the step.
In a preferred embodiment of the present invention, the production of this supersaturated solution is carried out in each step continuously, then, preferably still before precipitating fully, sodium acrylate makes this solution polymerization, preferably on tape, more preferably in continuous kneader or for example in spraying polymerization process.
In another embodiment of the present invention, the first step is carried out in batch reactor with the production of sodium acrylate solution in crossing.In second step, carry out continuously subsequently setting final degree of neutralization and solid content by adding vinylformic acid.Can use one or more batch reactors to carry out the first step in this method.And, follow continuous polymerization method herein after preferred this method and even before all sodium acrylates precipitations, reaction soln infeeded this continuous polymerization method.
During the special advantage of the method according to this invention was and sodium acrylate solution production period is most of or preferred all removing of neutralization heat, because obviously jeopardize quality product with the high starting temperature in the post-polymerization.The degree that is neutralized with sodium acrylate solution in crossing in the first step preferably surpasses 105mol%, more preferably surpasses 110mol%, more preferably surpasses 120mol%.The temperature of the first methacrylic acid salts solution is set to is lower than 40 ℃, preferably be lower than 35 ℃,, more preferably be lower than 25 ℃, particularly be lower than 20 ℃ more preferably less than 30 ℃.Only along with of the interpolation of other acid monomer second, in the consecutive steps, supersaturation just takes place in the method for the invention, and the fundamental principle of this method is that the sodium acrylate supersaturated solution that will so obtain does not have remarkable delay ground even supplied with continuous polymerization reactor before sodium acrylate precipitates fully.This has been avoided being separated and the obstruction of feeding line.Usually not exclusively, preferably only part (be less than 50% usually, preferably be less than 25%, particularly be less than 10%) is removed the heat that neutralization generates, particularly not by initiatively cooling.This supersaturated solution does not have delay ground to infeeding of polymerization reactor after producing by continuous mixing carries out.The residence time that enters the charging of polymerization reactor from mixture is less than 10 minutes, preferably is less than 5 minutes, more preferably less than 3 minutes and most preferably be less than 1 minute.
In another embodiment of the present invention, institute carries out separately in batch reactor in steps successively, preferably has the kneading reactor of, two or more shaft or other agitation elements.In this case, heat also can be by cooling off reactor wall and all or part of removing.
In yet another embodiment of the present invention, the first step, the production of 90-100mol% neutral monomer solution is carried out in being furnished with the steel basin of interchanger, gained solution is transferred in the batch reactor through stirring, and this reactor preferably has one, two or more shaft or other agitation elements.In batch reactor, carried out for second step then, the interpolation of acrylic acid solution and other component.In this case, heat also can be by cooling off reactor wall and all or part of removing.
In particularly preferred embodiments, method of the present invention and continuous kneader method are united use-described in WO01/38402 and WO02/32964-wherein each are all early stage broken and remove most of polymerization reaction heat by evaporation of water with gel earlier.In addition, the solution of so producing preferably is used in and sprays in the polymerization.
The supersaturation monomer solution or the sodium acrylate throw out that so obtain can not necessarily be contained other other component.These components can be water-soluble comonomers, for example methacrylic acid, toxilic acid, methylene-succinic acid, 2-acrylamide-2-methyl propane sulfonic acid; An alkali metal salt of described acid and ammonium salt and acid amides; The hydroxy alkyl ester of acrylic or methacrylic acid; N-vinyl formamide and diallyldimethylammonium chloride.The monomer solution for the treatment of sodium acrylate used according to the invention also can with water-insoluble monomer (methyl) acrylic ester copolymer of vinylbenzene and/or such monohydroxy-alcohol for example, i.e. for example n-butyl acrylate, tert-butyl acrylate or isobutyl acrylate, vinyl cyanide, methacrylonitrile and/or vinyl ester are as vinyl-acetic ester or propionate.This provides the aqueous liquid dispersion of hydrophobically modified polymkeric substance or aqueous solutions of polymers-the depend on amount that is used in the water-soluble monomer in the copolyreaction.
In the preferred version of this method, acrylate solution mixed with acidic comonomer such as vinylformic acid before polymerization.
According to the present invention, solid propenoic acid sodium also can all or part of quilt another kind of solid, water soluble salt replace, for example: ammonium acrylate or other alkali metal salts of acrylic acids, particularly potassium acrylate for example; Or vinylformic acid alkaline earth salt, particularly for example vinylformic acid magnesium, calcium acrylate, vinylformic acid strontium or vinylformic acid barium.Also can use zinc acrylate resin and vinylformic acid aluminium.Similarly, can make the solid propenoic acid an alkali metal salt planned and the polymerization of mixtures of solid propenoic acid alkaline earth salt.The supersaturated solution of these salt also can partly contain the acrylate (according to their solubleness) of higher concentration.Invention disclosed is more specifically described at sodium acrylate in the literary composition, but is also easily adjusted to be applicable to acrylic acid other salt by those skilled in the art.Similarly, the present invention also can be used for the mixture of methacrylate or acrylate and methacrylate.Preferred acrylate and the vinylformic acid of using.Preferred salt is ammonium salt and an alkali metal salt, particularly sodium salt and sylvite, especially sodium salt.
Wait to want used according to the invention and have or do not have acrylic acid sodium acrylate supersaturation monomer solution or aqueous dispersion is preferred for producing the water-insoluble cross-linked polymer gel.When the sodium acrylate supersaturated aqueous solution of waiting to want used according to the invention when 0.001 weight %～5 weight %, preferred 0.01 weight %-2 weight % contain in the presence of the monomer of two ethylenical unsaturated double bonds polymerization at least, obtain such polymer gel.Suitable linking agent is N, N '-methylene-bisacrylamide; Diacrylate or dimethacrylate with polyalkylene glycol of 100-1500 molar mass; Trimethylolpropane trimethacrylate; TriMethylolPropane(TMP) or the double methacrylateization at least of glycerine or the reaction product of methacrylated, particularly each OH group that each OH group has the 1-8mol ethylene oxide have TriMethylolPropane(TMP) or all acrylic esterization of glycerine or the reaction product of methacrylated of 2-6mol ethylene oxide; Sorbyl alcohol triallyl ether; Pentaerythritol triallyl ether; The polyoxyethylene glycol diallyl ether; Triallylamine or tetra allyl ammonium chloride.The method of producing crosslinked polymer gel is referring to the 6-7 page or leaf of the EP-B 372706 of for example prior art and 4-8 page or leaf and the WO01/38402 of WO-A-99/42494.Product is to have for example particle hydrogel of 45-1000 μ m median size, preferred 150-850 μ m, more preferably＜700 μ m.
For production has the particle hydrogel of high-gel strength, make the surface crosslinked operation in back of particle hydrogel experience.Suitable back, surface linking agent is a polyvalent alcohol, referring to US-A-4666983 and 2-oxazolidone, referring to WO99/42494.The back crosslinked of particle hydrogel is described in detail in the described reference.Usually with the spray solution of at least a linking agent in inert solvent, inert solvent for example is the mixture of water or water and monohydroxy-alcohol or polyvalent alcohol to the particle hydrogel.Crosslinked for carrying out the back, surface, will be heated to the 50-250 ℃ of temperature in the scope, preferred 115-190 ℃ with cross-linking agent solution treated water gel particle.
With solid propenoic acid sodium or by in the supersaturation and the sodium acrylate of partly precipitated prepare supersaturation monomer solution of the present invention.So generate highly spissated reaction mixture, compare with existing method, this mixture provides the space-time yield of raising because of the solid content that improves greatly.Reaction mixture of the present invention constitutes oversaturated, stable or unstabilized solution or precipitation, slurries or the dispersion liquid of sodium acrylate water soluble acrylic acid that forms from the sodium acrylate supersaturated solution.
Sodium acrylate supersaturated solution of the present invention is useful in all known polymerization processs.For example they are preferred in kneader method or the band method.Also can make polymerization in their thin layers on roller or on the travelling belt, they be sprayed with the drop form in the gas phase distribute and polymerization.
Acrylic acid salt all is stable in solid-state or in the aqueous solution, thereby does not have diacrylate to form at the aqueous solution lay up period of solid salt or salt.Polymkeric substance from this monomer production can be heated to high temperature,, and not increase the residual volume of vinylformic acid in polymkeric substance as 190-210 ℃.On the contrary, if make the acroleic acid polymerization that contains diacrylate, observe from the polymkeric substance of these monomer productions because counter the dissociating (back-cleavage) of poly-diacrylate and when heating, discharge vinylformic acid mutually.Thereby this base polymer has than high in the past residual monomer content afterwards at heat stress device (thermal stressor).In addition, need not sodium acrylate to be stablized and resist premature polymerization with inhibitor.
For example, the surface-crosslinked particle hydrogel that obtains afterwards has DIN 5033 colours of L 〉=90 and the colour of b＜10, preferred L 〉=93 and b＜8.
Crosslinked particulate saline flow conductivity behind the surface (Saline Flow Conductivity, SFC) value for example be＞25, preferably＞60, particularly＞100.
The remaining acrylic acid content through the particle hydrogel of crosslinked operation behind the surface for example is＜500ppm, and is preferred＜300ppm.
These particles have 20-40g/g after crosslinked behind the surface centrifugation keeps capacity (CRC) and the 16h extractable content value below the 20 weight %, below the preferred 15 weight %, more preferably below the 10 weight %, most preferably below the 7.5 weight %.
Measuring method
The 16h extractable content is measured according to ISO/DIS17190-10.SFC (saline flow conductivity) passes through US5, the test determines of 599,335 reports.
CRC (centrifugation maintenance capacity) and AUL (absorption under the load) are as WO99/42494 the 8th and 9 pages of the above mensuration.
Colour is measured (also referring to Richard S.Hunter, The Measurementof Appearance, Wiley NY 1975) according to DIN5033.Use Hunterlab S 5100 colourimeters.
Embodiment 1
Load the sodium hydroxide solution of 254g deionized water and 339.2g 50 weight % for the well-beaten laboratory reaction device of being furnished with cooling jacket.Drip 406.8g vinylformic acid then gradually, cool off so that the temperature of reaction soln is no more than 40 ℃ carefully simultaneously.The partly precipitated of fine sodium acrylate takes place thus, and it floats to the surface.Finish after the interpolation of alkali hydroxide metal water solution, then it is cooled to 20 ℃ and add 15 times of ethoxylated trimethylolpropane triacrylates of 0.407g (SR 9035, from Sartomer).
This reaction soln of 100g is put into little Stainless Steel Disc to the about 1cm of the degree of depth.After adding 0.10g Potassium Persulphate (being dissolved in few water), be placed on the about 120 ℃ hot platform of surface temperature with the brief stirring of solution and with plate.
Follow evaporation of water generation vigorous reaction this moment, slowly and fully dissolving is also poly-mutually for the precipitated solid sodium acrylate.After reaction finishes, hard thing is broken or be cut into the coarse fragments of about 1cm size with scissors, 140 ℃ of about 3h of drying down in stink cupboard.Counter weighing before and after dry calculates that the solid content of broken thing is about 68 weight % after the polymerization.
The polymkeric substance of mill-drying also is sized to the 150-850 micron.It has following character:
CRC=38g/g, AUL 0.3psi=10g/g, extractable content 3h=16 weight %
The polymkeric substance that 20g is pulverized under agitation sprays with the solution of 0.02g ethylene glycol diglycidylether in 1.0g water then, subsequently dry down in 150 ℃ in stink cupboard on the watch-glass.And then sieved 850 microns sieve to remove agglomerate.
This moment, this exsiccant polymkeric substance had following character:
CRC＝36g/g，AUL?0.3psi＝34g/g，AUL?0.7psi＝21g/g，
Extractable content 3h=8 weight %
Embodiment 2
Give well-beaten laboratory reaction device filling 254g deionized water and the 406.8g vinylformic acid of being furnished with cooling jacket.Drip the sodium hydroxide solution of 339.2g 50 weight % then gradually, cool off so that the temperature of reaction soln is no more than 40 ℃ carefully simultaneously.The partly precipitated of fine sodium acrylate takes place thus, and it floats to the surface.Finish after the interpolation of alkali hydroxide metal water solution, then it is cooled to 20 ℃ and add 15 times of ethoxylated trimethylolpropane triacrylates of 0.814g (SR 9035, from Sartomer).
This reaction soln of 100g is put into little Stainless Steel Disc to the about 1cm of the degree of depth.After adding 0.10g Potassium Persulphate (being dissolved in few water), be placed on the about 120 ℃ hot platform of surface temperature with the brief stirring of solution and with plate.
Follow evaporation of water generation vigorous reaction this moment, slowly and fully dissolving is also poly-mutually for the precipitated solid sodium acrylate.After reaction finishes, hard thing is broken or be cut into the coarse fragments of about 1cm size with scissors, 140 ℃ of about 3h of drying down in stink cupboard.Before and after dry, weigh, calculate that the solid content of broken thing is about 71 weight % after the polymerization.
The polymkeric substance of mill-drying also is sized to the 150-850 micron.And it has following character:
CRC=34g/g, AUL 0.3psi=15g/g, extractable content 3h=13 weight %
The polymkeric substance that 20g is pulverized under agitation sprays with the 0.02g ethylene glycol diglycidylether with the solution of 0.01g Span 20 (span 20) in 1.0g water then, subsequently on the watch-glass in stink cupboard in 150 ℃ times dryings.And then sieved 850 microns sieve to remove agglomerate.
This moment, this exsiccant polymkeric substance had following character:
CRC＝30g/g，AUL?0.3psi＝31g/g，AUL?0.7psi＝24g/g，
Extractable content 3h=6 weight %
Embodiment 3
Give the well-beaten laboratory reaction device filling 316g deionized water be furnished with cooling jacket, then 100g solid propenoic acid sodium is dissolved in wherein and adds 330g vinylformic acid-with chuck temperature is remained between 20 ℃ and 40 ℃ during this period.Drip 254g 50 weight % sodium hydroxide solutions then gradually, cool off so that the temperature of reaction soln is no more than 40 ℃ carefully simultaneously.The partly precipitated of fine sodium acrylate takes place thus, and it floats to the surface.Finish after the interpolation of alkali hydroxide metal water solution, then it is cooled to 20 ℃ and add 15 times of ethoxylated trimethylolpropane triacrylates of 0.407g (SR 9035, from Sartomer).
This reaction soln of 100g is put into little Stainless Steel Disc to the about 1cm of the degree of depth.After adding 0.10g Potassium Persulphate (being dissolved in few water), with brief stirring of solution and interpolation trace xitix (being dissolved in few water).The amount of xitix must remain on very little, is usually less than 0.01 weight % based on monomer, otherwise the startup of reaction will be very violent.
Follow evaporation of water generation vigorous reaction this moment, slowly and fully dissolving is also poly-mutually for the precipitated solid sodium acrylate.After reaction finishes, hard thing is broken or be cut into the coarse fragments of about 1cm size with scissors, 140 ℃ of about 3h of drying down in stink cupboard.Before and after dry, weigh, calculate that the solid content of broken thing is about 69 weight % after the polymerization.
The polymkeric substance of mill-drying also is sized to the 150-850 micron.It has following character:
CRC=37g/g, AUL 0.3psi=10g/g, extractable content 3h=14 weight %
Solution in 1.0g water under agitation sprays the polymkeric substance that 20g is pulverized with 0.02g ethylene glycol diglycidylether and 0.01g Span 20 then, subsequently dry down in 150 ℃ in stink cupboard on the watch-glass.And then sieved 850 microns sieve to remove agglomerate.
This moment, this exsiccant polymkeric substance had following character:
CRC＝35g/g，AUL?0.3psi＝33g/g，AUL?0.7psi＝20g/g，
Extractable content 3h=7 weight %
Embodiment 4
Solution in 1.0g water under agitation sprays with 0.03g N-hydroxyethyl-2-oxazolidone and 0.01g Span 20 with the alkaline polymer of the pulverizing of 20g embodiment 3, subsequently on the watch-glass in stink cupboard in 175 ℃ of dry 1h down.And then sieved 850 microns sieve to remove agglomerate.
This moment, this exsiccant polymkeric substance had following character:
CRC=30g/g, AUL 0.7psi=23g/g, extractable content 3h=5 weight %
Embodiment 5
Give VT 5R-MK ploughshare kneader (5l volume) filling 2154.3g 37.3 weight % sodium acrylate solution (100mol% neutralization).Under agitation add 109.2g sodium hydroxide solution (50 weight %).Add 336.5g vinylformic acid to this solution stirring soon.Gains are the warm supersaturated solution (75mol%) of part neutral sodium acrylate, isolate the sodium acrylate crystal gradually in cooling or during stirring.The temperature of sodium acrylate solution, sodium hydroxide solution and acrylic acid solution is between 21-24 ℃ before mixing.
This solution is mixed with 4.76g TriMethylolPropane(TMP)-18EO-triacrylate linking agent, wherein make it temporary transient passivation by nitrogen bubble is passed.Passivation in these highly spissated solution very may because oxygen during neutralization before by most of or all remove (between the reduction of solubleness and by being retained in the carbonate in the alkali hydroxide metallic solution) by heating period.If suitable, also can save passivation fully.
Be dissolved in 2.67g Sodium Persulfate (dilute aqueous soln) in the 10.66g water, be dissolved in the 0.057g xitix in the 2.8g water and the 0.048g hydrogen peroxide that is dissolved in the 2.33g water causes this warm solution by interpolation then.Kick off temperature is lower than 40 ℃ in the embodiment of table 1 5-18 situation.
After the initiation, heating jacket temperature closed circulation is controlled to be temperature of reaction in the reactor.After arriving top temperature, with batch of material restir 3 minutes and the most at last product before drawing off reactor, be cooled to and be lower than 50 ℃.Temperature with chuck internal cooling liquid is controlled at-12 ℃ for this purpose.
The loose gel that will finally obtain then in stink cupboard in about 1.5 hours of 160 ℃ of dryings.
The exsiccant alkaline polymer is ground, screen out excessive and too small material, thereby be classified to 300-600 μ m.
The character of alkaline polymer (300-600 μ m) is charged in the following table 1.
Sodium acrylate solution (100mol% neutralization) supersaturation and with the vinylformic acid of 100 weight % a great deal oves recall to of other monomer solution of embodiment by making 37.3 weight % a great deal oves with 50 weight % sodium hydroxide solutions obtains like the complete class in the table 1.
The alkaline polymer that similarly prepares inventive embodiments thus with embodiment 1 with various degree of neutralization and solid content.
So the data of all alkaline polymers of preparation are summarized in the following table 1.
The back is crosslinked
In Waring laboratory blender with blunt nosed agitation elements, by spraying or stirring each 20g of alkaline polymer with embodiment 7-18 with being dissolved in 30: 70 w/w 1,0.10 weight % (based on used polymkeric substance) ethylene glycol diglycidylether in the 2-propylene glycol/water mixture is wetting, use 5 weight % (based on used polymkeric substance) 1 altogether, 2-propylene glycol-water mixture.Then with the wet polymer particle in stink cupboard on watch-glass in 150 ℃ crosslinked 1 hour down, the sieve that sieved 850 μ m at last is to remove agglomerate.
The data of the polymkeric substance that these surface-backs are crosslinked provide in table 1 equally.
Wherein TMP-18EO-TA represents the triacrylate of 18 times of ethoxylated trimethylolpropane.
Gly-3EO-TA represents the triacrylate of 3 times of ethoxylated glycerols.
Remember that linking agent in table 1 and amount of initiator are based on the used monomer in vinylformic acid (AA).

Claims (16)

1. one kind prepares the method that comprises the unitary polymkeric substance of (methyl) acrylate, this method is undertaken by (methyl) acrylate Raolical polymerizable in aqueous medium under the situation that has or do not exist comonomer, comprising the supersaturated aqueous solution that uses (methyl) acrylate.
2. the described method of claim 1, wherein the supersaturated aqueous solution of (methyl) acrylate comprises part neutral (methyl) vinylformic acid that degree of neutralization is 40-90mol%.
3. the described method of claim 1, the supersaturated aqueous solution that wherein prepares (methyl) acrylate in this wise, promptly by at first producing neutral (methyl) acrylate solution under 40 ℃ being lower than, add (methyl) vinylformic acid subsequently continuously, and, before (methyl) acrylate that generates precipitates fully, supersaturated salt solution is infeeded polymerization reactor and polymerization.
4. the described method of claim 1, wherein solution on tape, mediating in the reactor continuously or spraying polymerization in the polymerization process.
5. the described method of claim 1 wherein will comprise (methyl) vinylformic acid that is no more than the 2000ppm dimer and is less than the 150ppm Hydroquinone monomethylether and be used as acid monomer.
6. the described method of claim 1, wherein supersaturated aqueous solution comprise 0.001-5 weight % one or more comprise the monomer of two or more ethylenical unsaturated double bonds.
7. the described method of claim 1, wherein monomeric supersaturated aqueous solution is with the preparation of solid water-free (methyl) acrylate.
8. the described method of claim 1, wherein supersaturated aqueous solution is with solid (methyl) the acrylate preparation of the water-content with 0.1-10 weight %.
9. the described method of claim 1, wherein (methyl) acrylate uses with the form of supersaturated aqueous solution or dispersion liquid, and this aqueous solution or dispersion liquid are by obtaining the neutralization of (methyl) vinylformic acid with hydroxide aqueous solution, oxyhydroxide, carbonate or supercarbonate.
10. the described method of claim 1, wherein said comonomer are selected from the group that following material is formed: hydroxy alkyl ester, N-vinyl formamide, diallyldimethylammonium chloride, n-butyl acrylate, tert-butyl acrylate or isobutyl acrylate, vinyl cyanide, methacrylonitrile and vinyl-acetic ester and the propionate of an alkali metal salt of methacrylic acid, toxilic acid, methylene-succinic acid, 2-acrylamide-2-methyl propane sulfonic acid, above-mentioned acid and ammonium salt and acid amides, acrylic or methacrylic acid.
11. each described method among the claim 1-10, wherein (methyl) acrylate and (methyl) vinylformic acid refer to acrylate and vinylformic acid.
12. each described method among the claim 1-10, wherein (methyl) acrylate refers to (methyl) alkali metal salts of acrylic acids.
13. the described method of claim 12, wherein (methyl) acrylate refers to (methyl) sodium acrylate.
14. one kind comprises the unitary particle aquogel polymer of (methyl) acrylate, it has DIN 5033 colours of L 〉=90 and the colour of b＜10, the centrifugation of 20-40g/g keeps capacity and the following ISO/DIS17190-1016h extractable content value of 20 weight %, by crosslinked the obtaining of described method of claim 1-13 and back, surface.
15. the purposes of solid (methyl) acrylate is used for by with solid (methyl) acrylate formation monomer soluble in water supersaturated aqueous solution and make the polymerization under the situation that has or do not exist comonomer of this monomer solution prepare polymkeric substance.
16. the described purposes of claim 15, wherein said comonomer are selected from the group that following material is formed: hydroxy alkyl ester, N-vinyl formamide, diallyldimethylammonium chloride, n-butyl acrylate, tert-butyl acrylate or isobutyl acrylate, vinyl cyanide, methacrylonitrile and vinyl-acetic ester and the propionate of an alkali metal salt of methacrylic acid, toxilic acid, methylene-succinic acid, 2-acrylamide-2-methyl propane sulfonic acid, above-mentioned acid and ammonium salt and acid amides, acrylic or methacrylic acid.
CN2005800035368A 2004-01-28 2005-01-18 Method for producing polymer Expired - Fee Related CN1914236B (en)

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DE102004004496.1 2004-01-28
DE102004004496A DE102004004496A1 (en) 2004-01-28 2004-01-28 Production of polymers containing (meth)acrylate salt units is improved by using a supersaturated aqueous solution of the (meth)acrylate salts
DE102004057280A DE102004057280A1 (en) 2004-11-26 2004-11-26 Production of polymers containing (meth)acrylate salt units is improved by using a supersaturated aqueous solution of the (meth)acrylate salts
DE102004057280.1 2004-11-26
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US20140121403A1 (en) 2012-10-31 2014-05-01 Celanese International Corporation Integrated Process for the Production of Acrylic Acids and Acrylates

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CN1042346A (en) * 1988-10-28 1990-05-23 日本触煤化学工业株式会社 Prepare acrylate and the method that contains acrylic ester polymer

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