# Patent

## Title
Neutralization process

## Abstract

The invention relates to a neutralization process in which at least one ethylenically unsaturated carboxylic acid is neutralized at least partly with a base and at least one stream of the neutralization is determined continuously, and also to an apparatus for carrying out the process.

## Background
The present invention relates to a neutralization process for ethylenically unsaturated carboxylic acids, wherein at least one stream of the neutralization is determined continuously, and to an apparatus for carrying out the process.
Further embodiments of the present invention can be taken from the claims and the description. It is evident that the features of the inventive subject matter which have been mentioned above and are yet to be explained below are usable not only in the combination specified in each case but also in other combinations without leaving the scope of the invention.
Water-absorbing polymers are especially polymers of (co)polymerized hydrophilic monomers, graft (co)polymers of one or more hydrophilic monomers on a suitable graft base, crosslinked cellulose ethers or starch ethers, crosslinked carboxymethylcellulose, partly crosslinked polyalkylene oxide or natural products swellable in aqueous liquids, for example guar derivatives, preference being given to water-absorbing polymers based on partly neutralized acrylic acid. Such polymers are used as products that absorb aqueous solutions to produce diapers, tampons, sanitary napkins and other hygiene articles, but also as water-retaining agents in market gardening.
The preparation of the water-absorbing polymers is described, for example, in the monograph “Modern Superabsorbent Polymer Technology”, F. L. Buchholz and A. T. Graham, Wiley-VCH, 1998, or in Ullmann's Encyclopedia of Industrial Chemistry, 6th Edition, Volume 35, pages 73 to 103. The preferred preparation process is solution or gel polymerization. In this technology, a monomer mixture is firstly prepared and is neutralized batchwise and then transferred to a polymerization reactor, or initially charged actually within the polymerization reactor. In the batchwise or continuous process which follows, the reaction is effected to give the polymer gel which, in the case of a stirred polymerization, is already in comminuted form. The polymer gel is subsequently dried, ground and sieved and then transferred to further surface treatment.
A continuous polymerization process forms the basis, for example, of WO 01/38402, in which the aqueous monomer solution is fed continuously to a mixing kneader with at least two axially parallel-rotating shafts.
Continuous gel polymerizations are also known from WO 03/004237, WO 03/022896 and WO 01/016197.
Both in the continuous and in the batchwise polymerization, the acrylic acid is neutralized batchwise in the case of preneutralization. Typically, the reactants (acrylic acid, water, optional comonomers and sodium hydroxide solution) are metered in and mixed batchwise in the polymerization reactor in the case of solution polymerization. In this step, the remaining course of the polymerization and also the expected polymer properties are laid down to a very substantial extent. The degree of crosslinking of the base polymer and the degree of neutralization are typically determined in this step. The degree of neutralization of the monomers is between 0 and 80 mol %. In the case of acidic polymerization, the resulting polymer gel is typically neutralized afterward to an extent of from 50 to 80 mol %, preferably to an extent of from 60 to 75 mol %, by adding sodium hydroxide or sodium carbonate solution to the acidic polymer gel and incorporating it.
Neutralization processes are described, for example, in EP-A 0 372 706, EP-A 0 574 260 and WO 03/051415.
EP-A 0 372 706 describes a three-stage neutralization process in which acrylic acid and sodium hydroxide solution are metered in simultaneously in a first stage in such a way that a degree of neutralization of from 75 to 100 mol % is maintained, the degree of neutralization is raised to from 100.1 to 110 mol % in a second stage in order to hydrolyze diacrylic acid present as an impurity in the acrylic acid used, and a degree of neutralization of from 20 to 100 mol % is established in a third stage by addition of further acrylic acid.
EP-A 0 574 260 discloses, on page 7, lines 38 to 41, that sodium hydroxide solution is advantageously initially charged in the neutralization and acrylic acid is subsequently added with cooling.
WO 03/051415 teaches a process for preparing water-absorbing polymers, in which the monomer solution has a minimum temperature of 40° C.
It is known that the reactivity of acrylic acid differs very greatly from that of its salts, which is why the course of the polymerization is also greatly dependent upon the pH at which it takes place. In a graphic illustration in the monograph “Modern Superabsorbent Polymer Technology”, F. L. Buchholz and A. T. Graham, Wiley-VCH, 1998, or in Ullmann's Encyclopedia of Industrial Chemistry, 6th Edition, Volume 35, page 35, the polymerization rate is plotted as a function of the pH. According to this, the polymerization rate passes through a minimum at a pH of from 6 to 7. However, this corresponds to the pH which is generally desired in the saleable products. This behavior is explained by the occurrence of electrostatic repulsion reactions, which are not present in the case of very substantially undissociated acrylic acid, between the charged monomers in salt form and the growing free-radical chain, which leads to slowing of the reaction.
It is also known that unneutralized acrylic acid can be polymerized more easily than preneutralized systems. However, this difference is reduced in the case of rising monomer concentration, in particular because a higher monomer concentration suppresses the dissociation of the acrylic acid salts.
In order to take account of all of these details of the reaction mechanism, compromises are typically entered into in conducting the reaction.
Generally, the degree of neutralization of the acrylic acid is established actually before it enters the continuous polymerization. The neutralization is effected batchwise. Batchwise neutralization has the advantage that acrylic acid and/or sodium hydroxide solution can be metered in under temperature control. This prevents overheating and undesired polymerization in the mixture vessel. The degree of neutralization is selected in accordance with the polymerization conditions and the desired absorption profile and, if desired, corrected in a subsequent neutralization which is usually effected on the polymer gel.
In the neutralization, degree of neutralization and solids content of the neutralized solution are adjusted to the desired value. This is typically done via the quantitative ratios of the feedstocks, i.e. quantity-controlled metered addition of, for example, acrylic acid, sodium hydroxide solution and water.
A problem in the customary quantitative metering is that possible concentration deviations of the feedstocks are not taken into account.
The content in commercial 50% by weight sodium hydroxide solution of sodium hydroxide is specified, for example, to be 50+/−0.5% by weight. This means that partly neutralized acrylic acid with a degree of neutralization of 75% can have a degree of neutralization of 75+/−0.75%. When this solution is used to prepare water-absorbing polymers, this deviation is transferred up to the end product, including possible deviations from the desired polymer properties.
When the feedstocks of the neutralization are sourced via a central pipeline system, the possibility exists that the concentration of the feedstocks is changed by residual water present in the line system. For safety reasons, the fine system is flushed with water before maintenance and repair measures. This water typically cannot be removed fully afterward and remains as residual water in the line system.
It was an object of the present invention to provide a neutralization process in which concentration deviations of the feedstocks which occur are recognized and, preferably automatically, corrected.
The object is achieved by a neutralization process in which at least one ethylenically unsaturated carboxylic acid is neutralized at least partly with a base, which comprises determining at least one stream of the neutralization continuously.
Determined means that at least the content of one component of the stream is determined, for example the content of sodium hydroxide in the sodium hydroxide solution used or the content of acrylic acid and sodium acrylate in the neutralized solution. The content of the desired components may be determined directly or indirectly.
One example of a possible direct process is NIR spectroscopy. From the NIR spectra obtained, the concentration of the components can be determined directly with reference to suitable calibration curves.
Preference is given to determining the content of ethylenically unsaturated carboxylic acid and salts thereof in the neutralized solution by means of NIR spectroscopy. These data are then the basis for determining degree of neutralization and solids content of the neutralized solution.
Indirect analysis processes utilize measurements which alone do not permit any conclusions on concentration. A classical indirect process is the regulation of distillation columns via temperatures. The temperatures themselves do not give any indication of concentrations. Only the knowledge of the boiling diagrams of a two-substance mixture to be separated enables clear assignment of temperature and concentration.
A possible indirect process is, for example, the determination of the alkali content in aqueous alkali via the density and the temperature. For example, for the content of sodium hydroxide in approx. 50% by weight sodium hydroxide solution, the relationship

c[% by wt.]=(0.10657×σ[g/cm3])+(0.07016×T[° C.])−114

applies, where c is the content of sodium hydroxide, σ the density of the sodium hydroxide solution and T the temperature of the sodium hydroxide solution.

Continuously means that a measurement is generated at regular intervals, typically at least once per 10 minutes, preferably at least once per minute, more preferably at least once per 10 seconds, most preferably once per second. Shorter intervals are possible. The measurements obtained by continuous analyses are utilized to regulate the neutralization, preferably using a commercial process control system.
For example, the regulation principle will be explained for the neutralization of acrylic acid with sodium hydroxide solution. The degree of neutralization is determined via the ratio of acrylic acid to sodium hydroxide solution and the solids content via the ratio of (acrylic acid+sodium hydroxide solution) to water.
When, for example, an excessively high degree of neutralization is determined, the metered addition of sodium hydroxide solution is reduced correspondingly and the metered addition of water increased correspondingly.
When, for example, an excessively high solids content is determined, the metered addition of sodium hydroxide solution and acrylic acid is reduced correspondingly and the metered addition of water increased correspondingly.
When, for example, the content of sodium hydroxide solution in the 50% by weight sodium hydroxide solution used is determined to be 52% by weight, the metered addition of the sodium hydroxide solution is reduced correspondingly and the metered addition of water increased correspondingly.
Preference is given to using ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid. Acrylic acid is particularly preferred.
The temperature of the ethylenically unsaturated carboxylic acid is typically from 0 to 40° C., preferably from 5 to 35° C., more preferably from 10 to 30° C., most preferably from 15 to 25° C., while ensuring sufficient distance from melting point. In the case of use of acrylic acid, the temperature should not go below 15° C. in any case.
A preferred base is aqueous alkali. Aqueous alkali is all aqueous solutions with an alkaline reaction, i.e. aqueous solutions with a pH of at least 8, preferably at least 10, more preferably at least 12, most preferably at least 14.
The alkaline salts usable in the aqueous neutralizing agent are preferably alkali metal hydroxides, alkali metal oxides, alkali metal carbonates and alkali metal hydrogencarbonates and mixtures thereof. Instead of alkali metal salts, it is also possible to use ammonium salts. Sodium and potassium are particularly preferred as alkali metals, but very particular preference is given to sodium hydroxide, sodium carbonate or sodium hydrogencarbonate and mixtures thereof. Typically, the alkali content in the aqueous alkali is at least 10% by weight, preferably at least 20% by weight, more preferably at least 30% by weight, most preferably at least 40% by weight.
The temperature of the aqueous alkali is typically from 0 to 45° C., preferably from 5 to 40° C., more preferably from 10 to 35° C., most preferably from 15 to 30° C., while avoiding oversaturations and thus precipitations.
When the alkali content of the aqueous alkali is at least 25% by weight, higher temperatures are advantageous, typically of from 10 to 60° C., preferably of from 20 to 55° C., more preferably of from 30 to 50° C., most preferably of from 40 to 45° C.
The ratio of ethylenically unsaturated carboxylic acid to base is typically selected such that the degree of neutralization of the ethylenically unsaturated carboxylic acid, after neutralization, is preferably from 25 to 85 mol %, preferentially from 27 to 80 mol %, more preferably from 27 to 30 mol % or from 40 to 75 mol %.
The degree of neutralization is the molar ratio of neutralized ethylenically unsaturated carboxylic acid after neutralization to the total amount of ethylenically unsaturated carboxylic acid used before neutralization.
The neutralization is preferably carried out continuously. This means that ethylenically unsaturated carboxylic acid and/or base are supplied to the neutralization region and neutralized solution is simultaneously withdrawn from the neutralization region. Of course, startup and shutdown operations of the continuous neutralization process are excluded from this.
The solution withdrawn continuously from the neutralization region is preferably at least partly transferred continuously into the polymerization.
The polymerization is preferably likewise carried out continuously.
The neutralization region is the region in which the neutralization takes place to a substantial extent, i.e. the region in which ethylenically unsaturated carboxylic acid and base react with salt formation (neutralization).
The neutralization has substantially been completed when the conversion of the neutralization is at least 90 mol %, preferably at least 95 mol %, more preferably at least 98 mol %, most preferably at least 99 mol %. The conversion can be determined easily via the heat of neutralization released by comparison with the theoretical exothermicity.
The preferably continuous neutralization is carried out in such a way that the temperature of the neutralized solution is preferably less than 60° C., preferentially less than 50° C., more preferably less than 40° C., most preferably less than 30° C., the temperature being the average temperature after neutralization, i.e. the mean temperature after full exothermicity.
In addition, the neutralized solution may be diluted with water. The dilution with water allows the solids content of the neutralized solution to be adjusted. The solids content is the sum of the proportions by weight of neutralized ethylenically unsaturated carboxylic acid and, if desired, excess ethylenically unsaturated carboxylic acid or excess base. The solids content of the neutralized solution is typically from 10 to 80% by weight, preferably from 20 to 70% by weight, more preferably from 30 to 60% by weight.
The temperature of the water is typically from above 0 to 40° C., preferably from 5 to 35° C., more preferably from 10 to 30° C., most preferably from 15 to 25° C.
Advantageously, the neutralized solution is cooled, in which case the heat exchangers usable for cooling are not subject to any restriction. The neutralized solution is cooled to a temperature of preferably less than 50° C., preferentially less than 40° C., more preferably less than 30° C., most preferably less than 20° C. The cooling should be as close as possible to the neutralization, since high residence times of the neutralized solution at high temperatures can thus be avoided.
Preference is given to premixing water and base. In this case, the heat of dissolution released can be removed actually before the neutralization, for example by means of suitable heat exchangers.
In a particularly preferred embodiment of the present invention, a portion of the neutralized solution is recycled into the neutralization, preferably cooled.
The recycling allows the heat of neutralization and the heat of dissolution to be distributed better and temperature peaks (peak temperature) in the mixture to be kept low. The proportion of recycled neutralized solution is typically from 25 to 99%, preferably from 33 to 98%, more preferably from 50 to 95%, most preferably from 80 to 90%, based in each case on the neutralized solution.
The ethylenically unsaturated carboxylic acid, the base and, if desired, the water may be metered into the recycled neutralized solution at any point. Preference is given to metering in the liquids in succession, particular preference to metering in base and ethylenically unsaturated carboxylic acid in succession, very particular preference to metering in water, base and ethylenically unsaturated carboxylic acid in succession. Advantageously, at least one of the reactants is metered in via two or more separate addition points.
For example, the reactants may be metered in via two, three, four, five or six addition points, the addition points preferably being arranged such that they have a common axis (for two addition points) or form a symmetrical star (for at least three addition points), and the axis or star is at right angles to the flow direction of the neutralized solution (multiple addition points).
The base is metered in particularly advantageously when two, three or four multiple addition points are arranged in succession.
The division into a plurality of addition points brings about more uniform mixing and lower temperature peaks, which reduces the risk of undesired polymerization.
In a further embodiment, water and base are metered in such that the water encloses the base on entry into the neutralization. To this end, for example, two tubes inserted into one another may be used, in which case the base is metered in through the inner tube and the water through the annular gap between inner and outer tube.
Advantageously, the neutralization comprises an additional vessel as a buffer vessel.
An exemplary inventive neutralization is shown by FIG. 1, the reference symbols having the following definitions:
















Z1 to Z3
feeds for reactants 1 to 3



A
outlet



B
vessel



M1 and M2
measuring units 1 and 2



P
pump



R
ring line



W
heat exchanger












By means of a pump P, neutralized solution is recycled partly via the ring line R. The rest of the neutralized solution is sent via the outlet A to further use. The vessel B serves as a buffer. 50% by weight sodium hydroxide solution is preferably metered in via inlet Z1, preferably acrylic acid via inlet Z2 and preferably water via inlet Z3.
The measuring units M1 and/or M2 generate the measurements needed for the analysis. In the process according to the invention, typically the measuring unit M1 is used alone, the measuring unit M2 is used alone or both are used.
In order that the reactants are mixed very intensively into the recycled neutralized solution, the flow at the point of mixing-in should be very turbulent. The mixing-in point is the place where the particular reactant meets the recycled neutralized solution.
In a preferred embodiment of the present invention, at least one of the reactants is metered into a Venturi tube; preferably, all reactants are metered into a Venturi tube; more preferably, all reactants are metered into a common Venturi tube.
A Venturi tube is a pipe constriction of a restricted length in which pressure drop is converted substantially reversibly to kinetic energy. To this end, the cross section F1 is reduced to the cross section F2 over the zone L1, the cross section F2 is kept constant over the zone L2 and the cross section F2 is widened again to the cross section F1 over the zone L3. The cross section F1 is greater than the cross section F2 and the length L3 is greater than the length L1.
The reactants for the neutralization are preferably metered in in the region of the zone L2 with the cross section F2.
The optimal design of a Venturi tube is known per se to those skilled in the art. The Venturi tube is preferably designed such that the pressure in the region of the zone L2 is less than the ambient pressure (suction conveying) and/or that the flow in the region of the zone L2 is turbulent, in which case the Reynolds number should be at least 1000, preferably at least 2000, more preferably at least 3000, most preferably at least 4000, and typically less than 10 000 000.
The neutralization process according to the invention enables neutralized solutions of uniform quality to be provided. The neutralization process according to the invention is very particularly suitable for continuous neutralizations.
The present invention further provides a process for preparing water-absorbing polymers by using a neutralized solution prepared by the neutralization process according to the invention as the monomer solution.
Preference is given to combining the inventive neutralization process with a continuous polymerization process, in which case preference is given to carrying out all process steps, such as neutralization, polymerization, drying, grinding, sieving, postcrosslinking and sieving, continuously.
The water-absorbing polymers are obtained, for example, by polymerization of a monomer solution comprising

    a) at least one ethylenically unsaturated carboxylic acid,
    b) at least one crosslinker,
    c) if desired one or more ethylenically and/or allylically unsaturated monomers copolymerizable with the monomer a), and
    d) if desired one or more water-soluble polymers onto which the monomers a), b) and if appropriate c) can be at least partly grafted.


Suitable ethylenically unsaturated carboxylic acids a) are, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid. Particularly preferred monomers are acrylic acid and methacrylic acid. Very particular preference is given to acrylic acid.
The monomers a), especially acrylic acid, comprise preferably up to 0.025% by weight of a hydroquinone monoether. Preferred hydroquinone monoethers are hydroquinone monomethyl ether (MEHQ) and/or tocopherols.
Tocopherol refers to compounds of the following formula:




where R1 is hydrogen or methyl, R2 is hydrogen or methyl, R3 is hydrogen or methyl and R4 is hydrogen or an acyl radical having from 1 to 20 carbon atoms.

Preferred R4 radicals are acetyl, ascorbyl, succinyl, nicotinyl and other physiologically tolerable carboxylic acids. The carboxylic acids may be mono-, di- or tricarboxylic acids.
Preference is given to alpha-tocopherol where R1=R2=R3=methyl, especially racemic alpha-tocopherol. R1 is more preferably hydrogen or acetyl. Especially preferred is RRR-alpha-tocopherol.
The monomer solution comprises preferably not more than 130 ppm by weight, more preferably not more than 70 ppm by weight, preferably not less than 10 ppm by weight, more preferably not less than 30 ppm by weight and especially about 50 ppm by weight of hydroquinone monoether, based in each case on acrylic acid, with acrylic acid salts being counted as acrylic acid. For example, the monomer solution can be prepared using acrylic acid having an appropriate hydroquinone monoether content.
The crosslinkers b) are compounds having at least two polymerizable groups which can be free-radically polymerized into the polymer network. Suitable crosslinkers b) are, for example, ethylene glycol dimethacrylate, diethylene glycol diacrylate, allyl methacrylate, trimethylolpropane triacrylate, triallylamine, tetraallyloxyethane, as described in EP-A-0 530 438, di- and triacrylates, as described in EP-A 0 547 847, EP-A 0 559 476, EP-A 0 632 068, WO 93/21237, WO 03/104299, WO 03/104300, WO 03/104301 and DE-A 103 31 450, mixed acrylates which, as well as acrylate groups, comprise further ethylenically unsaturated groups, as described in DE-A 103 31 456 and WO 04/013064, or crosslinker mixtures as described, for example, in DE-A 195 43 368, DE-A 196 46 484, WO 90/15830 and WO 02/32962.
Suitable crosslinkers b) include in particular N,N′-methylenebisacrylamide and N,N′-methylenebismethacrylamide, esters of unsaturated mono- or polycarboxylic acids of polyols, such as diacrylate or triacrylate, for example butanediol diacrylate, butanediol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate and also trimethylolpropane triacrylate and allyl compounds, such as allyl (meth)acrylate, triallyl cyanurate, diallyl maleate, polyallyl esters, tetraallyloxyethane, triallylamine, tetraallylethylenediamine, allyl esters of phosphoric acid and also vinylphosphonic acid derivatives as described, for example, in EP-A 0 343 427. Suitable crosslinkers b) further include pentaerythritol diallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, polyethylene glycol diallyl ether, ethylene glycol diallyl ether, glycerol diallyl ether, glycerol triallyl ether, polyallyl ethers based on sorbitol, and also ethoxylated variants thereof. In the process of the invention, it is possible to use di(meth)acrylates of polyethylene glycols, the polyethylene glycol used having a molecular weight between 300 and 1000.
However, particularly advantageous crosslinkers b) are di- and triacrylates of 3- to 15-tuply ethoxylated glycerol, of 3- to 15-tuply ethoxylated trimethylolpropane, of 3- to 15-tuply ethoxylated trimethylolethane, especially di- and triacrylates of 2- to 6-tuply ethoxylated glycerol or of 2- to 6-tuply ethoxylated trimethylolpropane, of 3-tuply propoxylated glycerol, of 3-tuply propoxylated trimethylolpropane, and also of 3-tuply mixed ethoxylated or propoxylated glycerol, of 3-tuply mixed ethoxylated or propoxylated trimethylolpropane, of 15-tuply ethoxylated glycerol, of 15-tuply ethoxylated trimethylolpropane, of 40-tuply ethoxylated glycerol, of 40-tuply ethoxylated trimethylolethane and also of 40-tuply ethoxylated trimethylolpropane.
Very particularly preferred crosslinkers b) are polyethoxylated and/or -propoxylated glycerols which have been esterified with acrylic acid or methacrylic acid to di- or triacrylates, as described, for example, in WO 03/104301. Di- and/or triacrylates of 3- to 10-tuply ethoxylated glycerol are particularly advantageous. Very particular preference is given to di- or triacrylates of 1- to 5-tuply ethoxylated and/or propoxylated glycerol. The triacrylates of 3- to 5-tuply ethoxylated and/or propoxylated glycerol are most preferred. These are notable for particularly low residual levels (typically below 10 ppm by weight) in the water-absorbing polymer and the aqueous extracts of the water-absorbing polymers produced therewith have an almost unchanged surface tension (typically not less than 0.068 N/m) compared with water at the same temperature.
The amount of crosslinker b) is preferably from 0.01 to 1% by weight, more preferably from 0.05 to 0.5% by weight, most preferably from 0.1 to 0.3% by weight, based in each case on the monomer a).
Examples of ethylenically unsaturated monomers c) which are copolymerizable with the monomers a) are acrylamide, methacrylamide, crotonamide, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminopropyl acrylate, diethylaminopropyl acrylate, dimethylaminobutyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoneopentyl acrylate and dimethylaminoneopentyl methacrylate.
Useful water-soluble polymers d) include polyvinyl alcohol, polyvinylpyrrolidone, starch, starch derivatives, polyglycols or polyacrylic acids, preferably polyvinyl alcohol and starch.
For optimal action, the preferred polymerization inhibitors require dissolved oxygen. Typically, the monomer solutions are substantially freed of oxygen before the polymerization (inertization), for example by means of flowing an inert gas, preferably nitrogen, through them. This distinctly weakens the action of the polymerization inhibitors. The oxygen content of the monomer solution is preferably lowered to less than 1 ppm by weight and more preferably to less than 0.5 ppm by weight before the polymerization.
The preparation of a suitable base polymer and also further suitable hydrophilic ethylenically unsaturated monomers d) is described in DE-A 199 41 423, EP-A 0 686 650, WO 01/45758 and WO 03/104300.
Water-absorbing polymers are typically obtained by addition polymerization of an aqueous monomer solution and, if desired, subsequent comminution of the hydrogel. Suitable preparation methods are described in the literature. Water-absorbing polymers are obtainable, for example, by

    
    
        gel polymerization in a batch process or tubular reactor and subsequent comminution in a meat grinder, extruder or kneader (EP-A-0 445 619, DE-A-198 46 413)
        addition polymerization in a kneader with continuous comminution by contrarotatory stirring shafts for example (WO 01/38402)
        addition polymerization on a belt and subsequent comminution in a meat grinder, extruder or kneader (DE-A-38 25 366, U.S. Pat. No. 6,241,928)
        emulsion polymerization, which produces bead polymers having a relatively narrow gel size distribution (EP-A-0 457 660)
        in situ addition polymerization of a woven fabric layer which, usually in a continuous operation, has previously been sprayed with aqueous monomer solution and subsequently been subjected to a photopolymerization (WO 02/94328, WO 02/94329).
    
    


The reaction is preferably carried out in a kneader as described for example in WO 01/38402, or on a belt reactor as described for example in EP-A 0 955 086.
Neutralization can also be carried out partly after the polymerization, at the hydrogel stage. It is therefore possible to neutralize up to 40 mol %, preferably from 10 to 30 mol % and more preferably from 15 to 25 mol % of the acid groups before the polymerization by adding a portion of the neutralizing agent to the monomer solution and setting the desired final degree of neutralization only after the polymerization, at the hydrogel stage. The monomer solution can be neutralized by mixing in the neutralizing agent. The hydrogel may be comminuted mechanically, for example by means of a meat grinder, in which case the neutralizing agent can be sprayed, sprinkled or poured on and then carefully mixed in. To this end, the gel mass obtained can be repeatedly ground in the meat grinder for homogenization. Neutralization of the monomer solution to the final degree of neutralization is preferred.
The neutralized hydrogel is then dried with a belt or drum dryer until the residual moisture content is preferably below 15% by weight and especially below 10% by weight, the water content being determined by EDANA (European Disposables and Nonwovens Association) recommended test method No. 430.2-02 “Moisture content”. If desired, drying can also be carried out using a fluidized bed dryer or a heated plowshare mixer. To obtain particularly white products, it is advantageous to dry this gel while ensuring rapid removal of the evaporating water. To this end, the dryer temperature must be optimized, the air feed and removal has to be controlled, and sufficient venting must be ensured in each case. The higher the solids context of the gel, the simpler the drying, by its nature, and the whiter the product. The solids content of the gel before the drying is therefore preferably between 30% and 80% by weight. It is particularly advantageous to vent the dryer with nitrogen or another nonoxidizing inert gas. If desired, however, it is possible simply just to lower the partial pressure of the oxygen during the drying in order to prevent oxidative yellowing processes. In general, though, adequate venting and removal of the water vapor also still lead to an acceptable product. A very short drying time is generally advantageous with regard to color and product quality.
The dried hydrogel is preferably ground and sieved, useful grinding apparatus typically including roll mills, pin mills or swing mills. The particle size of the sieved, dry hydrogel is preferably below 1000 μm, more preferably below 900 μm and most preferably below 800 μm, and preferably above 100 μm, more preferably above 150 μm and most preferably above 200 μm.
Very particular preference is given to a particle size (sieve cut) of from 106 to 850 μm. The particle size is determined according to EDANA (European Disposables and Nonwovens Association) recommended test method No. 420.2-02 “Particle size distribution”.
The base polymers are then preferably surface postcrosslinked. Postcrosslinkers suitable for this purpose are compounds comprising two or more groups capable of forming covalent bonds with the carboxylate groups of the hydrogel. Suitable compounds are, for example, alkoxysilyl compounds, polyaziridines, polyamines, polyamidoamines, di- or polyglycidyl compounds, as described in EP-A 0 083 022, EP-A 0 543 303 and EP-A 0 937 736, di- or polyfunctional alcohols, as described in DE-C 33 14 019, DE-C 35 23 617 and EP-A 0 450 922, or β-hydroxyalkylamides, as described in DE-A 102 04 938 and U.S. Pat. No. 6,239,230.
In addition, DE-A 40 20 780 describes cyclic carbonates, DE-A 198 07 502 2-oxazolidone and its derivatives, such as 2-hydroxyethyl-2-oxazolidone, DE-A 198 07 992 bis- and poly-2-oxazolidinones, DE-A 198 54 573 2-oxotetrahydro-1,3-oxazine and its derivatives, DE-A 198 54 574 N-acyl-2-oxazolidones, DE-A 102 04 937 cyclic ureas, DE-A 103 34 584 bicyclic amide acetals, EP-A 1 199 327 oxetanes and cyclic ureas and WO 03/031482 morpholine-2,3-dione and its derivatives, as suitable surface postcrosslinkers.
The postcrosslinking is typically carried out in such a way that a solution of the surface postcrosslinker is sprayed onto the hydrogel or onto the dry base polymer powder. After the spraying, the polymer powder is dried thermally, and the crosslinking reaction may take place either before or during drying.
The spraying with a solution of the crosslinker is preferably carried out in mixers having moving mixing implements, such as screw mixers, paddle mixers, disk mixers, plowshare mixers and shovel mixers. Particular preference is given to vertical mixers and very particular preference to plowshare mixers and shovel mixers. Suitable mixers are, for example, Lödige® mixers, Bepex® mixers, Nauta® mixers, Processall® mixers and Schugi® mixers.
The thermal drying is preferably carried out in contact dryers, more preferably shovel dryers and most preferably disk dryers. Suitable dryers are, for example, Bepex® dryers and Nara® dryers. It is also possible to use fluidized bed dryers.
The drying can be effected in the mixer itself, by heating the jacket or blowing in warm air. It is equally possible to use a downstream dryer, for example a tray dryer, a rotary tube oven or a heatable screw. It is also possible, for example, to utilize an azeotropic distillation as a drying process.
Preferred drying temperatures are in the range from 50 to 250° C., preferably in the range from 50 to 200° C. and more preferably in the range from 50 to 150° C. The preferred residence time at this temperature in the reaction mixer or dryer is below 30 minutes and more preferably below 10 minutes.
The present invention further provides an apparatus for carrying out the neutralization process according to the invention, comprising

    i) a ring line R,
    ii) at least one first inlet Z1 into the ring line R,
    iii) at least one second inlet Z2 into the ring line R,
    iv) at least one heat exchanger W in the ring line R, the heat exchanger W being disposed beyond the inlets Z1 and Z2 in flow direction,
    v) at least one measuring unit M1 for determining the degree of neutralization and/or solids content, the measuring unit M1 preferably being disposed beyond the inlets Z1 and Z2 and before the heat exchanger W in flow direction, and/or at least one measuring unit M2 for determining the alkali content, the measuring unit M2 being disposed in the inlet Z1 or Z2,
    vi) at least one outlet A from the ring line R, the outlet A being disposed beyond the heat exchanger W in flow direction,
    vii) a pump P and
    viii) if desired, a vessel B between the heat exchanger W and the outlet A,

where at least one first inlet Z1 means that reactant 1, for example sodium hydroxide solution, is supplied via one or more inlets Z1, and at least one second inlet Z2 means that reactant 2, for example acrylic acid, is supplied via one or more inlets Z2.



The measuring unit M1 is preferably an NIR spectrometer.
The measuring unit M2 is preferably a combination of densitometer and thermometer.
The ring line cross section Q is preferably from 20 to 2000 cm2, more preferably from 80 to 700 cm2, most preferably from 200 to 500 cm2. The ring line R preferably has a circular cross section.
The totality of the inlets Z1 has a cross section of preferably from 1.5 to 100 cm2, more preferably from 6 to 35 cm2, most preferably from 15 to 25 cm2. The inlets Z1 preferably have a circular cross section.
The totality of the inlets Z2 has a cross section of preferably from 1.5 to 100 cm2, more preferably from 6 to 35 cm2, most preferably from 15 to 25 cm2. The inlets Z2 preferably have a circular cross section.
The pump P has a delivery capacity of preferably from 1 to 1000 t/h, more preferably from 10 to 700 t/h, most preferably from 100 to 500 t/h.
The vessel B has a volume of preferably from 1 to 100 m3, more preferably from 10 to 100 m3, most preferably from 20 to 50 m3.
The inlets Z1 and Z2 are preferably arranged in succession, the inlets Z1 preferably being before the inlets Z2 in flow direction.
The distance between the inlets Z1 and Z2 is preferably from 10 to 500%, more preferably from 50 to 300%, most preferably from 80 to 200%, of the square root of the ring line cross section Q.
Preferably at least two inlets Z1 and/or Z2 are present, more preferably two, three, four, five or six inlets Z1 and Z2, the inlets Z1 and Z2 preferably being arranged such that they have a common axis (for two inlets Z1 and Z2) or form a symmetrical star (for at least three inlets Z1 and Z2) and the axis or star is at right angles to the flow direction of the neutralized solution (multiple addition points).
Particularly advantageously, two, three or four multiple addition points are arranged in succession.
For example, at least eight inlets Z1 may be present, in which case four inlets Z1 in each case open in a cross shape into the ring line R, the at least 2 groups of four inlets Z1 being arranged in succession and offset relative to one another.
Moreover, at least one third inlet Z3 may open into the ring line R, where at least one third inlet Z3 means that reactant 3, for example water, is supplied via one or more inlets Z3, and inlet Z3 is before inlet Z1 in flow direction and/or encloses inlet Z1.
The distance between inlets Z3 and Z1 is preferably from 10 to 500%, more preferably from 50 to 300%, more preferably from 80 to 200%, of the square root of the ring line cross section Q.
The ring line R is preferably configured as a Venturi tube at least one inlet Z1 to Z3.
The inlets more preferably open into a common Venturi tube.

## Claims

1. A neutralization process in which at least one ethylenically unsaturated carboxylic acid is neutralized at least partly with a base, which comprises continuously determining a content of at least one component in at least one stream of the neutralization, and regulating the neutralization based on results of the continuous determination.

2. The process according to claim 1, wherein a degree of neutralization and/or a solids content of the neutralized solution is determined continuously and is regulated by means of a metered addition of the base, the ethylenically unsaturated carboxylic acid, and/or water.

3. The process according to claim 2, wherein the degree of neutralization and/or the solids content of the neutralized solution is determined by means of near-infared spectra.

4. The process according to claim 1, wherein the base is an aqueous alkali.

5. The process according to claim 4, wherein an alkali content of the aqueous alkali is determined continuously and is regulated by means of a metered addition of water.

6. The process according to claim 5, wherein the content of aqueous alkali is determined by means of a measurement of density and temperature.

7. The process according to claim 4, wherein the ethylenically unsaturated carboxylic acid has a temperature of from 15 to 25° C. and/or the aqueous alkali has an alkali content of less than 25% by weight and a temperature of from 15 to 30° C., or the aqueous alkali has an alkali content of at least 25% by weight and a temperature of from 30 to 50° C., and/or, if used, the water has a temperature of from 15 to 30° C.

8. The process according to any of claim 4, wherein the aqueous alkali is a sodium hydroxide solution and/or the ethylenically unsaturated carboxylic acid is acrylic acid.

9. The process according to claim 1, wherein the neutralized solution is recycled partly into the neutralization.

10. The process according to claim 9, wherein between 25 and 95% of the neutralized solution is recycled.

11. The process according to claim 9, wherein the recycled neutralized solution, in the neutralization, is admixed with the base and the ethylenically unsaturated carboxylic acid.

12. The process according to claim 9, wherein the recycled neutralized solution, in the neutralization, is admixed with water, the base, and the ethylenically unsaturated carboxylic acid.

13. The process according to claim 1, wherein at least one metering point for the base, the ethylenically unsaturated carboxylic acid, and, if desired, water is designed as a Venturi tube.

14. A process for preparing water-absorbing polymers, comprising polymerizing a monomer solution neutralized according to the process of claim 1.