CN1708542A

CN1708542A - Absorbent polymer structure provided with an improved retention capacity and permeability

Info

Publication number: CN1708542A
Application number: CN200380101982.3A
Authority: CN
Inventors: J·哈伦; H·布雷姆; A·克尔克曼; S·拉姆洛
Original assignee: Chemische Fabrik Stockhausen GmbH
Current assignee: Evonik Super Absorbent Co ltd
Priority date: 2002-10-25
Filing date: 2003-10-24
Publication date: 2005-12-14
Anticipated expiration: 2023-10-24
Also published as: JP2006503948A; BR0315653A; DE10249821A1; CN1708542B; CN101885890A; JP4806191B2

Abstract

The invention relates to a method for producing an absorbent polymer structure (Pa) by treating the outer region of a non-treated absorbent polymer structure (Pu1), said method comprising the following steps: the outer region of the non-treated, absorbent polymer structure (Pu1) is brought into contact with an aqueous solution containing at least one chemical cross-linking agent and at least one inorganic compound in a colloidal form; and the absorbent polymer structure having an outer region which has been brought into contact with the aqueous solution is heated to a temperature of between 40 and 300 DEG C, such that the outer region of the absorbent polymer structure is more cross-linked than the inner region, and that the inorganic compound is at least partially immobilised in the outer region of the absorbent polymer structure.

Description

Maintenance capacity and infiltrative absorbent polymer structure with raising

The present invention relates to a kind of method of making absorbent polymer structure, a kind of can absorbent polymer structure obtained by this method, a kind of absorbent polymer structure, a kind of compound, a kind of method of making compound, a kind of can compound obtained by this method, the chemical products that contains this absorbent polymer structure or this compound, this absorbent polymer structure or the purposes of this compound in chemical products, a kind of aqueous solution, a kind of method of making this aqueous solution, a kind of can the aqueous solution obtained by this method, and the purposes of this aqueous solution in the absorbent polymer structure external treatment.

High absorption agent is the water-insoluble cross-linked polymer, and they can absorb a large amount of aqueous liquids, particularly body fluid by the generation of swelling and hydrogel, preferably urinates or blood, and possess them under certain pressure.Because mainly by adding sanitary product, for example baby diaper, incontinence article or cotton wool are to obtain application for these characteristics, these polymkeric substance.

Existing commercially available high-absorbent material is to be made by crosslinked polyacrylic acid or crosslinked starch-acrylic acid-grafted polymerisate substantially, and wherein carboxyl is partly neutralized by sodium hydroxide or potassium hydroxide.

For attractive in appearance and environment reason, more and more trend towards making littler thinner sanitary product.Total maintenance capacity in order to ensure sanitary product is constant, can only satisfy this demand by the ratio that reduces large volume fine hair thing.This means that further task falls the liquid of high absorption agent and shift and the distribution aspect, they may be summarized to be penetrating quality.

Perviousness in the high-absorbent material is meant the ability that under swollen state the liquid that adds is shifted and distributes on three-dimensional.Thereby this process is carried out capillary and is shifted and carry out in swollen high-absorbable gel by passing gap between the micelle.See through liquid that the high absorbent grains of swollen carries out itself and shift and follow the rule of diffusion and be process very slowly, it does not have any effect to distribution of liquid under the application state of sanitary product.For realizing the high-absorbent material that capillary shifts,, these materials guarantee that particle is disconnected from each other to prevent the gel caking phenomenon by being embedded fibrous matrix owing to lack gel stability.In upgrading the diaper configurations of several generations, absorption layer only contain seldom in addition fully not fibre shift to support liquid.Therefore, high absorption agent used herein must have sufficiently high stability under swollen state, makes the swollen gel still contain the capillary gap of capacity, and liquid can see through these spaces and shift.

In order to obtain to have the more high-absorbent material of high gel stability, can increase the degree of crosslinking of polymkeric substance on the one hand, the reduction that it causes the swelling ability inevitably and keeps capacity.Described in DE19646484, the optimum combination of different linking agents and comonomer can be improved penetrating quality really, but does not also reach the degree that the layer that optionally only is made of high absorption agent can be placed in the diaper configurations.

In addition, can use secondary treatment is carried out on the polymer beads surface method to improve the high-absorbable energy.Surface treatment can be known by prior art, for example from the teeth outwards secondary crosslinking of absorbent polymer structure, the surface contacted with mineral compound or carry out surperficial secondary crosslinking under the situation of mineral compound existing.

For example, EP-A-0450923, EP-A-0450922, DE-A-3523617, US 5,140,076 and US 4,734,478 described by among surperficial secondary crosslinking or make afterwards the surface contact the absorbable polymer surface handled with mineral compound (for example dispersive silicon-dioxide).Except improving the uptake rate part under pressure, this surface treatment can also improve the perviousness of this absorbable polymer.

DE 35 03 458 has described a kind of method of making improved absorbent resin, in the method, a kind of absorbent resin that contains monomeric unit (described monomer contains the carboxyl of free acid or salt form) as the resin moiety, can absorb crosslinking medium and water existing under the situation of metal oxide powder in small, broken bits, and the mixture that heating is made when stirring, thereby realize the crosslinked of resin and remove and anhydrate.Make the absorbent resin with good water-retaining capacity thus, it has good uptake rate simultaneously.

US 4,535,098 has described and has a kind ofly made absorbable polymer by absorbable polymer in the swelling under the situation that has dispersive colloid mineral compound (for example silica gel) or under by the situation that has dispersive colloid mineral compound, thereby increases the method for the gel strength of the high absorption agent of non-secondary crosslinking.

DE 198 05 447 discloses makes polyacrylonitrile hydrolyzed product and difunctional compound secondary crosslinking, make silicon-dioxide fixed method in the superabsorbent polymer surface structure simultaneously.Silicon-dioxide is contacted with the surface in water/alcohol mixture with crosslinking medium.By making silica stationary, can realize the reduction of absorbefacient raising and gel caking under the load.

DE 198 54 575 described before the polymerization, among or afterwards or in the neutralization of the part of high-absorbent material, add an alkali metal salt of silicic acid.By this surface treatment, obtained the perviousness that improves, yet this reduces owing to the part of the polymkeric substance confining force that can not the swelling additive causes mainly.

US 5,147, and 921 disclose the adding silicon sol as inert filler, and it can be scattered in treats in the polymeric monomer solution.

JP 1994-16822 has described with inorganic sol absorbable polymer has been carried out secondary surface preparation.Aspect the processing characteristics of the mixture that is easy to form agglomerate, add extra organic solvent component.Enumerated the monomethyl ether of glycol or dimethyl ether or glycol itself example as the organic solvent component.After the drying, in the simple experiment that does not have high absorption agent stress application to this, absorbable polymer should have the gel caking trend of higher gel stability, reduction and the water permeability of raising.

Description of the Prior Art or inorganic particle and high absorption agent done mix or inorganic particle is added in the secondary crosslinking process to prevent the agglomerant method of high absorbent grains by means of a large amount of part organic solvents.These methods still show some shortcomings, and promptly or must handle a large amount of solvents, this is from economical and all be unacceptable from ecological basis.In addition, be easy to agglomeration when superabsorbent polymer and a large amount of liquid mixing, the processing characteristics in this meeting grievous injury continuous flow procedure.On the other hand, cause decomposing with the simple fusion of inorganic material in small, broken bits or the shortcoming of airborne dust and so on.The aqueous solution itself that adds inorganic additives in crosslinked is difficult, because inorganic particle can deposit rapidly.In addition, be difficult to accurately measure inorganic dispersant.

Part is owing to the existence of disclosed inorganics in small, broken bits in the prior art, and the uneven distribution that produces chemical secondary crosslinking agent on the surface of absorbable polymer is with corresponding inhomogeneous crosslinked.This superabsorbent polymer that causes conversely obtaining has overall performance dissatisfactory, especially aspect retentivity and perviousness.Uniform distribution in the surface treatment method of prior art all is by using a large amount of aqueous solution that contains chemical cross-linking agent or alcoholic solution to realize in all cases.

Overall purpose of the present invention is to overcome the shortcoming that the prior art situation produces.

In addition, one object of the present invention is to provide following superabsorbent polymer: the high absorbed dose that it will be under pressure and be generally opposite performance (being high maintenance capacity and hypertonicity) and be combined into the performance combination, to satisfy requirement to the absorbable polymer of modern sanitary product, particularly diaper, incontinence article or cotton wool.Especially, these polymkeric substance should comprise minimum as far as possible poisonous monomer, for example acrylamide or vinyl cyanide, they can be washed out when superabsorbent polymer contacts with body fluid, and, for example be used under the situation of diaper at this superabsorbent polymer, can be in this way and the people's who wears diaper skin contact.

Another object of the present invention is to provide the sanitary product of diaper and so on, it is compared with known sanitary product in the prior art situation, more can possess the body fluid of absorption, absorbs liquid and make these liquid as far as possible rapidly and be evenly distributed in the sanitary product when absorbing liquid under pressure.

In addition, another object of the present invention is to create a kind of method, can make this absorbable polymer with minimum as far as possible organic solvent with this method.In this manufacturing process, the organic additive of adding should replace superabsorbent polymer at most only on a small quantity, and this can not have a negative impact to polymer performance.The solution that is used for that in the method the surface of absorbable polymer is handled should be able to be used as the single_phase system processing and add consistently.Applied high absorption agent should only form agglomerate and should be able to be used for the tempering step of operate continuously simply on slight extent in this treating processes.

The method of making absorbent polymer structure (Pa) by a kind of outside by the untreated polymer architecture of processing (Pu1) has realized above-mentioned purpose, and this method comprises the following steps:

-make untreated absorbent polymer structure (Pu1) the outside with comprise the aqueous solution of at least a chemical cross-linking agent and contact with the mineral compound of at least a dispersive colloid form;

-heat the absorbent polymer structure that its outside has contacted with the described aqueous solution 40 to 300 ℃ scopes, like this, preferably in this way, the outside of this absorbent polymer structure is compared crosslinked more strongly with inside, and mineral compound at least partial fixing in the outside of absorbent polymer structure.

Also can make the method realization above-mentioned purpose of absorbent polymer structure (Pa) by the outside of handling the absorbent polymer structure (Pu2) do not handle with the mineral compound of dispersoid form by a kind of, this method comprises the following steps:

-make absorbent polymer structure (Pu2) the outside with comprise the aqueous solution of at least a chemical cross-linking agent and contact with the mineral compound of at least a dispersive colloid form;

-heat the absorbent polymer structure that its outside has contacted with the described aqueous solution 40 to 300 ℃ temperature ranges, like this, preferably in this way, the outside of this absorbent polymer structure is compared crosslinked more strongly with inside, and mineral compound at least partial fixing in the outside of absorbent polymer structure.

According to absorbent polymer structure of the present invention (Pa) is fiber, foam or particle, wherein optimum fiber and particle, and particle is particularly preferred.By correspondingly using fiber, foam or particle to make absorbent polymer structure (Pu1) or (Pu2) obtaining the absorbent polymer structure (Pa) of these forms.

According to preferred absorbable polymer fiber of the present invention is such size: they can be inserted into or as the yarn that fabric is used, also can directly insert fabric.According to the present invention, the absorbable polymer fiber preferably has 1 to 500, the diameter of preferred 2 to 500, preferred especially 5 to 100 millimeters length and 1 to 200, preferred 3 to 100, preferred especially 5 to 60 DENIER.

According to preferred absorbent polymer particles of the present invention is such size: they have 10 to 3000, preferred 20 to 2000, preferred especially 150 to the 850 microns mean particle size according to ERT 420.1-99.

In the method for the invention, absorbent polymer structure (Pu1) or (Pu2) be preferably polymer architecture, its based on:

Monomer or its salt that (α 1) 20-99.999 weight %, preferred 55 to 98.99 weight %, the polymeric of preferred especially 70 to 98.79 weight %, ethylenic be undersaturated, contain acidic-group, or polymeric, ethylenic are undersaturated, the monomer that contains protonated nitrogen or quaternary nitrogen, or their mixture, the undersaturated monomer that contains acidic-group of ethylenic at least that wherein contains mixture, preferred vinylformic acid, be particularly preferred

(α 2) 0-80 weight %, preferred 0-44.99 weight %, preferred especially 0.1-44.89 weight % can with the polymeric of (α 1) copolymerization, single ethylenically unsaturated monomers,

One or more linking agents of (α 3) 0.001-5 weight %, preferred 0.01-3 weight %, preferred especially 0.01-2.5 weight %,

The water-soluble polymers of (α 4) 0-30 weight %, preferred 0-5 weight %, preferred especially 0.1-5 weight %, and

One or more additives of (α 5) 0-20 weight %, preferred 0-10 weight %, preferred especially 0.1-8 weight %, thus composition weight (α 1) to (α 5) and be 100 weight %.

The single ethylenically unsaturated monomers (α 1) that contains acidic-group can partially or completely be neutralized.Contain acidic-group the preferred 25 moles of % of single ethylenically unsaturated monomers, preferred especially 50 moles of %, more preferably 50-80 mole % is neutralized.With reference to DE 195 29 348, its disclosure is incorporated herein by this reference in this regard.Also can after polymerization, partially or completely neutralize.In addition, can neutralize with alkali metal hydroxide, alkaline earth metal hydroxides, ammonia and carbonate and supercarbonate.Can also use any other can generate the alkali of water-soluble salt with acid.Also can be with several alkali mixing neutralizations.Preferably with the neutralization of ammonia and alkali metal hydroxide, especially preferably with sodium hydroxide with use ammonia.

In addition, free acidic-group can account for major portion in polymkeric substance, makes the pH value of this polymkeric substance drop in the acidic region.This acidity water absorbent polymer can neutralize with polymkeric substance to the small part that contains free basic group (preferred amino), and it is alkaline that this polymkeric substance is compared with acidic polymer.In the document of for example " mixed bed ion exchange absorbable polymer " (Mixed-Bed Ion-Exchange AbsorbentPolymers) (MBIEA polymkeric substance), describe and in WO 99/34843, disclose these polymkeric substance especially.The disclosure of WO 99/34843 is incorporated herein by this reference and as a part of this disclosure.The MBIEA polymkeric substance usually produces following compound: it comprises the alkaline polymer that is positioned at the anionic position of exchange on the one hand, comprises on the other hand to compare with this alkaline polymer to be the tart polymkeric substance, and described acidic polymer is positioned at the position of exchange cation.This alkaline polymer contains basic group and usually makes by having the monomer polymerization that basic group maybe can change into the group of basic group.In these monomers, the most important thing is to contain the monomer of primary amine, secondary amine, tertiary amine or corresponding phosphine or at least two kinds of above-mentioned functional groups.This group monomer is particularly including ethylenamine, allylamine, diallyl amine, 4-aminobutene, alkyloxycycline, vinyl formamide, the amino amylene of 5-, carbodiimide, formaldacine, trimeric cyanamide and analogue and their secondary amine or tertiary amines derived thing.

Single ethylenic is undersaturated contain the monomer (α 1) of acidic-group can be partially or completely, preferred part is neutralized.The unsaturated acid group of single ethylenic preferably is neutralized at least 25 moles of %, especially preferably is neutralized at least 50 moles of %, most preferably is neutralized to 50-90 weight %.The neutralization of monomer (α 1) can also can carried out after polymerization before the polymerization.In addition, neutralization can be carried out with alkali metal hydroxide, alkaline earth metal hydroxides, ammonia and carbonate and supercarbonate.In addition, any other can also can use with the alkali that acid generates water-soluble salt.Also can be with different alkali mixing neutralizations.Preferably with ammonia or with alkali metal hydroxide neutralization, especially preferably with ammonia or use sodium hydroxide.

The undersaturated monomer (α 1) that contains acidic-group of preferred single ethylenic is a vinylformic acid, methacrylic acid, ethylacrylic acid, α-Lv Bingxisuan, alpha-cyanoacrylate, Beta-methyl vinylformic acid (Ba Dousuan), α-Ben Jibingxisuan, β-acryloxy propionic, sorbinic acid, c-chlorosorbinicacid, 2 '-methyl iso-crotonic acid, styracin, the p-chloro-cinnamic acid, β-stearic acid, methylene-succinic acid, citraconic acid, methylfumaric acid, propene dicarboxylic acid, equisetic acid, toxilic acid, fumaric acid, tricarboxythylene and maleic anhydride, wherein vinylformic acid and methacrylic acid especially vinylformic acid be particularly preferred.

Except these contain the monomer of carboxylate group, the undersaturated monomer (α 1) that contains acidic-group of other preferred single ethylenic is the unsaturated phosphonic acids monomer of ethylenic unsaturated sulfonic acid monomer or ethylenic.

Preferred ethylenic unsaturated sulfonic acid monomer is allyl sulphonic acid or aliphatic series or aromatic vinyl sulfonic acid or acrylic or methacrylic acid.Preferred aliphatic series or aromatic vinyl sulfonic acid are vinyl sulfonic acid, 4-vinyl benzyl sulfonic acid, vinyl toluene sulfonic acid and styrene sulfonic acid.Preferred acrylic or methacrylic acid is (methyl) vinylformic acid sulphur ethyl ester, (methyl) vinylformic acid sulphur propyl ester, 2-hydroxy-3-methyl acryloxy propyl sulfonic acid and 2-acrylamido-2-methyl propane sulfonic acid.

Other is the unsaturated phosphonic acids monomer of ethylenic preferably, for example vinyl phosphonate, allyl group phosphonic acids, vinyl benzyl phosphonic acids, (methyl) acrylamido alkyl phosphonic acid, acrylamido alkyl di 2 ethylhexyl phosphonic acid, (phosphonomethyl) vinyl-amine and (methyl) acryl phosphonate derivative.

The ethylenically unsaturated monomers (α 1) that preferably contains protonated nitrogen is (methyl) propenoic acid dialkyl amino ethyl ester hydrochloride of protonated form preferably, for example (methyl) dimethylaminoethyl acrylate hydrochloride or (methyl) dimethylaminoethyl acrylate hydrosulfate, and the dialkyl aminoalkyl of protonated form (methyl) acrylamide, for example dimethylaminoethyl (methyl) acrylamide hydrochloride or dimethylaminoethyl (methyl) acrylamide hydrosulfate.

The ethylenically unsaturated monomers (α 1) that preferably contains quaternary nitrogen is alkyl (methyl) the propenoic acid dialkyl ammonium of season form, for example ethyl (methyl) vinylformic acid TMA (TriMethylAmine)-methyl-sulfate (methosulfate) or methyl (methyl) vinylformic acid dimethyl second ammonium-ethyl sulfate (ethosulfate), and season form (methyl) acrylamido alkyl dialkylamine, for example chlorination (methyl) acrylamido propyl group TMA (TriMethylAmine) and sulfuric acid (methyl) acrylamido propyl group TMA (TriMethylAmine).

According to the present invention, preferably component (α 1) contains at least 50 weight %, preferred at least 70 weight %, the more preferably monomer that contains carboxylate group of at least 90 weight %.According to the present invention, particularly preferably be, component (α 1) contains the vinylformic acid of at least 50 weight %, preferred at least 70 weight %, and it preferably is neutralized at least 20 moles of %, especially preferably is neutralized at least 50 moles of %.

Preferably can be acrylamide and (methyl) acrylamide with single ethylenically unsaturated monomers (α 2) of (α 1) copolymerization.

Feasible (methyl) acrylamide is the derivative that alkyl replaces the aminoalkyl group replacement of (methyl) acrylamide or (methyl) acrylamide except that acrylamide and Methacrylamide, for example N-methylol (methyl) acrylamide, N, N-dimethylamino (methyl) acrylamide, dimethyl (methyl) acrylamide or diethyl (methyl) acrylamide.Feasible vinylamide is, for example, and N-vinylamide, N-vinyl formamide, N-vinyl acetamide, N-vinyl-N-methylacetamide, N-vinyl-N-methylformamide, vinyl pyrrolidone.In these monomers, acrylamide is particularly preferred.

Other can be the water dispersible monomer with single ethylenically unsaturated monomers (α 2) of (α 1) copolymerization preferably.Preferred water dispersible monomer is the ester of acrylic acid ester and methacrylic acid, for example (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate or (methyl) butyl acrylate, and polyoxyethylene glycol (methyl) methyl acrylate, methyl polyoxyethylene glycol allyl ethers, vinyl-acetic ester, vinylbenzene and iso-butylene.

According to preferred cross-linking agents of the present invention (α 3) is the compound (linking agent class I) that contains at least two ethylenic unsaturated groups in the molecule; The compound (linking agent class II) that contains at least two functional groups that can in condensation reaction (being the condensation cross-linking agent), addition reaction or ring-opening reaction, react with the functional group of monomer (α 1) or (α 2); The compound (linking agent class III) that contains the functional group that at least one ethylenic unsaturated group and at least one can react with the functional group of monomer (α 1) or (α 2) in condensation reaction (being the condensation cross-linking agent), addition reaction or ring-opening reaction; Or multivalent metal cation (linking agent class IV).Realize polymkeric substance crosslinked by the ethylenic unsaturated group of cross-linker molecules with the Raolical polymerizable of single ethylenically unsaturated monomers (α 1) or (α 2) with the compound of linking agent class I thus, and with the multivalent metal cation of the compound of linking agent class II and linking agent class IV condensation reaction (linking agent class II) or electrostatic interaction (linking agent class IV) the realization polymkeric substance of the functional group by multivalent metal cation and (α 1) or (α 2) crosslinked by the functional group of functional group and monomer (α 1) or (α 2).Compound with linking agent class III correspondingly passes through the Raolical polymerizable of ethylenic unsaturated group or realizes the crosslinked of polymkeric substance by the condensation reaction between the functional group of linking agent functional group and monomer (α 1) or (α 2) equally.

The preferred compound of linking agent class I is many (methyl) acrylate or many (methyl) acrylamide, they transform and make by the polyvalent alcohol that makes polyvalent alcohol (for example ethylene glycol, propylene glycol, TriMethylolPropane(TMP), 1,6-hexylene glycol, glycerol, tetramethylolmethane, polyoxyethylene glycol or polypropylene glycol), amino alcohol, polyalkylenepolyamines (for example diethylenetriamine or Triethylenetetramine (TETA)) or pure salinization with acrylic or methacrylic acid.The more preferably compound of linking agent class I is (methyl) acrylate of polyvinyl compound, poly-(methyl) allylic cpd, mono-vinyl compound (methyl) acrylate or single (methyl) allylic cpd, is preferably list (methyl) allylic cpd many alcohol or amino alcohol.In this respect, with reference to DE 195 43 366 and DE 195 43 368.These openly are incorporated herein by this reference and as a part of this disclosure.

The example of the compound of linking agent class I is specified thiazolinyl two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate for example, 1, ammediol two (methyl) acrylate, 1,4-butyleneglycol two (methyl) acrylate, 1,3-butyleneglycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, 1,10-decanediol two (methyl) acrylate, 1,12-dodecanediol two (methyl) acrylate, 1,18-octadecandiol two (methyl) acrylate, ring pentanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, two (methyl) vinylformic acid methylene ester or tetramethylolmethane two (methyl) acrylate; Thiazolinyl two (methyl) acrylamide, for example N-methyl two (methyl) acrylamide, N, N '-3-methyl butylidene two (methyl) acrylamide, N, N '-(1,2-dihydroxyl ethylidene) two (methyl) acrylamide, N, N '-hexylidene two (methyl) acrylamide or N, N '-methylene radical two (methyl) acrylamide; Many alkoxyl groups two (methyl) acrylate, for example two (methyl) vinylformic acid glycol ether ester, two (methyl) vinylformic acid triethyleneglycol ester, two (methyl) vinylformic acid Tetraglycol 99 ester, two (methyl) vinylformic acid dipropylene glycol ester, two (methyl) vinylformic acid tripropylene glycol ester or two (methyl) vinylformic acid, four propylene glycol esters; Bisphenol-A-two (methyl) acrylate, ethoxylation bisphenol-A two (methyl) acrylate, two (methyl) vinylformic acid benzene methylene ester, 1,3-two (methyl) acryloyl-oxy propyl alcohol-2, Resorcinol two (methyl) acrylate, preferred every hydroxyl is with two (methyl) acrylate of 1 to the 30 oxyalkylated TriMethylolPropane(TMP) of mol of alkylene oxide, be preferably two (methyl) acrylate of the TriMethylolPropane(TMP) of ethoxylation, THIOGLYCOL two (methyl) acrylate, sulfo-propylene glycol two (methyl) acrylate, sulfo-polyoxyethylene glycol two (methyl) acrylate, sulfo-polypropylene glycol two (methyl) acrylate; Divinyl ether, for example 1,4-butyleneglycol divinyl ether; Divinyl ester, for example hexanodioic acid divinyl ester; The straight chain diene, divinyl or 1 for example, 6-hexadiene; Vinylstyrene; Two (methyl) allylic cpd, for example phthalic acid two (methyl) allyl ester or succsinic acid two (methyl) allyl ester; The homopolymerization of chlorination two (methyl) allyl dimethyl base ammonium and the homopolymerization and the multipolymer of multipolymer and chlorination diethyl (methyl) allyl amino methyl (methyl) ammonium acrylate; Vinyl (methyl) acrylic compound, for example (methyl) vinyl acrylate; (methyl) allyl group (methyl) acrylic compound, for example (methyl) vinylformic acid (methyl) allyl ester, every hydroxyl are with (methyl) vinylformic acid (methyl) allyl ester of 1 to 30 moles of ethylene oxide ethoxylation; Two (methyl) allyl ester of many carbonic acid, for example toxilic acid two (methyl) allyl ester, fumaric acid two (methyl) allyl ester, succsinic acid two (methyl) allyl ester or terephthalic acid two (methyl) allyl ester; The compound that has 3 or the more undersaturated free redical polymerization group of ethylenic, three (methyl) vinylformic acid glyceryl ester for example, every hydroxyl is preferably used (methyl) acrylate of the glycerine of 1 to 30 moles of ethylene oxide ethoxylation, trimethylolpropane tris (methyl) acrylate, every hydroxyl is preferably used three (methyl) acrylate of 1 to the 30 oxyalkylated TriMethylolPropane(TMP) of mol of alkylene oxide, be preferably three (methyl) acrylate of the TriMethylolPropane(TMP) of ethoxylation, the trimethylammonium acrylamide, two (methyl) vinylformic acid (methyl) allylidene ester, 3-allyloxy-1,2-propylene glycol two (methyl) acrylate, cyanogen urea acid three (methyl) allyl ester, isocyanuric acid three (methyl) allyl ester, tetramethylolmethane four (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, every hydroxyl is preferably used the methacrylic ester of the tetramethylolmethane of 1 to 30 moles of ethylene oxide ethoxylation, three (2-hydroxyethyl) isocyanuric acid ester three (methyl) acrylate, the tri trimellitate vinyl acetate, three (methyl) allylamine; Two (methyl) allyl group alkylamine, for example two (methyl) allyl group methylamine; Tricresyl phosphate (methyl) allyl ester, four (methyl) allyl group quadrol, poly-(methyl) allyl ester, four (methyl) allyloxy ethane or halogenation four (methyl) allyl-ammonium.

The preferred compound of linking agent class II be contain at least two can with the functional group of monomer (α 1) or (α 2), preferably with the acidic-group of monomer (α 1) in condensation reaction (being the condensation cross-linking agent), at the compound of the addition reaction or the functional group of in ring-opening reaction, reacting.The example of these functional groups of the compound of linking agent class II can be alcohols, amino, aldehyde, Racemic glycidol, isocyanic ester, carbonic ether or table chlorine official energy.

The example of the compound of linking agent II can be mentioned polyvalent alcohol, for example ethylene glycol; Many ethylene glycol, for example glycol ether, triglycol, Tetraglycol 99; Propylene glycol; Many propylene glycol are as dipropylene glycol, tripropylene glycol or four propylene glycol; 1,3-butyleneglycol, 1.4-butyleneglycol, 1,5-pentanediol, 2,4-pentanediol, 1,6-hexylene glycol, 2,5-hexylene glycol, glycerine, Polyglycerine, TriMethylolPropane(TMP), polyoxypropylene, oxygen ethene-oxypropylene-segmented copolymer, sorbitan-fat acid esters, polyoxyethylene sorbitan-fat acid esters, tetramethylolmethane, polyvinyl alcohol and Sorbitol Powder; Amino alcohol is as thanomin, diethanolamine, trolamine or Propanolamine; Polyamine compounds, for example 1, diethylenetriamine, Triethylenetetramine (TETA), tetren or penten; Polyglycidyl ether compound, for example ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, glycerol diglycidylether, glycerol polyglycidylether, tetramethylolmethane polyglycidyl ether, propylene glycol diglycidylether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, hexylene glycol glycidyl ether, trimethylolpropane polyglycidylether, sorbitol polyglycidylether; O-phthalic acid diglycidyl ester; The hexanodioic acid diglycidylether; 1,4-phenylene two (2-oxazoline); Racemic glycidol; Polyisocyanates is preferably for example vulcabond of 2,4 toluene diisocyanate and hexamethylene diisocyanate; Many aziridine cpds, for example 2,2-dihydroxymethyl butanols-three [3-(1-'-aziridino) propionic ester], 1,6-hexa-methylene diethylidene urea and ditan-two-4,4 '-N, N '-diethylidene urea; Halogenated epoxide, for example Epicholorohydrin and epibromohydrin and Alpha-Methyl Epicholorohydrin; Alkylene carbonates, for example 1,3-dioxolane-2-ketone (ethylene carbonate), 4-methyl isophthalic acid, 3-dioxolane-2-ketone (Texacar PC); 4,5-dimethyl-1,3-dioxolane-2-ketone, 4,4-dimethyl-1,3-dioxolane-2-ketone, 4-ethyl-1,3-dioxolane-2-ketone, 4-methylol-1,3-dioxolane-2-ketone, 1,3-dioxolane-2-ketone, 4-methyl isophthalic acid, 3-diox-2-ketone, 4,6-dimethyl-1,3-diox-2-ketone, 1,3-dioxolane-2-ketone, poly--1,3-dioxolane-2-ketone; Poly-quaternary amine, for example condensation product of dimethylamine and Epicholorohydrin.In addition, other preferred compound of linking agent class II is for example 1,2-Ya Yi Ji bisoxazoline and so on De Duo oxazoline, the linking agent that has silylation of γ-Huan Yangbingyangbingjisanjiayangjiguiwan and γ-An Bingjisanjiayangjiguiwan for example, for example 2-oxazolidone, two-2-oxazolidone and many-2-oxazolidone and so on De oxazolidone, and silicic acid glycol ether ester.

The preferred compound of class III is to contain hydroxyl or amino (methyl) acrylate, for example (methyl) vinylformic acid 2-hydroxyl ethyl ester, and (methyl) acrylamide that contains hydroxyl or amino, or the list of glycol (methyl) allylic cpd.

The multivalent metal cation of linking agent class IV is preferably derived from single electric charge or multi-charge positively charged ion, and unicharged special in for example basic metal of potassium, sodium, lithium, wherein lithium is preferred.Preferred double charge positively charged ion is from the alkaline-earth metal of zinc, beryllium, for example magnesium, calcium, strontium, and wherein magnesium is preferred.Other positively charged ion that has higher electric charge according to available of the present invention is from the positively charged ion of aluminium, iron, chromium, manganese, titanium, zirconium and other transition metal and the mixture of these cationic double salt or described salt.Preferred aluminium salt and vitriol and various hydrate, for example AlCl of using ₃6 H ₂O, NaAl (SO ₄) ₂12H ₂O, KAl (SO ₄) ₂12 H ₂O or Al ₂(SO ₄) ₃14-18 H ₂O.

The particularly preferred Al that is to use ₂(SO ₄) ₃And hydrate is as the linking agent of class IV linking agent.

Preferred absorbent polymer structure (Pu1) or (Pu2) be following polymer architecture, its linking agent by following linking agent class or the linking agent by following linking agent class combination carry out crosslinked: I, II, III, IV, I II, I III, I IV, I II III, I II IV, I III IV, II III IV, II IV or III IV.The combination of above-mentioned linking agent class produces the preferred embodiment of the linking agent of polymkeric substance separately.

Absorbent polymer structure (Pu1) or more preferred (Pu2) are the crosslinked polymer architectures of any above-mentioned linking agent by linking agent class I.Wherein, water-soluble cross-linker is preferred.In this regard, particularly preferably be N, allyl group nine EDIAs that N '-methylene diacrylamine, polyoxyethylene glycol two (methyl) acrylate, chlorination triallyl first ammonium, chlorination tetraallyl ammonium and the acid of every mol propylene are made with 9 moles of ethylene oxide.

About water-soluble polymers (α 4), preferably following water-soluble polymeric product can be aggregated to absorbent polymer structure of the present invention (Pu1) or (Pu2) in: for example contain partially or completely saponified polyvinyl alcohol, polyvinylpyrrolidone, starch or starch derivative, polyglycol or polyacrylic water-soluble polymeric product.The molecular weight of these polymkeric substance is not crucial, as long as they are water miscible.Preferred water-soluble polymers is starch or starch derivative or polyvinyl alcohol.Water-soluble polymers, preferably synthetic quasi-polyethylene alcohol also can be as the fishplate bar basis for the treatment of polymerization single polymerization monomer.

About additive (α 5), be used for the absorbent polymer structure (Pu1) of the inventive method or (Pu2) preferred package suspending agent-containing, tensio-active agent, smell tackiness agent (odour binders), filler or antioxidant.

According to the present invention, particularly preferably be, absorbent polymer structure (Pu1) or (Pu2) be the following particulate crosslinked polypropylene that makes: (wherein acrylic acid content is 5 to 80 weight % of aqueous solution weight at the aqueous solution by vinylformic acid and non-essential a kind of above-mentioned linking agent, preferred 10 to 70 weight %, preferred especially 20 to 50 weight %) polymerization in, then the polymer gel of making is reduced to small shreds, with being reduced to the gel drying of small shreds, optionally the exsiccant polymer gel is further ground then.The absorbent polymer structure preferred feature that makes by this way is that water-content is 0.5 to 25 weight %, preferred 1 to 10 weight %.

In a preferred embodiment of the invention, with absorbent polymer structure (Pu1) or (Pu2) be neutralized at least 50 weight %, preferably be neutralized at least 75 weight %, most preferably be neutralized at least 90 weight %, this is based on vinylformic acid, it preferably is neutralized at least 20 moles of %, especially preferably at least 50 moles of %.

More preferably, absorbent polymer structure (Pu1) or (Pu2) be not based on polyacrylonitrile milk sap.Wherein preferably, absorbent polymer structure (Pu1) or (Pu2) be based on be lower than 37 moles of %, especially preferably be lower than 20 moles of %, more preferably less than 10 moles of %, preferably be lower than acrylamide and/or the acrylonitrile monemer of 5 moles of % again.In this respect, more preferably, absorbent polymer structure (Pu1) or (Pu2) contain be lower than 1000ppm, especially preferably be lower than 500ppm, more preferably less than 100ppm, preferably be lower than solvable monomer or the polymkeric substance of 10ppm again based on vinyl cyanide and/or acrylamide monomer.

Can make absorbent polymer structures (Pu1) or (Pu2) by various polymerization methodses by above-mentioned monomer and linking agent.For example, in this respect, that can mention has mass polymerization, solution polymerization, spray polymerization, inverse emulsion polymerization and an inverse suspension polymerization that preferably carries out in the reactor of kneading of for example extruding machine.Solution polymerization is preferably carried out in as the water of solvent.Solution polymerization can be carried out continuously or discontinuously.From prior art, can collect a large amount of feasible programs aspect the reaction conditions of temperature for example initiator and reaction soln, type and quantity.Typical method: US 4,286,082, DE 27 06 135, US 4,076,663, DE3503458, DE 40 20 780, DE 42 44 548, DE 43 23 001, DE 43 33 056, DE44 18 818 have been described in following patent specification.These openly are incorporated herein by this reference and constitute a part of this disclosure thus.

Another kind of make absorbent polymer structure (Pu1) or (Pu2) may be at first preferably to make noncrosslinking, linear polymkeric substance particularly by the free radical mode by above-mentioned single ethylenically unsaturated monomers (α 1) or (α 2), then with serve as the reagent of linking agent (α 3), preferably the linking agent with class II and IV transforms them.If polymer architecture is at first handled in the figuration process, for example, with formation fiber, film or other two dimensional structure (for example fabric, knitted fabrics, fabric or pile fabric), and crosslinked with this form, so preferably use this scheme.

By common initiator initiated polymerization.All initiators that form free radical under polymerizing condition can cause this polymeric initiator with acting on, and these initiators are usually used in making high absorption agent.Also is feasible by electron beam to the effect initiated polymerization of the polymerizable aqueous solution.Really can be under the situation of the initiator that does not have the above-mentioned type, by at the effect initiated polymerization that has the high energy beam under the condition of light trigger.Can use dissolving or be dispersed in polymerization starter in the monomer solution of the present invention.Can use well known by persons skilled in the art all resolve into the compound of free radical as initiator.Particularly following superoxide, hydroperoxide, hydrogen peroxide, persulphate/ester, azo-compound and so-called redox catalyst.The preferred water-soluble catalyst that uses.In some cases, advantageously use the mixture of different polymerization starters.In these mixtures, preferably contain the mixture of hydrogen peroxide and Sodium persulfate or potassium, they can use with any amount ratio that can expect.Suitable organo-peroxide preferably diacetone peroxide, methylethyl ketone peroxide, t-butyl hydroperoxide, hydrogen phosphide cumene, cross the PIVALIC ACID CRUDE (25) tert-pentyl ester, cross the PIVALIC ACID CRUDE (25) tert-butyl ester, cross new hecanoic acid t-butyl ester, tert-butyl isobutyrate, mistake-2-ethyl tert-butyl isobutyrate, cross the different n-nonanoic acid tert-butyl ester, tert butyl permaleic acid, the perbenzoic acid tert-butyl ester, 3,5, the 5-tri-methyl hexanoic acid tert-butyl ester and mistake neodecanoic acid pentyl ester.Other preferred polymerization initiator is: azo-compound; as two hydrochlorinates 2; 2 '-azo two (2-amidine propane), two hydrochlorinates azo-diamidino propane, two hydrochlorinates 2; 2 '-azo, two (N; the N-dimethylene) NSC 18620,2-(formamyl azo) isopropyl cyanide and 4,4 '-azo two (4-cyanovaleric acid).Described compound uses with positive usual amounts, is preferably to treat 0.01 to 5 of polymeric amount of monomer, preferred 0.1 to 2 mole of %.

Redox catalyst contains at least a above-mentioned mistake-compound (per-compound) as oxidation component, with preferred xitix, glucose, sorbose, seminose, ammonium or alkali-metal hydrosulphite, vitriol, thiosulphate, thiosulphate (hyposulfite) or sulfide, metal-salt, for example iron (II) ion or silver ions or methylol sodium hydrosulfite 90min are as reduction components.Be preferably used as redox catalyst reduction components be xitix or Sodium Pyrosulfite.Based on monomeric amount used in the polymerization, use 1 * 10 ^-5Redox catalyst reduction components and 1 * 10 to 1 mole of % ^-5Redox catalyst oxidation component to 5 moles of %.Can use one or more preferred water miscible azo-compounds to replace the oxidation component of redox catalyst, perhaps outside the oxidation component of redox catalyst, also use described azo-compound.

If the effect initiated polymerization by high energy beam uses so-called light trigger usually.These can comprise that for example so-called α-disintegrating agent, H-extract system (H-abstracting systems) or also comprise trinitride.The example of these initiators is benzophenone derivates, phenanthrene derivative, fluorine derivative, anthraquinone derivative, thioxanthone derivates, α-benzofuranone derivatives, benzoin ether and the derivative thereof of for example Michler's keton, for example azo-compound, the Hexaarylbiimidazole or the acylphosphine oxide of replacement of above-mentioned radical former.The embodiment of trinitride is: 2-(N; the N-dimethylamino) ethyl-4-azido-laurate; 2-(N; the N-dimethylamino) ethyl-4-azido-naphthyl ketone; 2-(N; the N-dimethylamino) ethyl-4-triazobenzene manthanoate; 5-azido--1-naphthyl-2 '-(N; the N-dimethylamino) ethyl sulfone; N-(4-sulfonyl azide phenyl) maleimide; N-ethanoyl-4-alkylsulfonyl azido-aniline; 4-alkylsulfonyl nitrine aniline; 4-nitrine aniline; 4-azido benzoyl monobromomethane; right-azidobenzoic acid; 2; 6-two (to the nitrine benzylidene) pimelinketone and 2,6-two (to the nitrine benzylidene)-4-methylcyclohexanone.If use light trigger, its consumption are generally 0.01 to the 5 weight % that treats polymerization single polymerization monomer.

The redox system of preferably using according to the present invention comprises hydrogen peroxide, Sodium persulfate and xitix.Usually azo-compound is preferably as initiator of the present invention, and wherein two hydrochlorinate azos two (amidine propane) are particularly preferred.

Usually use the initiator initiated polymerization at 30 to 90 ℃.

Under being in 100 to 200 ℃ of temperature in the scope usually with the polymer gel drying to reach the water content of 0.5 to 25 weight %, preferred 1 to 10 weight %.

In preferred embodiments, the absorbent polymer structure (Pu1) that uses in the method for the present invention or (Pu2) have at least a (ERT=EDANA recommend test) in the following character:

(A) according to ERT 440.1-99 to the maximum absorption of the NaCl solution of 0.9 weight % at least 10 to 1000, preferred 15 to 500, preferred especially 20 to 300g/g,

(B) part that can extract with the NaCl solution of 0.9 weight % according to ERT 470.1-99 for be lower than absorbent polymer structure (Pu1) or 30 weight % (Pu2), preferably be lower than 20 weight %, especially preferably be lower than 10 weight %,

(C) according to the tap density of ERT 460.1-99 be 300 to 1000, preferred 310 to 800, preferred especially 320 to 700 grams per liters,

(D) 1 gram absorbent polymer structure (Pu1) or (Pu2) in 1 premium on currency the time pH value according to ERT400.1-99 be 4 to 10, preferred 5 to 9, preferred especially 5.5 to 7.5.

(E) crc value according to ERT 441.1-99 is 10 to 100, and is preferred 15 to 80, and preferred especially 20 to 60g/g.

The properties of combination of two or more character that produced by above-mentioned character has produced the preferred embodiment of the inventive method separately.More particularly preferred embodiment is following method, wherein absorbent polymer structure (Pu1) or (Pu2) have following letter character or letter character the combination shown in following character or properties of combination: A, B, C, D, E, AB, AC, AD, AE, ABC, ABD, ABE, ACD, ACE, ADE, ABCD, ABCE, ABDE, ACDE, ABCDE.

Preferably make absorbent polymer structure (Pu1) in the method for the invention or (Pu2) contact with the aqueous solution by the aqueous solution and absorbent polymer structure (Pu1) or well blend (Pu2).This aqueous solution does not preferably contain organic solvent substantially, does not particularly contain the pure and mild multi alkylidene diol ether of multivalence, does not especially preferably contain diethylene glycol monomethyl ether and 1,3 butylene glycol.Particularly preferably be in this respect, the aqueous solution is considered to be meant that the content of water accounts in the aqueous solution all respectively and at room temperature is at least 50 weight %, the preferred especially at least 60 weight % of the component total amount of liquid, more preferably at least 70 weight %, the solution of preferred at least 90 weight % again.

Chemical cross-linking agent can be present in the aqueous solution of the mineral compound that contains the dispersoid form from the beginning thus.But chemical cross-linking agent and dispersoid mineral compound also can be individually but preferred the contact with absorbent polymer structure (Pu1) or (Pu2) simultaneously.In this case; preferred two kinds of solution that separate---wherein a kind of chemical cross-linking agent that contains; another kind contains the mineral compound of dispersoid form---and the preferred while mixes with absorbent polymer structure (Pu1) or (Pu2), but must guarantee the uniform distribution of the mineral compound of chemical cross-linking agent and dispersoid form thus.

The mixing device that is applicable to applied component is, for example, Patterson-Kelley mixing machine, DRAIS turbulent flow mixing machine, L dige mixing machine, Ruberg mixing machine, mixing screw, pan mixer and thermopnore mixing machine and move vertical mixer continuously, wherein polymer architecture utilizes revolving scraper to mix (Schugi mixing machine) with fast frequency.In the methods of the invention absorbent polymer structure (Pu1) or (Pu2) with account at the most absorbent polymer structure (Pu1) or (Pu2) weight 20 weight %, preferred especially and 15 weight % at the most, more preferably with 10 weight % at the most, more preferred and 5 weight % at the most with most preferably contact with the water that is lower than 3 weight %.

Using absorbent polymer structure (Pu1) with the form that is preferably spheroidal particle or (Pu2) time, according to the present invention, further preferably contact in the following manner: the outside of particle shape absorbent polymer structure but not inner contact only with the mineral compound of dispersoid form.In this respect, it is the part with following characteristics that the outside of polymer architecture preferably is understood as: each spatial point in this part and the distance at particle center equal at least 50% of particle shape absorbent polymer structure radius, especially preferably at least 75%, more preferably at least 90%, more preferably at least 95%.The dispersoid mineral compound of Shi Xianing inhomogeneous fixing on polymer architecture thus, contact realization according to the present invention with the aqueous solution by making the exsiccant polymer architecture, and only use a spot of water, the amount of water is so few to make only in the outside absorption that realizes the aqueous solution of absorbable polymer.

In the method for the invention further preferably, at least 30 weight %, preferred especially at least 60 weight %, most preferably the granularity of the dispersoid mineral compound of at least 90 weight % be 1 to 100, preferred 5 to 80, most preferably 6 to 50 nanometers.

According to method of the present invention, mineral compound preferably with account for absorbent polymer structure (Pu1) or 0.001 to 10 weight % (Pu2), preferred especially 0.01 to 5 weight %, most preferably the amount of 0.05 to 1.5 weight % contacts with absorbent polymer structure (Pu1) or (Pu2).

About mineral compound, can use all to meet the water-insoluble mineral compound of following condition---can obtain stable, dispersive colloidal state by it, preferred single-phase water solution, this aqueous solution is under 20 ℃ and normal pressure, in at least 6 hours, preferred at least 24 hours, preferred at least 72 hours to 6 months especially time bar, do not show and be separated, for example the sedimentary deposition of solid inorganic.

Dispersive colloidal solution is meant that preferably containing particle diameter is 100-1000 (10 ^-4To 10 ^-5Centimetre) particulate solution.These solution have the character that makes by light beam scattering on all directions of solution, so just can follow the tracks of path (Tyndall effect by the light beam of solution, referring to Hollemann-Wiberg, Lehrbuch der anorganischen Chemie, 91st-100thedition, de Gruyter-Verlag, the 765th page).

The particularly preferred dispersoid mineral compound that is used for the inventive method is the particle that contains poly-silicic acid.Can for example following acquisition contain this particulate dispersive colloidal solution (silicon sol): by the careful acidifying of the sodium silicate solution that reacts as alkali that causes by hydrolysis, or by molecule silicic acid is water-soluble and may make the dispersive colloidal solution stabilization of making subsequently.The accurate manufacturing of this silicon sol is well known by persons skilled in the art, and for example at Jander Blasius, Lehrbuch deranalytischen und pr  parativen anorganischen Chemie, S.Hirzel Verlag describes among the Stuttgart to some extent.

Except the dispersive colloid silicic acid,, be hydrous iron oxide (III) colloidal sol, aqua oxidation tin (IV) colloidal sol or more preferably based on the colloidal sol of silver halide, particularly silver chloride as the dispersoid mineral compound according to the present invention.

Chemical cross-linking agent (it is included in the aqueous solution in the methods of the invention) preferably is meant the compound that contains at least two functional groups, these two functional groups can with the functional group of polymkeric substance in condensation reaction (condensation cross-linking agent), react in addition reaction or in ring-opening reaction, perhaps be meant the multivalent metal cation that can make crosslinked polymer by the electrostatic interaction of multivalent metal cation and polymers functionality.Be used for the absorbent polymer structure (Pu1) or (Pu2) chemical cross-linking agent of outside secondary crosslinking in the method for the invention and---be also referred to as that " secondary crosslinking agent "---is preferably the linking agent of mentioning as the linking agent of linking agent class II and IV at the context of linking agent (α 3).

In these compounds, the condensation cross-linking agent is particularly preferred secondary crosslinking agent, glycol ether for example, triglycol, polyoxyethylene glycol, glycerine, Polyglycerine, propylene glycol, diethanolamine, trolamine, polyoxypropylene, oxygen ethene-oxypropylene segmented copolymer, sorbitan aliphatic ester, the polyoxyethylene sorbitan aliphatic ester, TriMethylolPropane(TMP), tetramethylolmethane, polyvinyl alcohol, Sorbitol Powder, 1,3-dioxolane-2-ketone (ethylene carbonate), the 4-methyl isophthalic acid, 3-dioxolane-2-ketone (Texacar PC), 4,5-dimethyl-1,3-dioxolane-2-ketone, 4,4-dimethyl-1,3-dioxolane-2-ketone, 4-ethyl-1,3-dioxolane-2-ketone, 4-methylol-1,3-dioxolane-2-ketone, 1,3-dioxane-2-ketone, the 4-methyl isophthalic acid, 3-dioxane-2-ketone, 4,6-dimethyl-1,3-dioxane-2-ketone, 1,3-dioxolane-2-ketone, gather-1,3-dioxolane-2-ketone.

What be preferably used as the secondary crosslinking agent especially is ethylene carbonate.

In the method for the invention the preferable amount of secondary crosslinking agent be absorbent polymer structure (Pu1) or (Pu2) 0.01 to 30, preferred especially 0.1 to 20, most preferably 0.3 to 5 weight %.

After the aqueous solution of chemical cross-linking agent and inorganic-containing compound with absorbent polymer structure (Pu1) or (Pu2) contacts, in the methods of the invention by the secondary crosslinking reaction taking place at 40 to 300 ℃, preferred 80 to 250 ℃, preferred especially 150 to 220 ℃ of heating absorbent polymer structures.Can easily investigate the best time length of second-heating at various linking agent types and dispersive colloid mineral compound.When the required performance situation of high absorption agent being suffered damage, reach the second-heating time limit owing to heat collapse.Can in typical moisture eliminator or baking oven, heat-treat, for example round shape rotary oven, fluid bed furnace, disk dryer, pedal-type dryer or infrared dryer.

According to the present invention preferably, because thermal treatment, the outside of absorbent polymer structure is more crosslinked more strongly than inside, and by thermal treatment, and partial fixing is externally at least for mineral compound.More preferably outside in this article radius is less than three times of the inner radial value.

In another embodiment of the inventive method, with contain before or after the aqueous solution of chemical cross-linking agent with the mineral compound of dispersoid form contacts, preferred after, make absorbent polymer structure outside with contain Al ³⁺The contact of ionic compound.Wherein preferably contain Al ³⁺Compound respectively with the amount of 0.01 to the 30 weight % that accounts for absorbent polymer structure weight, preferred especially with the amount of 0.1 to 20 weight %, most preferably the amount with 0.3 to 5 weight % contacts with polymer architecture.

Preferably by absorbent polymer structure (Pa) is mixed under drying conditions with compound or by make absorbent polymer structure (Pa) with contain solvent (preferably water, water miscibility organic solvent, for example methyl alcohol or ethanol or wherein at least two kinds mixture) and contain Al ³⁺The contact of the fluid of ionic compound, with the outside of carrying out absorbent polymer structure with contain Al ³⁺The contact of ionic compound, wherein contact is preferably by carrying out with fluid spray polymer beads and mixing.In this article, more preferably in two-step approach, make absorbent polymer structure (Pa) contain Al with containing ³⁺The fluid contact of compound.Wherein two-step approach comprises first mixing process (wherein multiple absorbent polymer structure mixes with fluid) and second mixing process (wherein making fluid in the inner homogenizing of polymer beads), wherein in first mixing process with making the kinetic energy of single polymer beads in the medium greater than the speed mixing of polymer particles of the adhesion energy between the single polymer beads, and in second mixing process, use the speed thorough mixing polymer beads lower than first mixing process.

By above-mentioned two-step approach with containing Al ³⁺The fluid handling absorbent polymer structure (Pa) of ionic compound can obtain the absorbent polymer structure that absorptive character improve.

Do not consider crystalline water, contain Al ³⁺The ionic compound preferably content in fluid is respectively 0.1 to 50 weight % of fluid gross weight, is preferably 1 to 30 weight % especially.Further preferably, the amount that this fluid contacts with absorbent polymer structure (Pa) is respectively 0.01 to 15 weight % of absorbent polymer structure (Pa) weight, is preferably 0.05 to 6 weight % especially.

Contain Al ³⁺Preferred compound be AlCl ₃6 H ₂O, NaAl (SO ₄) ₂12 H ₂O, KAl (SO ₄) ₂12 H ₂O or Al ₂(SO ₄) ₃14-18 H ₂O.

Foregoing invention further relates to can be by the absorbent polymer structure (Pa) of aforesaid method acquisition of the present invention.

In addition, the absorbent polymer structure (Pa) that the present invention relates to comprise inside and center on the outside of this inside, wherein outside crosslinked more strongly than inside, partial fixing is externally at least for mineral compound, preferably only externally and not in inside, and wherein this absorbent polymer structure (Pa) has at least a in the following character:

(β 1) for according to the CRC of ERT 441.1-99 less than 26g/g, SFC is at least 80 * 10 ^-7, preferably at least 100 * 10 ^-7, especially preferably at least 120 * 10 ^-7Cm ³Sg ^-1,

(β 2) for according to ERT 441.1-99 more than or equal to 26 to CRC less than 27g/g, SFC is at least 70 * 10 ^-7, preferably at least 90 * 10 ^-7, especially preferably at least 110 * 10 ^-7Cm ³Sg ^-1,

(β 3) for according to ERT 441.1-99 more than or equal to 27 to CRC less than 28g/g, SFC is at least 60 * 10 ^-7, preferably at least 80 * 10 ^-7, especially preferably at least 100 * 10 ^-7Cm ³Sg ^-1,

(β 4) for according to ERT 441.1-99 more than or equal to 28 to CRC less than 29g/g, SFC is at least 45 * 10 ^-7, preferably at least 65 * 10 ^-7, especially preferably at least 85 * 10 ^-7Cm ³Sg ^-1,

(β 5) for according to ERT 441.1-99 more than or equal to 29 to CRC less than 30g/g, SFC is at least 30 * 10 ^-7, preferably at least 50 * 10 ^-7, especially preferably at least 70 * 10 ^-7Cm ³Sg ^-1,

(β 6) for according to ERT 441.1-99 more than or equal to 30 to CRC less than 31g/g, SFC is at least 20 * 10 ^-7, preferably at least 40 * 10 ^-7, especially preferably at least 60 * 10 ^-7Cm ³Sg ^-1,

(β 7) for according to the CRC of ERT 441.1-99 more than or equal to 31g/g, SFC is at least 10 * 10 ^-7, preferably at least 20 * 10 ^-7, especially preferably at least 30 * 10 ^-7Cm ³Sg ^-1

The properties of combination of two or more character that produced by above-mentioned character has produced the preferred embodiment of absorbent polymer structure of the present invention (Pa) respectively.According to the present invention more particularly preferred embodiment be following absorbent polymer structure (Pa), it has with following character or the properties of combination shown in following letter character or the letter character combination: β 1, β 2, β 3, β 4, β 5, β 6, β 7, wherein β 2, β 3, β 4, β 5 and β 6 are particularly preferred.

According to the present invention further preferably, absorbent polymer structure (Pa) is 18g/g at least according to the pressurized absorptivity (AAP) of ERT 442.1-99 under the pressure of 50 gram/square centimeters, be preferably 20g/g at least especially, most preferably is 22g/g at least.

For absorbent polymer structure of the present invention, further preferably outer radius is less than two times of the inner radial value.

In the particularly preferred embodiment of absorbent polymer structure (Pa), it is the part with following characteristics that the outside of polymer architecture preferably is understood as: the distance at each spatial point and particle center equals at least 50% of particle shape absorbent polymer structure radius in this part, especially preferably at least 75%, more preferably at least 90%, more preferably at least 95%.

According to the present invention at least partial fixing can be the water-insoluble mineral compound at the outside mineral compound of absorbent polymer structure (Pa), can obtain the stable dispersoid aqueous solution by it.

According to the present invention at least partial fixing be the condenses of poly-silicic acid at the outside particularly preferred mineral compound of absorbent polymer structure (Pa).

Further preferably, the above-mentioned characteristic of absorbent polymer structure of the present invention (Pa) is effective too for the absorbent polymer structure (Pa) that can obtain by the method according to foregoing invention.

According to the embodiment of method of the present invention and absorbent polymer structure of the present invention (Pa), preferably only provide lower limit eigenwert of the present invention on be limited to 20 times to, be preferably 10 times to, especially be preferably 5 times to, most preferably equal this lower value.

The invention further relates to a kind of matrix material that contains above-mentioned absorbent polymer structure (Pa) and base material.Polymer architecture of the present invention (Pa) and base material preferably combine securely.Base material is preferably film, metal, non-woven material, fine hair thing, tissue paper, fabric, natural or synthon or other foams of being made by polymkeric substance (for example polyethylene, polypropylene or polymeric amide).

Preferred composite materials of the present invention is sealing material, cable, absorbent core and diaper and the sanitary product that contains them.

Sealing material is preferably the water-absorbent film, wherein absorbent polymer structure is inserted in the polymeric matrix or fibrous matrix as base material.This is preferably as follows and carries out: by absorbent polymer structure (Pa) being mixed with the polymkeric substance (Pm) of polymkeric substance or formation fibrous matrix and finally making them combine (optionally being undertaken by thermal treatment).Under the situation of using fibrous absorbent structure, can make yarn by it, yarn can be spun into line with other fiber that contains another kind of material as base material, for example combines by braiding or weaving then, or directly combine, promptly be not spun into line with other fiber.The typical method that is used for this is people such as H.Savano, International Wire﹠amp; Cable Symposium Proceedings 40,333 to 338 (1991); People International Wire ﹠amp such as M.Fukuma; Cable Symposium Proceedings describes in 36,350 to 355 (1987) and at US 4,703,132 to some extent.These openly are incorporated herein by this reference and constitute a part of this disclosure thus.

At this matrix material is in the embodiment of cable, can directly use granular absorbent polymer structure (Pa), preferably uses below the cable isolator.In another embodiment of cable, can use the anti-absorbent polymer structure (Pa) of opening form of yarns of swellable.According to the another embodiment of cable, can use the absorbent polymer structure (Pa) of swellable form of film.In another embodiment of cable, can use the absorbent article core of absorbent polymer structure in addition as the cable center.Under the situation that is cable, base material has formed all component of the cable that does not contain absorbent polymer structure (Pa).Below comprise conduit (for example conduit or photoconductive tube), light or electrically insulating material and the cable-assembly of guaranteeing the machine applications of cable, for example open reticulated structure, fiber or fabric that material makes and by rubber or prevent the isolator that outside other material that damages of cable is made by for example synthetic materials anti-.

If composite structure is an absorbent core, then absorbent polymer structure (Pa) is inserted in the base material.This base material is preferably the filamentary material form.The available filamentary material comprises natural fiber (modification or unmodified) and synthon in foregoing invention.The suitable unmodified and example modified natural fiber comprises cotton, Spanish grass, sugarcane, kemp, flax, silk, wool, Mierocrystalline cellulose, chemical modification paper pulp, jute, artificial silk, ethyl cellulose and rhodia.Suitable synthon can be by polyvinyl chloride, fluorinated ethylene propylene, tetrafluoroethylene, poly(vinylidene chloride), polyacrylic ester (Orion for example ^), polyvinyl acetate, poly-ethyl vinyl acetate, solvable or insoluble polyvinyl alcohol, (for example polyethylene is (as PULPEX for polyolefine ^) and polypropylene), polymeric amide (for example nylon), polyester (DACRON for example ^Or Kodel ^), polyurethane(s), polystyrene etc. make.Used fiber can only comprise natural fiber, only comprise synthon or comprise natural fiber and any compatible array configuration of synthon.

The fiber that uses in foregoing invention can be hydrophilic or hydrophobic, or they can comprise the combination of hydrophilic fibers and hydrophobic fiber.Liquid, aqueous (for example aqueous body fluids) the wetting fiber or the fiber surface that can be deposited on these fibers described in term used herein " wetting ability ".Wetting ability and wettability define with relevant liquid and solid contact angle and surface tension usually.In the publication (copyright 1964) of the American Chemical Society that this title in Robert F.Gould publication is " contact angle, wettability and sticking power " (ContactAngle, Wettability and Adhesion) detailed argumentation is arranged.If the contact angle between liquid and fiber or its surface is less than 90 °, perhaps liquid inclination spontaneously distributes from the teeth outwards in self, and just by liquid wetting (being that it is hydrophilic), wherein two conditions are normally simultaneous for fiber or fiber surface.On the other hand, if contact angle can not spontaneously be expanded on fiber surface greater than 90 ° and liquid, fiber or fiber surface just are considered to be hydrophobic.

According to the preferred fiber of the present invention is hydrophilic fibre.Suitable hydrophilic fibre comprises cellulosic fibre, modified cellulose fibre, artificial silk, trevira (for example polyethylene terephthalate, for example DACRON ^), hydrophilic nylon (HYDROFIL ^) etc.Suitable hydrophilic fibre also can be by obtaining its hydrophilization with tensio-active agent or with silica treatment hydrophobic fibre (for example thermoplastic fibre, they are based on the polyolefine of for example polyethylene or polypropylene and so on or based on polyacrylic ester, polymeric amide, polystyrene, polyurethane(s) etc.).Owing to operability and cost reason, cellulosic fibre, particularly paper pulp fiber is preferred for foregoing invention.Other hydrophilic fibre that preferably is used for foregoing invention is the cellulosic fibre of chemicosolidifying.Term " cellulosic fibre of chemicosolidifying " is described herein to be to utilize the chemical mediator sclerosis to improve the cellulosic fibre of fiber in drying and the rigidity under aqueous conditions.This medium can be a chemical hardening agent, and it for example covers and/or injects fiber.They also can be to realize the hardened chemical hardening agent by the chemical structure (for example producing by the crosslinked of polymer chain) that changes fiber.Polymkeric substance-the stiffening agent that can cover or inject cellulosic fibre comprises: can be available from National Starch and Chemical Corp., Bridgewater, NJ, the cationic starch that contains nitrogen-containing group (for example amino) of USA, latex, Moisture barrier resins is polyamide epichlorohydrin resin (Kymene  557H for example for example, Hercules, Inc., Wilmington, Delaware, USA), as US 3, polyacrylamide resin described in 556,932, commercially available polyacrylamide, for example American Cyanamid Co., Stanfort, CT, the Parez  of USA, urea-formaldehyde resin, and terpolycyantoamino-formaldehyde resin.For example describing with independent form by crosslinked connection hardened fiber (being independent hardened fiber and their manufacture method) among US 3,224,926, US 3,440,135, US 3,932,209 and the US 4,035,147.Preferred cross-linking agents be glutaraldehyde, oxalic dialdehyde, formaldehyde, oxoethanoic acid, oxygen two Succinic Acid (oxydisuccinic acid) and citric acid.Vulcanized fiber cellulose fiber by crosslinked or coating, injection or crosslinked acquisition can twisting or coiling, the preferred twisting of fiber and coiling.

Except above-mentioned filamentary material, this core can also comprise thermoplastic material.During fusion, usually because capillary gradient, to this thermoplastic material of small part from being penetrated into the crossover sites of fiber between the fiber.These crossover sites become the bonding site of thermoplastic material.If this element cooling, thermoplastic material solidifies in these crossover sites, forms fibrous matrix in each layer or tissue bond bonding site together.This thermoplastic material can be various forms of, for example the combination of particle, fiber or particle and fiber.These materials can comprise multiple thermoplastic polymer, for example are selected from polyethylene (PULPEX for example ^) and polyacrylic polyolefine, polyester, copolyesters, polyvinyl acetate, poly-ethyl vinyl acetate, polyvinyl chloride, poly-inclined to one side 1, the multipolymer of 1-Ethylene Dichloride, polyacrylic ester, polymeric amide, copolyamide, polystyrene, polyurethane(s) and above-mentioned materials, for example vinylchlorid/vinyl-acetic ester etc.For core, can mainly use by Mierocrystalline cellulose, the material that the Mierocrystalline cellulose of optimum fiber matter is made is as base material.

In another embodiment of this core, this core also comprises flour except base material and absorbent polymer structure (Pa) part, for example, and as smell binding, zeolite, inorganic salt or organic salt or the analogous material of cyclodextrin and so on.

In an embodiment of absorbent core, absorbent polymer structure (Pa) is inserted with the amount that accounts for this core 10 to 90 weight %, preferred 20 to 80 weight %, preferred especially 40 to 70 weight %.In an embodiment of this core, in core, insert granular absorbent polymer structure (Pa).Absorbent polymer structure (Pa) can be evenly distributed in the filamentary material thus, and they can be with layer mode between filamentary material, and perhaps the concentration of absorbent polymer structure (Pa) can have a gradient among filamentary material.In another embodiment of core, in core, insert fibrous absorbent polymer structure (Pa).

Can optionally use several simultaneously for example in uptake rate, perviousness, maintenance capacity, pressurized absorptivity, size distribution or in different absorbent polymer particles different aspect the chemical constitution.These different polymer beads can mix the different positions that adds in the absorption pad or be arranged in core.This difference location can produce at the thickness direction of core or the length and the width of core.

Can be by traditional method well known by persons skilled in the art, for example common method known to those skilled in the art among the drum method of forming utilizes the feed design that forms wheel, formation bag and product form (productforms) and suitably revise that core is merged.In addition, also has modern set method, for example so-called air becomes net (airlaid) method (for example EP 850 615, US 4,640,810), adopt the combination of feed, fiber laydown and for example hydrogen bonding (for example DE 197 50 890), thermal bond, latex combination (for example EP 850 615) and the hydridization bonding of form of ownership; So-called wet laid random web (wetlaid) method (for example WO 99/49905), combing method, moltenly blow method, spin the method for blowing, and in order to make the high-absorbable non-woven fabrics (at EDANA, on the definition meaning of Brussels) similar approach, also have the combination of these methods and the common method of making core.Other operable method is to be manufactured on broadest laminating material and to extrude and coextrusion, wet method and dry method and other enhanced structure.

In another embodiment of absorbent core, this core is except base material and insert storing the absorbent polymer structure (Pa) of layer as body fluid in the base material, also comprises being preferred for the absorption layer that absorbs rapidly and liquid is distributed in core.Therefore, this absorption layer can directly be placed in and store on the layer, also can absorption layer be separated with the storage layer with preferred liquid stabilising interface.This interface is at first as absorption layer and the support base material that stores layer.Preferred boundary material is the pile fabric that is spun into of polyester or the pile fabric of being made by polypropylene, polyethylene or nylon.

In an embodiment of core of the present invention, absorption layer does not contain absorbable polymer.This absorption layer can have any suitable size, and can not surpass total length or the width that stores layer.This absorption layer can be as strip or sheet.But total absorption layer is preferably and hydrophilicly also can contains hydrophobic components.This absorption layer can contain the material of textile materials, pile fabric or another kind of suitable type.This absorption layer is preferably based on the cellulosic fibre of hydrophobicity dacron fibre (PET fiber), chemicosolidifying or based on the mixture of these fibers.Other suitable material is polypropylene, polyethylene, nylon or biological fiber.If absorption layer contains the pile fabric material, described layer can be by multiple different methods manufacturing.These methods comprise wet laid random web, use, use, form the pile fabric, the combing (this comprises thermal bonding, engages or engage with melt-spinning method with solvent) that are spun in airflow in melts.When needs were fiber arranged in absorption layer, the method for mentioning at last (pile fabric that formation is spun into and combing) was preferred, because be easy on single direction fiber arranged in this method.The particularly preferred material of absorption layer is the pile fabric that is spun into by PET.

At matrix material is in the embodiment of diaper, and the diaper component different with absorbent polymer structure comprises the base material of this matrix material.In preferred embodiments, diaper comprises above-mentioned core.In this case, the diaper component different with this core comprises the base material of this matrix material.Usually the matrix material as diaper comprises the preferred hydrophilic upper strata of fluid-tight low layer, porous and contains absorbent polymer structure (Pa) that absorbent polymer structure (Pa) is placed between lower floor and the upper strata.This layer that contains absorbable polymer is preferably the above core.Low layer can comprise all material well known by persons skilled in the art, and wherein polyethylene or polypropylene are preferred.The upper strata also can comprise all materials that are fit to well known by persons skilled in the art, and wherein polyester, polyolefine, viscose glue etc. are preferred, and they have produced enough porous layers to guarantee the gratifying hydraulic permeability in upper strata.In this regard, can be with reference to US 5,061, disclosing in 295, US Re.26,151, US 3,592,194, US 3,489,148 and US3,860,003.These openly are incorporated herein by this reference and constitute a part of this disclosure thus.

The present invention further comprises the method for making matrix material, and absorbent polymer structure of the present invention and base material and non-essential suitable additive are contacted with each other.Preferably become net method, compression method, extrusion molding and hybrid system to realize contacting by wet laid random web and air.

In addition, the present invention includes can be by the matrix material of aforesaid method acquisition.

The present invention comprises that also the chemical products, particularly foam that contain absorbent polymer structure of the present invention (Pa) or above-mentioned base material, formed body, fiber, sheet material, film, cable, sealing material, imbibition sanitary product, plant or mushroom growth regulate carrier, additives for building materials, packing material or soil additive that medium or plant protection product are used.

The present invention comprises that also absorbent polymer structure of the present invention (Pa) or above-mentioned base material are used for the purposes of chemical products, regulates in carrier, additives for building materials, packing material or the soil additive that medium or plant protection product use especially for foam, formed body, fiber, sheet material, film, cable, sealing material, imbibition sanitary product, plant or mushroom growth.

When regulating the carrier that medium or plant protection product use as plant or mushroom growth, preferably, plant or mushroom growth are regulated the carrier that medium or plant protection product use can discharge for some time under the control of carrier.

The present invention also comprises the aqueous solution of the mineral compound that contains at least a chemical cross-linking agent and at least a dispersoid form, and wherein chemical cross-linking agent and mineral compound are equivalent to those chemical cross-linking agents or the mineral compound mentioned in the method for aforementioned manufacturing absorbent polymer structure of the present invention (Pa).

The content of the chemical cross-linking agent in the aqueous solution of the present invention is preferably 5 to 70 weight % of the water yield in the aqueous solution, is preferably 20 to 60 weight % especially, most preferably is 30 to 50 weight %.

The content of the mineral compound in the aqueous solution of the present invention is preferably 1 to 40 weight % of the water yield in the aqueous solution, preferred especially 1.5 to 35 weight %, most preferably 2.5 to 32 weight %.

Foregoing invention also relates to the method for making this aqueous solution, and the aqueous solution that wherein will contain the mineral compound of at least a dispersoid form mixes with at least a chemical cross-linking agent.In this method of the present invention, this chemical cross-linking agent can be like this and the aqueous solution of the mineral compound that contains the dispersoid form, perhaps mixes with the form of the aqueous solution.

The invention still further relates to can be by the aqueous solution of aforesaid method acquisition.

The invention further relates to the purposes of the aqueous solution of the mineral compound that contains at least a chemical cross-linking agent and at least a dispersoid form, maybe the purposes of the aqueous solution that can make by the method for the above-mentioned manufacturing aqueous solution is used to handle absorbent polymer structure (Pu1) or outside (Pu2).With previous of the present invention that above set forth, be used to handle absorbent polymer structure (Pu1) or (Pu2) outside mode and method carry out described processing.This absorbent polymer structure (Pu1) or (Pu2) comprise of the present invention that above set forth, be used to handle absorbent polymer structure (Pu1) or (Pu2) outside absorbent polymer structure (Pu1) or (Pu2).

The present invention comprises the purposes of the aqueous solution of the mineral compound that contains at least a chemical cross-linking agent and at least a dispersoid form at last, or the purposes of the aqueous solution that can make according to the method described above, be used for making the following aqueous solution: this aqueous solution is used for adjusting absorbent polymer structure (Pu1) or at least a following character (Pu2):

(γ 1) salt solution water conservancy diversion (SFC),

(γ 2) centrifugal maintenance capacity (CRC) or

(γ 3) pressurized absorptivities (AAP)

The properties of combination that produces by above-mentioned character or two or more character produced respectively the aqueous solution of the present invention according to advantageous applications mode of the present invention.About other embodiment of the present invention, particularly preferably be the purposes that this aqueous solution is used to adjust following character or properties of combination: γ 1, γ 2, γ 3, γ 1 γ 2, γ 1 γ 3, γ 2 γ 3, γ 1 γ 2 γ 3.

Further illustrate the present invention by embodiment, but be not limited to these embodiment.

Embodiment

Untreated absorbent polymer structure (Pu1) or manufacturing (Pu2)

Powders A

To contain 280 grams and be neutralized to the monomer solution nitrogen purge deoxidation of vinylformic acid, 466.8 gram water, 1.4 gram polyoxyethylene glycol-300-diacrylates and the 1.68 gram allyloxy polyethylene glycol acrylate of 70 moles of %, and be cooled to 4 ℃ starting temperature with sodium hydroxide.After reaching starting temperature, (0.1 gram, two hydrochlorinates 2,2 '-azo, two-2-amidine propane is at 10 gram H to add initiator solution ₂Solution among the O, 0.3 gram Sodium persulfate is at 10 gram H ₂Solution among the O, the solution of 0.07 gram, 30% hydrogen peroxide is at 1 gram H ₂Solution among the O and 0.015 gram xitix are at 2 gram H ₂Solution among the O).After reaching about 100 ℃ outlet temperature, the gel of making is reduced to small pieces and 150 ℃ of dryings 90 minutes.With exsiccant polymerisate corase grind, fine grinding and to sieve into granularity be 150 to 850 microns powder.

The maintenance capacity of powders A is 28.8g/g.

Powder B

To contain 280 grams and be neutralized to the monomer solution nitrogen purge deoxidation of vinylformic acid, 467.6 gram water, 0.98 gram polyoxyethylene glycol-300-diacrylate and the 1.26 gram allyloxy polyethylene glycol acrylate of 70 moles of %, and be cooled to 4 ℃ starting temperature with sodium hydroxide.After reaching starting temperature, (0.1 gram, two hydrochlorinates 2,2 '-azo, two-2-amidine propane is at 10 gram H to add initiator solution ₂Solution among the O, 0.3 gram Sodium persulfate is at 10 gram H ₂Solution among the O, the solution of 0.07 gram, 30% hydrogen peroxide is at 1 gram H ₂Solution among the O and 0.015 gram xitix are at 2 gram H ₂Solution among the O).After reaching about 100 ℃ outlet temperature, the gel of making is reduced to small pieces and 150 ℃ of dryings 90 minutes.With exsiccant polymerisate corase grind, fine grinding and to sieve into granularity be 150 to 850 microns powder.

The maintenance capacity of powder B is 31.2g/g.

Powder C

To contain 280 grams and wash deoxidation with nitrogen, and be cooled to 4 ℃ starting temperature with the monomer solution that sodium hydroxide is neutralized to vinylformic acid, 468.6 gram water, 0.42 gram polyoxyethylene glycol-300-diacrylate and the 0.84 gram allyloxy polyethylene glycol acrylate of 70 moles of %.After reaching starting temperature, (0.1 gram, two hydrochlorinates 2,2 '-azo, two-2-amidine propane is at 10 gram H to add initiator solution ₂Solution among the O, 0.3 gram Sodium persulfate is at 10 gram H ₂Solution among the O, the solution of 0.07 gram, 30% hydrogen peroxide is at 1 gram H ₂Solution among the O and 0.015 gram xitix are at 2 gram H ₂Solution among the O).After reaching about 100 ℃ outlet temperature, make the gel division of making and 150 ℃ of dryings 90 minutes.With exsiccant polymerisate corase grind, fine grinding and to sieve into granularity be 150 to 850 microns powder.

The maintenance capacity of powder C is 37.1g/g.

Each component in the following example (for example linking agent, water or silicic acid sol) is used to handle untreated absorbent polymer structure (Pu1) or outside (Pu2), and the amount that wherein provides should be understood to based on untreated absorbent polymer structure (Pu1) or weight (Pu2).

The external treatment of untreated absorbent polymer structure (Pu1) is to retentivity; The absorbefacient influence of perviousness and pressurized

Embodiment 1:

By using Krups cake mixer (cake mixer) vigorous stirring, 50 gram powders A and 0.5 gram ethylene carbonate, 0.42 are restrained silicic acid sol (from the product Levasil of Bayer AG ^200, about 30 weight % of solid ingredient) and the solution of 1.08 gram water mix and finally heating 30 minutes in being made as 180 ℃ baking oven.

Embodiment 2:

By using Krups cake mixer vigorous stirring, 50 gram powders A and 0.5 gram ethylene carbonate, 0.84 are restrained silicic acid sol (from the product Levasil of Bayer AG ^200, about 30 weight % of solid ingredient) and the solution of 0.66 gram water mix and finally heating 30 minutes in being made as 180 ℃ baking oven.

Embodiment 3:

By using Krups cake mixer vigorous stirring, 50 gram powder B and 0.5 gram ethylene carbonate, 0.42 are restrained silicic acid sol (from the product Levasil of Bayer AG ^200, about 30 weight % of solid ingredient) and the solution of 1.08 gram water mix and finally heating 30 minutes in being made as 180 ℃ baking oven.

Embodiment 4:

By using Krups cake mixer vigorous stirring, 50 gram powder B and 0.5 gram ethylene carbonate, 0.84 are restrained silicic acid sol (from the product Levasil of Bayer AG ^200, about 30 weight % of solid ingredient) and the solution of 0.66 gram water mix and finally heating 30 minutes in being made as 180 ℃ baking oven.

Embodiment 5:

By using Krups cake mixer vigorous stirring, 50 gram powder C and 0.5 gram ethylene carbonate, 0.42 are restrained silicic acid sol (from the product Levasil of Bayer AG ^200, about 30 weight % of solid ingredient) and the solution of 1.08 gram water mix and finally heating 30 minutes in being made as 180 ℃ baking oven.

Comparative Examples 1:

By using Krups cake mixer vigorous stirring, the solution of 50 gram powders A with 0.5 gram ethylene carbonate and 1.5 gram water are mixed, and finally in being made as 180 ℃ baking oven, heated 30 minutes.

Comparative Examples 2:

By using Krups cake mixer vigorous stirring, 50 gram powder B are mixed with the solution of 0.5 gram ethylene carbonate and 1.5 gram water, and finally in being made as 180 ℃ baking oven, heated 30 minutes.

Comparative Examples 3:

Under vigorous stirring, will restrain silicic acid sol (from the product Levasil of Bayer AG by the cross-linked polymer structures and 0.84 that Comparative Examples 2 obtains ^200, the about 30 weight % of solid ingredient) and 0.16 gram water mixing.This product is without any final tempering step.

Comparative Examples 4:

Under vigorous stirring, will restrain silicic acid sol (from the product Levasil of Bayer AG by the cross-linked polymer structures and 0.84 that Comparative Examples 2 obtains ^200, about 30 weight % of solid ingredient) and 0.16 gram water mix and finally heating 60 minutes in being made as 100 ℃ baking oven.

Comparative Examples 5:

By using Krups cake mixer vigorous stirring, 50 gram powder B and 0.5 gram ethylene carbonate, 0.125 are restrained Aerosil ^The solution of (from the pyrolysis silicic acid sol of Degussa AG) and 2 gram water mixes, and finally heating 30 minutes in being made as 180 ℃ baking oven.Must increase the water yield to make Aerosil ^Suspension in water.However still can not obtain the suspension that is easy to add, because used Aerosil ^Very rapidly the deposition and can not add in heterogeneity among the powder B.The polymkeric substance of coating is easy to form grumeleuse and is uneven.

Comparative Examples 6:

By using Krups cake mixer vigorous stirring, 50 gram powder C are mixed with the solution of 0.5 gram ethylene carbonate and 1.5 gram water, and finally in being made as 180 ℃ baking oven, heated 30 minutes.

Comparative Examples 7:

By using Krups cake mixer vigorous stirring, 50 gram powder B and 0.25 gram diethylene glycol monomethyl ether, 0.25 are restrained silicic acid sol (from the product Levasil of Bayer AG ^200, about 30 weight % of solid ingredient) and 1.25 gram water mix and finally heating 30 minutes in being made as 120 ℃ baking oven.This processing is equivalent to the processing according to the embodiment 1 of JP 1994/16822.

Comparative Examples 8:

By using Krups cake mixer vigorous stirring, 50 gram powder B and 0.25 gram 1,3 butylene glycol, 0.25 are restrained silicic acid sol (from the product Levasil of Bayer AG ^200, about 30 weight % of solid ingredient) and 1.25 gram water mix and finally heating 30 minutes in being made as 120 ℃ baking oven.This processing is equivalent to the processing according to the embodiment 2 of JP 1994/16822.

The character of the absorbent structure that obtains in embodiment 1 to 4 and the Comparative Examples 1 to 8 is summarised in the following table 1.

Compare with under the situation that does not have silicic acid sol, making outside crosslinked product according to the absorbent polymer structure that the present invention makes, under even the condition that improves identical at retentivity, show the perviousness (SFC) (embodiment 1 to 4, Comparative Examples 1 to 2) of obvious raising.No matter whether carry out thermal treatment subsequently, with silicic acid crosslinked polymer architecture is carried out secondary treatment and can not produce required result (Comparative Examples 3,4 and 6).

In the secondary crosslinking process, add Aerosil ^Can not produce good equally high absorbent properties (Comparative Examples 5).In addition, the Aerosil of increase ^But amount can not redispersion in the water of receiving amount, no longer be dispersible therefore.

Comparative Examples 7 and 8 shows in according to the inventive embodiment of not examining JP 1994/16822, can not obtain good polymer performance aspect perviousness and retentivity.

Table 1

	?????????SFC ??(10 ^-7·cm ³·s·g ^-1)	50g/cm ²The time AAP (g/g)	??CRC ??(g/g)
	?????????SFC ??(10 ^-7·cm ³·s·g ^-1)	50g/cm ²The time AAP (g/g)	??CRC ??(g/g)	Embodiment 1	??140	??23.5	??27
Embodiment 2	??150	??23.5	??27.2	Embodiment 1	??140	??23.5	??27
Embodiment 2	??150	??23.5	??27.2	Embodiment 3	??100	??24	??29
Embodiment 4	??110	??24	??29	Embodiment 3	??100	??24	??29
Embodiment 4	??110	??24	??29	Comparative Examples 1 (without silicic acid sol)	??50	??24.5	??26.4
Comparative Examples 2 (without silicic acid sol)	??30	??25	??27.8	Comparative Examples 1 (without silicic acid sol)	??50	??24.5	??26.4
Comparative Examples 2 (without silicic acid sol)	??30	??25	??27.8	Comparative Examples 3 (after using the silicic acid sol secondary crosslinking)	??25	??24	??28.1
Comparative Examples 4 (using silicic acid sol secondary crosslinking and heating back)	??30	??24	??28.7		??25	??24	??28.1
	??30	??24	??28.7	Comparative Examples 5 (pyrolysis silicic acid)	??55	??23	??29
Comparative Examples 6 (without silicic acid sol)	??17	??25	??31.6	Comparative Examples 5 (pyrolysis silicic acid)	??55	??23	??29
Comparative Examples 6 (without silicic acid sol)	??17	??25	??31.6	Comparative Examples 7 (JP 1994/16822)	??0	??9	??31.3
Comparative Examples 8 (JP 1994/16822)	??0	??9	??31.2	Comparative Examples 7 (JP 1994/16822)	??0	??9	??31.3

The external treatment of untreated absorbent polymer structure (Pu1) is to the influence of the agglomeration trend of polymer architecture

Embodiment 6:

By using Krups cake mixer vigorous stirring, 50 gram powder B and 0.5 gram ethylene carbonate, 0.125 are restrained silicic acid sol (from the product Levasil of Bayer AG ^200, about 30 weight % of solid ingredient) and the solution of 1.38 gram water mix.Finally, measure its density and destroy the required pressure of this rolled-up stock by preparing rolled-up stock with the contacted absorbent polymer structure of the aqueous solution.

Embodiment 7:

By using Krups cake mixer vigorous stirring, 50 gram powder B and 0.5 gram ethylene carbonate, 0.125 are restrained silicic acid sol (from the product Levasil of Bayer AG ^200, about 30 weight % of solid ingredient) and the solution of 1.25 gram water mix.Finally, measure its density and destroy the required pressure of this rolled-up stock by preparing rolled-up stock with the contacted absorbent polymer structure of the aqueous solution.

Comparative Examples 9:

By using Krups cake mixer vigorous stirring, 50 gram powder B are mixed with the solution of 0.5 gram ethylene carbonate and 1.5 gram water.Finally, measure its density and destroy the required pressure of this rolled-up stock by preparing rolled-up stock with the contacted absorbent polymer structure of the aqueous solution.

Embodiment 5 and 6 and Comparative Examples 9 in be summarised in the following table 2 with the character of the contacted absorbent polymer structure of the aqueous solution:

Table 2

	Rolled-up stock density (kilogram/cubic centimetre)	Applied pressure (pascal)
	Rolled-up stock density (kilogram/cubic centimetre)	Applied pressure (pascal)	Embodiment 6	??486	??8,795
Embodiment 7	??474	??4,575	Embodiment 6	??486	??8,795
Embodiment 7	??474	??4,575	Comparative Examples 9	??410	??16,295

The result shows the generation that has obviously suppressed stable agglomerate by the adding silicic acid sol.By interpolation make absorbent polymer structure (Pu1) or (Pu2) can stand volume more water and can be owing to caking damages processing characteristics.

Testing method

Perviousness under the swollen state (SFC test)

Carry out perviousness mensuration (salt solution water conservancy diversion=SFC) swollen state under according to the method for describing among the WO 95/22356.Be weighed into about 0.9 gram high-absorbent material in the cylinder that has at the bottom of the screen cloth and carefully be distributed on the screen surface.Make high-absorbent material under the pressure of 20 gram/square centimeters in the synthetic urine of JAYCO swelling 1 hour.Write down the swelling height of high absorption agent, make the NaCl solution of 0.118M under the constant fluid static pressure, from horizontal storage vessel, pass through the swell gel layer then.The swelling glue-line is covered by special screen drum in measuring process, and its NaCl solution of guaranteeing 0.118M is being equal to distribution and is guaranteeing condition relevant with gel bed state in measuring process constant (measuring 20-25 ℃ of temperature) on the gel.The pressure that acts on the high absorption agent of swelling is 20 gram/square centimeters constantly.By means of computer and balance, in 10 minutes 20 seconds serving as that record becomes the amount of liquid that passes through gel film of function with the time at interval.By the slope extrapotation and in 2-10 minute the center of flow when the time point t=0 measure and carry out regression analysis, measure flow velocity Grams Per Second thus by the swell gel layer.The unit of SFC value (K) is cm ³Sg ^-1And be calculated as follows:

K = \frac{F_{s} (t = 0) \cdot L_{0}}{r \cdot A \cdot Δ P_{1}} = \frac{F_{s} (t = 0) \cdot L_{0}}{139506}

F wherein _s(t=0) be that unit is the flow velocity of Grams Per Second,

L ₀The gel coat thickness that unit is centimetre,

The density of R NaCl solution (1.003 gram/cubic centimetre),

The upper surface of the gel coat of A in graduated cylinder (28.27 square centimeters),

The hydrostatic pressure that Δ P applies gel coat (4920 dynes/cm) and

K SFC value.

Agglomeration trend is measured

Indiciser by J.R.Johanson Inc. company measures the trend that the high absorption agent that scribbles liquid forms agglomerate.Therefore make covering secondary crosslinking agent solution and the final 50 gram powder that use in upward this research that cover to be studied on the high absorption agent.This device is to use 160 by imprinter in 5.23 centimetres the hollow metal tube at internal diameter, and the qualification pressure preparation of 000Pa highly is about 2 centimetres rolled-up stock.Making this rolled-up stock is 4.2 centimetres second cylinder by diameter, thus with its final destruction, and measures necessary power.

Claims

1. make the method for absorbent polymer structure (Pa) by the outside of handling untreated absorbent polymer structure (Pu1), this method may further comprise the steps:

-make untreated absorbent polymer structure (Pu1) the outside with contain the aqueous solution of at least a chemical cross-linking agent and contact with the mineral compound of at least a dispersoid form;

-the absorbent polymer structure that contacted its outside of temperature range internal heating of 40 to 300 ℃ with the described aqueous solution, thereby it is crosslinked more strongly to make the outside of this absorbent polymer structure compare with inside, and described mineral compound at least partial fixing in the outside of this absorbent polymer structure.

2. the method for the outside manufacturing absorbent polymer structure (Pa) by handling the absorbent polymer structure of handling with the mineral compound of dispersoid form (Pu2), this method may further comprise the steps:

-make absorbent polymer structure (Pu2) the outside with contain the aqueous solution of at least a chemical cross-linking agent and contact with the mineral compound of at least a dispersoid form;

3. according to the method for claim 1 or claim 2, absorbent polymer structure (Pu1) or (Pu2) be based on wherein:

Monomer or its salt that polymeric, the ethylenic of (α 1) 20-99.999 weight % be undersaturated, contain acidic-group, or contain polymeric, the ethylenically unsaturated monomers of protonated nitrogen or quaternary nitrogen, or their mixture,

(α 2) 0-80 weight % can with the polymeric of (α 1) copolymerization, single ethylenically unsaturated monomers,

One or more linking agents of (α 3) 0.001-5 weight %,

A kind of water-soluble polymers of (α 4) 0-30 weight %, and

One or more additives of (α 5) 0-20 weight %,

Wherein composition weight (α 1) to (α 5) and equal 100 weight %.

4. according to the method for one of aforementioned claim, absorbent polymer structure (Pu1) or (Pu2) have at least a in the following character wherein:

(A) maximum absorption of the NaCl solution of 0.9 weight % is at least 10 to 1000g/g.

(B) part of the NaCl solution extraction of available 0.9 weight % is lower than absorbent polymer structure (Pu1) or 30 weight % (Pu2),

(C) tap density is 300 to 1000 grams per liters,

(D) 1 gram absorbent polymer structure (Pu1) or the pH value (Pu2) in 1 premium on currency the time are 4 to 10,

(E) crc value is 10 to 100g/g.

5. according to the method for one of aforementioned claim, wherein absorbent polymer structure (Pu1) or (Pu2) with account for absorbent polymer structure (Pu1) or (Pu2) the described aqueous solution of 20 weight % at the most of weight contact.

6. according to the method for one of aforementioned claim, two kinds of aqueous solution that separate---wherein a kind of chemical cross-linking agent that contains wherein, another kind contains the mineral compound of dispersoid form---contacts with absorbent polymer structure (Pu1) or (Pu2) simultaneously.

7. according to the method for one of aforementioned claim, wherein with the aqueous solution that absorbent polymer structure (Pu1) or outside (Pu2) contact in the mineral compound of at least 30 weight % comprise the particle that granularity is 1 to 100 nanometer.

8. according to the method for one of aforementioned claim, wherein when handling absorbent polymer structure (Pu1) or (Pu2) outside, the consumption of mineral compound is absorbent polymer structure (Pu1) or 0.001 to 10 weight % (Pu2).

9. according to the method for one of aforementioned claim, wherein use the particle that contains poly-silicic acid as described mineral compound.

10. according to the method for one of aforementioned claim, wherein use the condensation cross-linking agent as described chemical cross-linking agent.

11. the absorbent polymer structure (Pa) that can make by the method for one of claim 1 to 10.

12. comprise inside and around the absorbent polymer structure (Pa) of the outside of this inside, wherein outside crosslinked more strongly than inside, a kind of mineral compound at least partial fixing externally, and wherein this absorbent polymer structure (Pa) has at least a in the following character:

(β 1) for the CRC less than 26g/g, SFC is at least 80 * 10 ^-7Cm ³Sg ^-1,

(β 2) for more than or equal to 26 to the CRC less than 27g/g, SFC is at least 70 * 10 ^-7Cm ³Sg ^-1,

(β 3) for more than or equal to 27 to the CRC less than 28g/g, SFC is at least 60 * 10 ^-7Cm ³Sg ^-1,

(β 4) for more than or equal to 28 to the CRC less than 29g/g, SFC is at least 45 * 10 ^-7Cm ³Sg ^-1,

(β 5) for more than or equal to 29 to the CRC less than 30g/g, SFC is at least 30 * 10 ^-7Cm ³Sg ^-1,

(β 6) for more than or equal to 30 to the CRC less than 31g/g, SFC is at least 20 * 10 ^-7Cm ³Sg ^-1,

(β 7) for the CRC more than or equal to 31g/g, SFC is at least 10 * 10 ^-7Cm ³Sg ^-1

13. according to the absorbent polymer structure (Pa) of claim 12, wherein the pressurized absorptivity (AAP) of absorbent polymer structure under the pressure of 50 gram/square centimeters is 18g/g at least.

14. according to the absorbent polymer structure (Pa) of claim 12 or 13, wherein said mineral compound is the condenses of poly-silicic acid.

15. a matrix material, it contains according to absorbent polymer structure of claim 11 or 12 (Pa) and base material.

16. be used to make the method for matrix material, wherein make according to the absorbent polymer structure (Pa) of claim 11 or 12 and base material and non-essential additive to contact with each other.

17. the matrix material that can make by the method for claim 16.

18. a chemical products, it contains according to the absorbent polymer structure of claim 11 or 12 (Pa) or according to the matrix material of claim 15 or 17.

19. according to the absorbent polymer structure (Pa) of claim 11 or 12 or according to the purposes of matrix material in chemical products of claim 15 or 17.

20. an aqueous solution, it contains the mineral compound of at least a chemical cross-linking agent and at least a dispersoid form.

21. make the method according to the aqueous solution of claim 20, the aqueous solution that wherein will comprise the mineral compound of at least a dispersoid form mixes with at least a chemical cross-linking agent.

22. according to the method for claim 21, wherein said chemical cross-linking agent uses with the form of the aqueous solution.

23. the aqueous solution that can make by the method for claim 21 or 22.

24. according to the aqueous solution of claim 20 or 23, wherein said mineral compound is the particle form that contains poly-silicic acid.

25., be used for the outside processing of untreated absorbent polymer structure (Pu1) according to the purposes of the aqueous solution of claim 20 or 23.

26., be used for the outside processing of not handling as yet of absorbent polymer structure (Pu2) with the mineral compound of dispersoid form according to the purposes of the aqueous solution of claim 20 or 23.

27., be used to adjust at least a following character of untreated absorbent polymer structure (Pu1) according to the purposes of the aqueous solution of claim 20 or 23:

(γ 1) salt solution water conservancy diversion (SFC),

(γ 2) centrifugal maintenance capacity (CRC) or

(γ 3) pressurized absorptivities (AAP).

28., be used to adjust as yet not at least a following character of the absorbent polymer structure of handling with the mineral compound of dispersoid form (Pu2) according to the purposes of the aqueous solution of claim 20 or 23:

(γ 1) salt solution water conservancy diversion (SFC),

(γ 2) centrifugal maintenance capacity (CRC) or

(γ 3) pressurized absorptivities (AAP).