CN1768028A - Mixtures of polyalkoxylated trimethylolpropane (meth)acrylate and use thereof - Google Patents

Abstract

The invention relates to a mixture of at least two compounds each having at least two double bonds, said mixture having a GFV from 200 to 600 g/mol of double bond and at least two of said compounds each comprising at least two (meth)acrylic esters as double bond component, GFV being given by the formula (I), wherein alpha <i> is corresponding to molecular fraction of the compounds (i) in the mixture; n is the number of the compounds in the mixture and n is not less than 2; Z<i> is the number of the double bonds of the compounds (i); and MW<i> represents the molecular weight of the compounds (i).

Description

The mixture and uses thereof that comprises the compound of at least two two keys

The present invention relates at least two kinds of model mixtures that respectively have the compound of at least two two keys, the WFR that described mixture has is the two keys of 200-600g/mol, and at least two kinds of described compounds respectively contain at least two (methyl) acrylate as two key components, and WFR is provided by following formula:

$\underset{i=1}{\overset{n}{\mathrm{\&Sigma;}}}{\mathrm{\&alpha;}}_i\&times;{\mathrm{MW}}_i/Z_i=\mathrm{WFR},$ Wherein

$\underset{i=1}{\overset{n}{\mathrm{\&Sigma;}}}{\mathrm{\&alpha;}}_i=1$

α _iEqual the molar fraction of compound (i) in described mixture, n equals compound (linking agent component) number in the described mixture, and n 〉=2, Z _iEqual the double key number order in the described compound (i), MW _iEqual the molecular weight of described compound (i), the invention still further relates to the purposes of simplified method with the reaction mixture that can obtain thus of these esters of preparation.

The addition polymer of formation swellable hydrogel that is known as high water absorbency polymer or SAP is known by prior art.They are the network of flexible wetting ability addition polymer, and it can be ionic and nonionic in essence.They can absorb by forming hydrogel and in conjunction with liquid, aqueous, and therefore are preferred for producing tampon, diaper, cotton wool, Inconvenient article, children and are used for the hygienic articles of absorbed body fluid with training pants, the interior end of footwear and other.High water absorbent also is used to the other technologies field, and wherein liquid, especially water or the aqueous solution are absorbed.These fields for example comprise storage, packing, transportation (water sensitivity goods wrapping material, for example flowers transportation, concussion protection); Field of food (the transportation of fish, fresh meat; Absorb water, blood in fresh fish/pork pies dress); Medicine (wound gypsum, be used to burn dressing or other ooze out the water-absorbing material of wound), makeup (solid support material, rheumatism gypsum, ultrasonic gel, cooling gel, makeup thickening material, the sun-screening agent that are used for medicine and medicament); The thickening material that is used for oil-in-water or water-in-oil emulsion; Textiles (end in the moisture content adjusting in gloves, sweat shirt, the textiles, the footwear); (fixing, the agglomeration of the catalyzer used of organic reaction, big functionality molecule (enzyme) with hydrophilic component, dispersion agent, liquefying agent in tackiness agent, heat-storage medium, flocculating aids, the polymer laminate) used in chemical process industry; Building and build, device (powder injection molding, based on the linging of clay, suppress the vibration medium, be used for auxiliary agent, the cable sheath of holing) on the aqueous ground of richness; Water treatment, waste treatment (the particularly curing of aqueous waste), water are removed (deicer, can use the sand bag again); Cleaning; Agricultural industry (wood protection of the maintenance of irrigation, thawing water and dew condensation thing, composting additive, opposing fungi and infestation by insect, activeconstituents discharge the delay of plant); Fire prevention (spark that flies upward) (covers house or room wall with the SAP gel, because glassware for drinking water has high thermal capacity, so can prevent to ignite; At fire, for example spray the SAP gel under the situation of hill fire); Coextrusion agent in thermoplastic polymer (hydrophilization of multilayer film); Can absorb the production (for example, can store the agricultural film of rain and dew) of the film and the thermoplastic molded product of water; What be used for preserving the fresh fruit that can be packaged in moist film and vegetables contains the SAP film; The water that SAP puts up stores of fruits and vegetables discharge and do not form the drop that condenses, and part emits fruits and vegetables again, so that neither can be smelly, also can not wither; SAP-polystyrene coextrusion thing for example is used for food (as meat, fish, poultry, fruit and vegetables) packing; Carrier substance in active ingredient formulations (medicine, Crop protection).In hygienic articles, high water absorbent places absorbent core usually, and it comprises other materials, comprises fiber (cellulosic fibre), the liquid invader that it applies with storage spontaneity immediately as liquid vessel, and be intended to guarantee body fluid effective channelizing to high water absorbent in absorbent core.

Existing trend in the diaper design is the constantly thinner structure development to the hydrogel content of cellulose fiber content with reduction and increase.Constantly the trend of thinner diaper configurations has changed the needed over several years performance form of water swellable hydrophilic polymer substantially.Though when beginning to develop the high-hydroscopicity hydrogel, only interest is concentrated on high swellable at first, the ability that determined high water absorbent conveying and distributing liquid afterwards also has decisive meaning.Determined conventional high water absorbent with liquid when wetting, can be in the surface swelling greatly so that damaged substantially or stoped the conveying of liquid fully to granule interior.This class feature of high water absorbent is called as the gel blocking effect.In hygienic articles, the relatively large polymkeric substance of per unit area must not cause swollen polymer to form barrier layer to follow-up liquid.Product with good transportation performance will be guaranteed the optimum utilization of whole hygienic articles.This has prevented from will cause the gel blocking-up of hygienic articles seepage under extreme case.Therefore, liquid conveying and distribution have decisive meaning to the initial absorption of body fluid.

The hydrogel that for example has high-gel strength under solvent swelling state has good transportation performance.The gel that lacks intensity can be at institute's applied pressure, for example because the distortion down of the pressure due to the wearer body weight of hygienic articles, and blocks the hole in the SAP/ cellulosic fibre water-retaining agent and has therefore stoped the lasting absorption of liquid.The gel-strength that improves is usually through obtaining than high-crosslinking-degree, although this can reduce the water retention property of product.A kind of ingenious mode that improves gel-strength is that the back, surface is crosslinked.In the method, make dry high water absorbent carry out extra cross-linking step with average cross-linking density.The back, surface is crosslinked to increase cross-linking density in high-hydroscopicity particulate sheath, and the water-absorbent under load is promoted to higher level.Though absorptive capacity reduces in high-hydroscopicity particle sheath, owing to exist removable polymer chain, core to have improved absorptive capacity (comparing) with sheath, so that protector configurations is guaranteed improved liquid conveying and the gel blocking effect can not taken place.The total volume of wishing very much high water absorbent is not occupied not spontaneously, but along with time lag is occupied.Because hygienic articles repeatedly attacked by urine usually, so the absorptive capacity of high water absorbent should dexterously can be promptly not depleted after discharging for the first time.

The hydrophilic hydrogel of high swelling especially (is total to) polymkeric substance of polymerization hydrophilic monomer, grafting (be total to) polymkeric substance of one or more hydrophilic monomers on suitable grafting base-material, crosslinked Mierocrystalline cellulose or starch ethers, crosslinked carboxymethyl cellulose, partial cross-linked polyoxyalkylene, or in liquid, aqueous swollen natural product, for example guar gum derivatives.With such hydrogel as the product that absorbs the aqueous solution producing diaper, tampon, cotton wool and other hygienic articles, and in gardening market, be used as water-holding agent.

Be to improve performance, for example rewetting in the diaper and AUL carry out behind the afterwards crosslinked or gel in surface crosslinked to the high swelling hydrophilic hydrogel usually.This back is crosslinked, and itself is known and preferably carry out in mutually or to grind and crosslinked the carrying out in back, surface of fractionated polymer beads at aqueous gel by those skilled in the art.

WO 90/15830 has described the linking agent mixture of methylene-bisacrylamide and diallyl tartramide.

WO 02/32964 has described the linking agent mixture between acrylate glycol and allylic cpd.

DE 19646484 has described the linking agent mixture of allyl ethers acrylate glycol and acrylate or allyl amine.

Allylic is reactive relatively poor in polymerization, and usually causes the toughness gel.

WO 93/21237 discloses the alkoxylate poly-hydroxy C that can be used as linking agent ₂-C ₁₀(methyl) acrylate of hydro carbons.Used TriMethylolPropane(TMP) linking agent is corresponding to SR 351, SR 454, SR502, SR 9035 and SR 415.These linking agents have 0,3,9,15 or 20 EO unit/TMP.WO 93/21237 has described has 3 times to 2-7 EO unit/TMP, and especially having 3 times is favourable to 4-6 EO unit/TMP.

The shortcoming of these compounds is expensive, and needs inconvenient purification process so that small part is removed raw material and by product; The acrylic acid content of the linking agent that uses in the document of being quoted is lower than 0.1 weight %.

Well-known be by in the presence of inhibitor/inhibitor system and solvent such as benzene, toluene or hexanaphthene exist or not in the presence of (methyl) vinylformic acid and corresponding pure acid catalyzed esterification are produced such senior (methyl) acrylate.

Therefore because known ester is formed based on balanced reaction by (methyl) vinylformic acid and alcohol, in order to obtain industrial transformation efficiency a kind of raw material of common excessive use and/or by removing esterification water and/or the target ester that forms in the balance.

Therefore, in the production of senior (methyl) acrylate, remove reaction water usually and use excessive (methyl) vinylformic acid.

US 4 187 383 has described (methyl) vinylformic acid and organic polyhydric alcohol esterification method, and it is under 20-80 ℃ temperature of reaction, and use 2: 1-3: 1 equivalent is excessive to carry out.

The shortcoming of this method is that low reaction temperatures meaned the reaction times up to 35 hours, and the excess acid in the reaction mixture is separated subsequently and removes by neutralization.

WO 2001/14438 (DErwent makes a summary 2001-191644/19 number) and WO2001/10920 (chemistry summary 134:163502) have described in the presence of acid and polymerization retarder (methyl) vinylformic acid and pol yalkylene glycol monoalkyl ether with 3: 1-50: 1 ratio esterification, and behind the passivation an acidic catalyst, pH be under the 1.5-3.5 with the method for (methyl) acrylate and (methyl) acrylic acid residue copolymerization, and described residue is as the purposes of cement additire.

The shortcoming of these methods is that they are restricted to pol yalkylene glycol monoalkyl ether, necessary catalyst deactivation, and this analog copolymer can not be as the linking agent of hydrogel, because they only have a functionality.

The purpose of this invention is to provide can be used as and be used for polymkeric substance, other compounds of using of the free-radical crosslinking agent of high water absorbent especially, and simplify the preparation method of the material that can be used as the free-radical crosslinking agent that is used for high water absorbent.Also should further provide stability to hydrolysis height and/or while in the production process of high water absorbent, to produce the linking agent of very easily separable gel.The proof of variation in production operation and product should also provide performance and is easy to improved linking agent, because will cause fringe cost and inconvenience minimum.

We have found that this purpose realizes by at least two kinds of mixtures that respectively have the compound of two two keys at least, the WFR of described mixture is the two keys of 200-600g/mol, and at least two kinds of described compounds respectively contain at least two (methyl) acrylate as two key components, and WFR is provided by following formula:

$\underset{i=1}{\overset{n}{\mathrm{\&Sigma;}}}{\mathrm{\&alpha;}}_i\&times;{\mathrm{MW}}_i/Z_i=\mathrm{WFR},$ Wherein

$\underset{i=1}{\overset{n}{\mathrm{\&Sigma;}}}{\mathrm{\&alpha;}}_i=1$

α _iEqual the molar fraction of compound (i) in described mixture, n 〉=2, Z _iEqual the double key number order in the described compound (i), MW _iEqual the molecular weight of described compound (i).

WFR is the ratio of weight-functionality, corresponding to two key functionality of required compound or linking agent mixture.If the equational linear system of gained has one or more separating, then it can solve by the Gauss algorithm that is used for normal conditions (n component).This mixture is the optimization by the relative mark that changes component of mixture easily.Therefore, the specific linking agent performance of mixture also can be as required in the production of crosslinked polypropylene (for example high water absorbent), by simple change its known and the mark of permission component and identical change of amount that for example keeps used mixture simultaneously.Up to now, change consumption at the specific novel crosslinker of this purpose and synthetic and permission under a little cost and inconvenience.

The particular case of 2 component mixtures obtains following simple system:

α ₁* MW ₁/ Z ₁+ α ₂* MW ₂/ Z ₂=WFR and α ₂=1-α ₁,

It is simplified to α at last ₁=(WFR-MW ₂/ Z ₂)/(MW ₁/ Z ₁-MW ₂/ Z ₂).

Work as MW ₁/ Z ₁≠ MW ₂/ Z ₂And MW ₁/ Z ₁＜WFR＜MW ₂/ Z ₂Or MW ₂/ Z ₂＜WFR＜MW ₁/ Z ₁The time, this system has unique separating.

Preferred its lower limit is preferably 210,220,230 or 240, and the upper limit is preferably 550,500,450 or 400 said mixture, and the WFR that this mixture preferably has is the two keys of 240-400g/mol.Special preferred lower limit is 250,260,270,280 or 290, on be limited to 390,380,370,360 or 350, preferred especially WFR is the two keys of 250-350g/mol.Preferred especially 300-330/340.

Preferably wherein n is 2,3 or 4, more preferably 2 said mixture.

The preferred wherein ratio of the MW/Z of two kinds of compounds differs at least 50,60,70,80 or the two keys of 90g/mol, preferably at least 100,110,120,130,140,150,160,170,180,190,200,210,220,230, the two keys of 240g/mol, more preferably at least 250,260,270,280,290,300,310,320,330, the two keys of 340g/mol, especially 350,360,370,380,390 or the said mixture of the two keys of 400g/mol.

The preferred wherein ratio of a kind of MW/Z of compound is lower than the two keys of 400g/mol, preferably is lower than the two keys of 300g/mol, more preferably less than the two keys of 200g/mol, especially is lower than the said mixture of the two keys of 150g/mol.

The preferred wherein ratio of a kind of MW/Z of compound is higher than the two keys of 400g/mol and is lower than the two keys of 10000g/mol, preferably is higher than the two keys of 600g/mol and is lower than the said mixture of the two keys of 1000g/mol.

In mixture of the present invention, be preferably at the most 10 with number n, for example 9,8,7 or 6, more preferably 5 or still less, or 4 or still less, most preferably 3, especially 2 greater than 1% each compound that exists of mixture weight.

When each component of mixture forms the Gaussian distribution of each compound, above discuss the mid point value that preferably is applicable to each component.

The preferred wherein Z of at least a compound is 2-6, preferred 2,3 or 4 said mixture, and especially both are all at the said mixture of this scope.

The preferred ester F of compound wherein for obtaining by polyvalent alcohol Ai and (methyl) acrylic acid esterification _iSaid mixture, each polyvalent alcohol A wherein _iHas Z _iAn individual hydroxy functional group and especially 2-50 carbon atom.

The molecular weight of operable polyvalent alcohol unless have describedly in addition, otherwise is usually less than 5000g/mol, preferably is lower than 2500g/mol, more preferably less than 1500g/mol, most preferably is lower than 1000g/mol, especially is lower than 800g/mol.

Preferred polyhydric alcohols A is polyvalent alcohol, functionalized polyvalent alcohol, alkoxylated polyol, sugar alcohol, the oxyalkylated sugar alcohol of part, Aethoxy Sklerol, polyesterols, to oxyalkylated polyesterols of small part and partly-hydrolysed at least alkoxylate polyesterols.

Examples of polyhydric alcohols is a tri hydroxy methyl butane, TriMethylolPropane(TMP), trimethylolethane, neopentyl glycol, the hydroxy new pentane acid DOPCP, tetramethylolmethane, glycerine, 1,2-ethylene glycol, 1, the 2-propylene glycol, 1, ammediol, 1, the 2-butyleneglycol, 1, the 3-butyleneglycol, 1, the 4-butyleneglycol, 2-ethyl-1, ammediol, the 2-methyl isophthalic acid, ammediol, quinhydrones, dihydroxyphenyl propane, Bisphenol F, bisphenol b, 2, two (4-hydroxy-cyclohexyl) propane of 2-, 1, the 1-cyclohexanedimethanol, 1, the 2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol and 1, the 4-cyclohexanedimethanol, 1, the 2-cyclohexanediol, 1,3-cyclohexanediol or 1, the 4-cyclohexanediol, but-2-ene-1,4-two pure and mild fourth-2-alkynes-1, the 4-glycol has the sugar alcohol such as the Sorbitol Powder of C4-C6 chain.

Polyvalent alcohol can have other functional groups, for example ether functional group (O-), carboxyl functional group (COOH) or C ₁-C ₄Alkoxy carbonyl functional group (ester group), C herein ₁-C ₄Alkyl is represented methyl, ethyl, sec.-propyl, n-propyl, normal-butyl, isobutyl-, sec-butyl or the tertiary butyl.

Such functionalized examples of polyhydric alcohols is two (trishydroxymethyl) propane, Dipentaerythritol, dimethylol propionic acid, dimethylolpropionic acid, trishydroxymethyl acetate, hydroxy new pentane acid, and described these sour 2-hydroxyethyls-or C ₁-C ₄Alkyl ester.

Preferred polyhydric alcohols is those of formula (I):

Wherein

R ¹, R ²Be hydrogen, C independently ₁-C ₁₀Alkyl, preferred C ₁-C ₄Alkyl, C ₁-C ₁₀Hydroxyalkyl, preferred hydroxyl-C ₁-C ₄Alkyl, carboxyl or C ₁-C ₄Alkoxy carbonyl, preferred hydrogen, methylol and C ₁-C ₄Alkyl, more preferably methylol and C ₁-C ₄Alkyl.

Alkyl can respectively do for oneself straight chain or branching.

R ¹And R ²Example be hydrogen, methyl, ethyl, sec.-propyl, n-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, positive decyl, methylol, carboxyl, methoxycarbonyl, ethoxy carbonyl or n-butoxy carbonyl, preferred hydrogen, methylol, methyl and ethyl, more preferably methylol, methyl and ethyl.

Particularly preferred formula (I) polyvalent alcohol is a tri hydroxy methyl butane, TriMethylolPropane(TMP), trimethylolethane, neopentyl glycol, tetramethylolmethane, 2-ethyl-1, ammediol, the 2-methyl isophthalic acid, ammediol, 1, ammediol, 1, the 4-butyleneglycol, dimethylol propionic acid, the dimethylol propionic acid methyl esters, the dimethylol propionic acid ethyl ester, dimethylolpropionic acid, dimethylolpropionic acid methyl esters or dimethylolpropionic acid ethyl ester, preferred neopentyl glycol, TriMethylolPropane(TMP), tetramethylolmethane and dimethylol propionic acid, even more preferably neopentyl glycol, TriMethylolPropane(TMP) and tetramethylolmethane, especially TriMethylolPropane(TMP) and tetramethylolmethane.

The example of sugar alcohol is Sorbitol Powder, mannitol, maltose alcohol, Palatinitol, Glycerol dimer, threitol, erythritol, adonitol (ribitol), arabitol (lysol sugar alcohol (1yxitol)), Xylitol and galactitol (melampyrum).

The example of Aethoxy Sklerol is that molar mass is 162-2000, preferred 162-1458, more preferably 162-1098, more preferably 162-738 also, the polytetrahydrofuran of 162-378 most preferably, molar mass is 134-1178, preferred 134-888, more preferably 134-598, most preferably poly-1 of 134-308, ammediol and poly-1, the 2-propylene glycol, molar mass is 106-898, preferred 106-458, more preferably 106-400, the also more preferably polyoxyethylene glycol of 106-235, most preferably glycol ether, triglycol and Tetraglycol 99.

Useful polyesterols for example comprises can pass through poly carboxylic acid, the polyesterols of preferred dicarboxylic and above-mentioned polyvalent alcohol esterification preparation.

The raw material of such polyesterols is known by those skilled in the art.The poly carboxylic acid that can preferably use is oxalic acid, toxilic acid, fumaric acid, succsinic acid, pentanedioic acid, hexanodioic acid, sebacic acid, dodecanedioic acid, phthalic acid, m-phthalic acid, terephthalic acid, 1,2,4-benzenetricarboxylic acid, nonane diacid, 1,4-cyclohexane cyclohexanedimethanodibasic or tetrahydrophthalic acid, its isomery object and hydrogenated products, but and esterified derivative such as acid anhydrides or dialkyl such as C ₁-C ₄Alkyl ester, preferable methyl, ethyl or n-butyl.

Useful hydroxyl carboxylic acid or lactone comprise 4-hydroxy-benzoic acid, 6-hydroxyl-2-naphthoic acid, pivalolactone or caprolactone.Useful polyvalent alcohol comprises above-mentioned polyfunctional alcohol, preferred neopentyl glycol, TriMethylolPropane(TMP), trimethylolethane, tetramethylolmethane, dimethylol propionic acid or dimethylolpropionic acid.

The preferred embodiment of such polyesterols is the polyesterols of formula (IIIa-c):

Wherein

R ¹And R ²Each as defined above, and

Y is the alkylidene group that contains 2-20 carbon atom or the optional cycloalkylidene that contains 6-12 carbon atom or the arylidene or the singly-bound that replaces of the optional replacement of straight chain or branching.

The example of Y is singly-bound, methylene radical, ethylene, trimethylene, tetramethylene, 1,6-hexylidene, 1, the inferior heptyl of 7-, octamethylene, suitable-1,2-vinylidene, anti--vinylene, 1,2-, 1,3-or 1,4-phenylene, 1, the inferior hexamethylene of 2--1-thiazolinyl, 1,2-, 1,3-or 1,4-cyclohexylidene, 4-carboxyl-1,2-phenylene, 2-carboxyl-1,4-phenylene or 1-carboxyl-2,4-phenylene.

Preferred Y group is ethylene, tetramethylene and 1,2-, 1,3-or 1,4-phenylene.

It should be understood that production method can produce usually may additionally contain rudimentary and mixture higher oligomers.

In a further preferred embodiment, the reaction mixture of the polyesterols of near small part hydrolysis is as the polyvalent alcohol A that produces ester F.

Therefore, for example use suitable alkali, choose wantonly subsequently after removing the alkali components that residues in the reaction mixture with carboxylic acid B esterification with the partial hydrolysis at least of above-mentioned polyesterols.

Useful alkali comprises for example NaOH, KOH, Ca (OH) ₂, milk of lime, Na ₂CO ₃Or K ₂CO ₃, it for example is solid, solution or suspension, preferably is 10-50 weight % solution form, more preferably is 20-40 weight % aqueous solution form.

The degree that ester group is hydrolyzed (being cracking) in the polyesterols for example is at least 10% (based on the ester group in the initial compounds), preferably at least 25%, more preferably at least 50%, even more preferably at least 75%, most preferably at least 90%.

Work as alkaline components, when for example the basic salt of carboxylic acid will be removed from reaction mixture, this can for example pass through ion-exchanger, and for example acidity or strongly-acid ion-exchanger carry out.

Reaction mixture is used above-mentioned carboxylic acid B acidifying and esterification subsequently.

For example as described in the EP-A 279 303, polyester (methyl) acrylate can be multistage or single-stage by (methyl) vinylformic acid, poly carboxylic acid and polyvalent alcohol preparation.

Useful polyvalent alcohol further comprises alkoxylated polyol and polyesterols, and it can be by polyvalent alcohol or polyesterols and at least a reactions of alkylene oxide and obtains.

The present invention further provides the reaction mixture of formula VII compound:

R ⁸-(O(CH(R ¹⁰)CH(R ¹⁰)O) _y-C(＝O)-R ⁹) _x (VII)

Wherein

R ⁸Be multivalence straight chain or branching C ₂-C ₁₀Alkyl,

R ⁹Be straight chain or branching C in each case independently ₂-C ₁₀Alkenyl,

R ¹⁰Be hydrogen or methyl in each case independently,

X be independently in each case 〉=2 positive integer and

Y to x=2, is the number of 3-8 independently, and to x 〉=3, is the number of 2-7 in each case.

The alcohol for the treatment of esterification of its subordinate has formula VIIa:

R ⁸-(O(CH(R ¹⁰)CH(R ¹⁰)O)y-H)x (VIIa)

R wherein ⁸, R ¹⁰, x and y separately as defined above.

Formula (VII) compound be generally by a 2-8 oxyalkylene units/hydroxy alkoxy baseization and wherein the terminal hydroxy group of each oxyalkylene chain by C ₂-C ₁₀The C of unsaturated carboxylic acid or ester esterification ₂-C ₁₀Polyvalent alcohol VIIa.Initial alcohol is preferably the C that preferably has 2-4 hydroxyl ₃-C ₆Polyvalent alcohol.Initial alcohol is TriMethylolPropane(TMP), glycerine, tetramethylolmethane, 1 more preferably, ammediol, 1,2-propylene glycol, 1,4-butyleneglycol or butyleneglycol.Most preferably TriMethylolPropane(TMP), glycerine and tetramethylolmethane are as initial alcohol.

Useful oxyalkylene comprises for example ethylene oxide, propylene oxide, oxidation iso-butylene, vinyl oxyethane and/or Styrene oxide 98min..

Oxyalkylene chain can preferably be made of ethylene oxide, propylene oxide and/or oxybutylene unit.This chain can be made of the mixture of a kind of oxyalkylene or oxyalkylene.When using mixture, different oxyalkylene units can random form or with various types of block arrangement.Preferred oxyalkylene is ethylene oxide, propylene oxide or its mixture, more preferably ethylene oxide or propylene oxide, most preferably ethylene oxide.Therefore, preferred each oxyalkylene units R ⁹Group is a hydrogen, and another is methyl or hydrogen, more preferably two R ⁹Group is hydrogen simultaneously.

The preferred number of oxyalkylene units in each chain depends on the number of chain.

Esterifying agent is C ₂-C ₁₀Straight or branched ethylenically unsaturated carboxylic acids or ester, preferred C ₂-C ₄, more preferably C ₂-C ₃Ethylenically unsaturated carboxylic acids, even more preferably vinylformic acid, methacrylic acid or ester, most preferably vinylformic acid.

Formula VII compound usually exists with the mixture of the by product that obtains by the described compound of this formula with by preparation process.

The compound that in these compound VI I, especially preferably hereinafter is called compound VI Ib, its with 6 at the most, more preferably at the most 4,4 ethylene oxide unit/hydroxyl reactions most preferably.These compound VI Ib has the stability to hydrolysis of raising.

The preferred similarly compound VI I of compound VI Ic hereinafter referred to as:

-for x=2, its with＞8, more preferably＞10, even more preferably＞12, especially be no less than 15 an ethylene oxide units/hydroxyl reaction, or

-for x＞3, its with＞7, more preferably＞9, even more preferably＞12, most preferably be no less than 15 an ethylene oxide units/hydroxyl reaction, because these compound VI Ic has solubleness in the water of raising usually.

What also can expect is wherein for x=2, and y is 0,1 or 2, and for x=3, y is 0 or 1 compound VI I.

Particularly advantageous is the mixture of compound VI Ib and VIIc, and for example the VIIb:VIIc weight ratio is 10: 90-90: 10, preferred 20: 80-80: 20, more preferably 30: 70-70: 30, most preferably 40: 60-60: 40 mixture.Yet this ratio of mixture is mainly by the performance decision of the required end product of polymkeric substance.

The preferred embodiment of such alkoxylated polyol is the alkoxylated polymerization product (IIa), (IIb) of formula (I) polyvalent alcohol or (IIc)

Wherein

R ¹And R ²Respectively as defined above,

K, l, m and q are 1-10 independently, preferred 1-5, and the more preferably integer of 3-5, most preferably 4,

And

Each Xi, for i=1-k, 1-l, 1-m and 1-q can be independently selected from :-CH ₂-CH ₂-O-,-CH ₂-CH (CH ₃)-O-,-CH (CH ₃)-CH ₂-O-,-CH ₂-C (CH ₃) ₂-O-,-C (CH ₃) ₂-CH ₂-O-,-CH ₂-CHVin-O-,-CHVin-CH ₂-O-,-CH ₂-CHPh-O-and-CHPh-CH ₂-O-is preferably selected from-CH ₂-CH ₂-O-,-CH ₂-CH (CH ₃)-O-and-CH (CH ₃)-CH ₂-O-, more preferably-CH ₂-CH ₂-O-,

Wherein Ph is that phenyl and Vin are vinyl.

It is heavy that described compound is preferably 1-5, and more preferably 3-5 is heavy, most preferably 4 heavily ethoxylations, propoxylation or mixing ground ethoxylation and propoxylation, the especially only neopentyl glycol of ethoxylation, TriMethylolPropane(TMP), trimethylolethane or tetramethylolmethane.

Such polyvalent alcohol of wherein special preferred formula (IIb).

Preferred similarly 1-20 is heavy, preferred 1-10 is heavy, more preferably 2-10 is heavy, even more preferably 2-5 is heavy, especially 3-5 is heavy, particularly 3-4 weighs alkoxylate, preferred ethoxylation, propoxylation or mixing ground ethoxylated/propoxylated, the more preferably glycerine of ethoxylation (herein exceptionally in alkoxyl group mole number/mole of glycerin).

Shown in extent of alkoxylation separately based on average extent of alkoxylation.

The number-average molecular weight M of alkoxylated polyol _nPreferably be not more than 1000g/mol,, most preferably be not more than 550g/mol more preferably no more than 800g/mol.

Here about number average and weight-average molecular weight M _nAnd M _wStatement based on gel permeation chromatography measurement, use polystyrene as standard substance, tetrahydrofuran (THF) is as moving phase.This method is described in Ahalytiker Taschenbuch the 4th volume, and the 433-442 page or leaf is among the Berlin 1984.

The example of alkoxylate sugar alcohol is can be by sugar alcohol, for example by above-mentioned sugar alcohol by for example with above-mentioned oxyalkylene, preferably with ethylene oxide and/or propylene oxide, the compound that obtains with the ethylene oxide alkoxylate most preferably.

The example is:

-cited tetrol, it is by average 2-30, preferred 2-20, more preferably 3-10, especially 3,4,5,6,7 or 8 oxyalkylene units/mole sugar alcohol alkoxylates,

-cited pentol, it is by average 3-35, preferred 3-28, more preferably 4-20, especially 4,5,6,7,8,9 or 10 oxyalkylene units/mole sugar alcohol alkoxylates,

-senior sugar alcohol, it is by average 4-50, preferred 6-40, more preferably 7-30, even more preferably 8-20, most preferably 10-15 oxyalkylene units/mole sugar alcohol alkoxylate.

The preferred alkoxylated sugar alcohol is at least one hydroxyl alkoxylate sugar alcohol of alkoxyization not as yet of wherein sugar alcohol.

The preferred embodiment of alkoxylate polyesterols is the alkoxylate polyesterols of formula (IVa-c):

Wherein

R ¹, R ²With Y each as defined above,

K, l, m, q, r and s are 1-30 independently, preferred 1-20, more preferably 1-10, most preferably the integer of 1-5 and

Each Xi, for i=1-k, 1-l, 1-m, 1-q, 1-r and 1-s can independently be selected from :-CH ₂-CH ₂-O-,-CH ₂-CH (CH ₃)-O-,-CH (CH ₃)-CH ₂-O-,-CH ₂-C (CH ₃) ₂-O-,-C (CH ₃) ₂-CH ₂-O-,-CH ₂-CHVin-O-,-CHVin-CH ₂-O-,-CH ₂-CHPh-O-and-CHPh-CH ₂-O-is preferably selected from-CH ₂-CH ₂-O-,-CH ₂-CH (CH ₃)-O-and-CH (CH ₃)-CH ₂-O-, more preferably-CH ₂-CH ₂-O-,

Wherein Ph is that phenyl and Vin are vinyl.

Not alkoxylate or 1-10 that described compound is preferably neopentyl glycol, TriMethylolPropane(TMP), trimethylolethane or tetramethylolmethane and hexanodioic acid, phthalic acid, terephthalic acid or m-phthalic acid are heavy, more preferably heavily ethoxylation of 2-5, propoxylation or mixing ground ethoxylation and propenoxylated esterification products.

Alcohol is that those skilled in the art are known with the reaction of oxyalkylene itself.Feasible program can be referring to Houben-Weyl, Methoden der Organischen Chemie, and the 4th edition, 1979, Thieme Verlag Stuttgart, Heinz Kropf edits, 6/1a volume, part 1,373-385 page or leaf.

When use mixing the oxyalkylated alcohol in ground, be present in different alkoxyl groups 0.05-20 for example wherein: 1, preferred 0.1-10: 1, more preferably 0.2-5: 1 mol ratio is distributed.

Viscosity to polyvalent alcohol that can be used according to the invention does not have special requirement, but it should easily be pumped to about 80 ℃, and preferably it should have the 1000mPas of being lower than, and preferably is lower than 800mPas, most preferably is lower than the viscosity of 500mPas.

When the polyvalent alcohol that is used for esterification had 3 or more a plurality of hydroxyl, it can be used as free-radical crosslinking agent dexterously according to the present invention, because of its only by partial esterification.In other words, under the situation of n unit polyvalent alcohol, have only at least 2 in n the hydroxyl by carboxylic acid B esterification.

For n=3, gamma value is at least 2; For n=4, be at least 2, preferably at least 2.5, more preferably at least 3; For n 〉=5, be at least 2, preferably at least 3, more preferably at least 4.

In this case, the excessive target gamma value that depends on of the target stoichiometry of carboxylic acid B, therefore for example under the situation of n times of polyvalent alcohol, for above-mentioned gamma value be 2 molar excess 2/n doubly.In case it should be understood that to reach required gamma value, esterification also can for example be ended by cooling or dilution.

Can be used for ethylenically unsaturated carboxylic acids B of the present invention and comprise having at least one, a preferred carboxyl (COOH), and at least one, the compound of a preferred ethylenically unsaturated group.

Can be used for carboxylic acid of the present invention can be aliphatic series, cyclic aliphatic or aromatics, and preferred aliphatic series or cyclic aliphatic are most preferably aliphatic, straight chain or branching and the optional carboxylic acid that is replaced by functional group.

Described carboxylic acid has 3-10 carbon atom usually, preferred 3-5 carbon atom, more preferably 3-4 carbon atom.

The example of ethylenically unsaturated carboxylic acids B is vinylformic acid, methacrylic acid, ethylacrylic acid, toxilic acid, maleic anhydride, fumaric acid, methylene-succinic acid, citraconic acid, methylfumaric acid, vinylacetic acid, allyl acetic acid and Ba Dousuan.

Preferred carboxylic acid B is α, beta-unsaturated carboxylic acid.

Special preferable methyl vinylformic acid and vinylformic acid are called (methyl) vinylformic acid herein, most preferably vinylformic acid.

The preferred ester of other of polyvalent alcohol is as follows:

Wherein AO is EO or PO in each case independently,

Wherein EO is O-CH2-CH2-,

PO be independently in each case O-CH2-CH (CH3)-or

O-CH(CH3)-CH2-，

P1+p2+p3 is the integer of 0-5, preferred 0 or 3,4 or 5,

R1, R2, R3 are H or CH3 independently.

EO and PO unit are to form polyethers but not the mode of superoxide is introduced.

Preferably wherein AO is the above-mentioned ester F of EO or PO, especially EO.

Preferred p1 wherein, the ester F of p2+p3=3 or p1=p2=p3=0.

Also preferably wherein at least one AO be PO, and at least one other AO is the above-mentioned ester F of EO.

We have found that the ester F of the further through type Ib of this purpose realizes:

Wherein EO is O-CH2-CH2-

PO is O-CH2-CH (CH3)-or O-CH (CH3)-CH2-in each case independently

M1+m2+m3+n1+n2+n3 is 3,4 or 5,

M1+m2+m3 is 1,2,3 or 4,

R1, R2, R3 are H or CH3 independently.

Perhaps, the ester F of this purpose through type Ic realizes:

Wherein EO is O-CH2-CH2-

PO is O-CH2-CH (CH3)-or O-CH (CH3)-CH2-in each case independently

M1+m2+m3+n1+n2+n3 is 3,4 or 5,

M1+m2+m3 is 1,2,3 or 4,

R1, R2, R3 are H or CH3 independently.

The ester F that preferred wherein m1+m2+m3+n1+n2+n3 or p1+p2+p3 equal 3 in above-mentioned ester.

The ester F that preferred wherein m1+m2+m3+n1+n2+n3 or p1+p2+p3 equal 5 in above-mentioned ester.

Especially preferably wherein always have 3 unitary ester F of PO.

Very particularly preferably wherein at the ester F that respectively has at least one PO of 3 oxyalkyl chains of glycerine.

Very particularly preferably wherein R1, R2 are identical with R3, especially the ester F when R1, R2 and R3 are H.

Further be preferably as follows ester:

Or

Wherein in formula Id and Ie, EO is O-CH2-CH2-,

PO is O-CH2-CH (CH3)-or O-CH (CH3)-CH2-in each case independently,

N1+n2+n3 is 28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43,44,45,46,47,48,49,50,51,52,53,54,55,56,57,58,59 or 60,

M1+m2+m3 is 4,5,6,7,8,9,10,11,12 or 13,

R1, R2, R3 are H or CH3 independently.

EO and PO unit are with the formation polyethers, but not the mode of superoxide is introduced.

Preferred wherein n1, n2, n3 are 9,10,11,12,13,14,15,16,17,18,19 or 20 above-mentioned ester F independently.

Preferred especially wherein n1, n2, n3 are 9,10 or 11 above-mentioned ester F independently.

Preferred especially wherein n1, n2, n3 are 15,16,17,18,19 or 20 above-mentioned ester F independently.

The above-mentioned ester F that preferred wherein n1+n2+n3 equals 28,29,30,31 or 32.

The above-mentioned ester F that preferred especially wherein n1+n2+n3 equals 45,46,47,48,49,50,51,52,53,54,55,56,57,58,59 or 60.

The above-mentioned ester F that preferred especially wherein n1+n2+n3 equals 30.

The above-mentioned ester F that preferred especially wherein n1+n2+n3 equals 50.

Especially the preferred wherein above-mentioned ester F of n1=n2=n3=10.

Especially the above-mentioned ester F of preferred wherein n1=n2=17 and n3=16.

Also preferred wherein m1, m2, m3 are 1,2,3,4 or 5 above-mentioned ester F independently.

Preferred especially wherein m1, m2, m3 are 1,2 or 3 above-mentioned ester F independently.

Preferred especially wherein m1, m2, m3 are 2,3,4 or 5 above-mentioned ester F independently.

The above-mentioned ester F that preferred wherein m1+m2+m3 equals 4,5 or 6.

The above-mentioned ester F that preferred wherein m1+m2+m3 equals 7,8,9,10,11,12 or 13.

The above-mentioned ester F that preferred especially wherein m1+m2+m3 equals 5.

The above-mentioned ester F that preferred especially wherein m1+m2+m3 equals 10.

Especially preferably m wherein _i=m _k=3 and m _l=4, wherein i, k, l are different entirely, and are selected from 1,2,3 above-mentioned ester F.

Especially preferably m wherein _i=m _k=2 and m _l=1, wherein i, k, l are different entirely, and are selected from 1,2,3 above-mentioned ester F.

Very particularly preferably wherein R1, R2 are identical with R3, especially the ester F when R1, R2 and R3 are H.

Also preferred following ester:

Wherein EO is O-CH2-CH2-,

PO is O-CH2-CH (CH3)-or O-CH (CH3)-CH2-in each case independently,

N1, n2, n3 are 4,5 or 6 independently,

N1+n2+n3 is 14,15 or 16,

M1, m2, m3 are 1,2 or 3 independently,

M1+m2+m3 is 4,5 or 6,

R1, R2, R3 are H or CH3 independently.

EO and PO unit are with the formation polyethers, but not the mode of superoxide is introduced.

The above-mentioned ester F that preferred wherein n1+n2+n3 equals 15.

The preferred especially wherein above-mentioned ester F of n1=n2=n3=5.

The above-mentioned ester F that also preferred wherein m1+m2+m3 equals 5.

The above-mentioned ester F of also preferred especially wherein m1=m2=2 and m3=1.

Very particularly preferably wherein R1, R2 are identical with R3, especially the ester F when R1, R2 and R3 are H.

Also preferred following ester:

Wherein AO be independently in each case-O-CHR3-CHR4-or-CHR3-CHR4-O-, wherein R3 and R4 are H, linearity or branching C1-C8 alkyl independently,

P1 is 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30,31,32,33,34 or 35,

P2 is 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30,31,32,33,34 or 35,

N is 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43,44,45,46,47,48,49,50,51,52,53,54,55,56,57,58,59,60,61,62,63,64,65,66,67,68,69,70,71,72,73,74,75,76,77,78,79,80,81,82,83,84,85,86,87,88,89,90,91,92,93,94,95,96,97,98,99,100

R1 and R2 are H or CH3 independently,

Wherein at least one AO is present among (AO) p1, and at least one AO is present among (AO) p2,

Wherein R3 and R4 are not H simultaneously.

The AO unit is with the formation polyethers, but not the mode of superoxide is introduced.

Preferably wherein for all AO, R3 and R4 have the above-mentioned ester F of identical meanings independently, i.e. the above-mentioned ester F that for example can obtain by ethylene glycol or polyoxyethylene glycol and only a kind of oxyalkylene such as propylene oxide alkoxylate.

Preferred wherein R3 or R4 are the above-mentioned ester F of H.

Preferably wherein R3 or R4 are CH3, CH2CH3, (CH2) 2-CH3 or (CH2) 7-CH3 independently, the above-mentioned ester F of preferred CH3.

Also preferably wherein p1 be 1,2,3,4 or 5, more preferably 1,2 or 3, especially 1, or be the above-mentioned ester F of the number of 14-27.

Also preferably wherein p2 be 1,2,3,4 or 5, more preferably 1,2 or 3, especially 1, or be the above-mentioned ester F of the number of 14-27.

Preferably wherein n is 2-50, the above-mentioned ester F of the number of preferred 5-30, especially 10-26.

Preferred diol component (AO) p1-[-O-CH2-CH2-wherein] molecular-weight average of n-O-(AO) p2 is 300-500, especially about 400 above-mentioned ester F.

Preferred diol component (AO) p1-[-O-CH2-CH2-wherein] molecular-weight average of n-O-(AO) p2 is 2000-4000, the more preferably above-mentioned ester F of 2500-3500.

In above-mentioned ester F, preferred diol component just has symmetric construction with regard to (AO) p1 and (AO) p2 each other.Symmetry is meant that p1 and p2 are equal substantially, and promptly the absolute difference between p1 and p2 is 3 or littler, preferred 2 or littler, more preferably 1 or littler, especially equal 0.

In above-mentioned ester F, further preferred diol component is (AO) p1 and (AO) have each other on the structure with regard to the p2 and similarly construct just.Similarly on the structure be meant each (AO) p1 and (AO) the p2 component is by synthetic simultaneously preparation on (gather) ethylene glycol, and therefore the two can synthesize (block (AO) p component) by the mixture (random (AO) p component) of different alkoxides or order and obtains.The diol component that preferred especially wherein all AO all have identical meanings and preferably formed by propylene oxide.

Preferably wherein R1 is identical with R2, is preferably the above-mentioned ester F of H.

According to the present invention, the ester F with said structure formula of described implication can be used for preparing the polymkeric substance that forms hydrogel, and described polymkeric substance can absorb liquid, aqueous, especially as internal crosslinking agent.Other preferred internal crosslinking agents are for having 2,3,4 or 5, especially two of 2 or 3 unitary polypropylene glycols of propylene glycol (methyl) acrylate, especially diacrylate.

In said mixture, a kind of compound preferably can be represented by one of following structural:

Or

Wherein AO be independently in each case-O-CHR7-CHR8-or-CHR7-CHR8-O-, wherein R7 and R8 are H, linearity or branching C1-C8 alkyl independently,

R5 and R6 are H, linearity or branching C1-C8 alkyl independently,

N is 1,2 or 3,

P1 is 0,1 or 2,

P2 is 0,1 or 2,

P3 is 0,1 or 2,

P4 is 0,1 or 2,

R1, R2, R3, R4 are H or CH3 independently,

Similarly, the ester in the mixture preferably can be represented by one of following structural:

Or

Wherein AO be independently in each case-O-CHR7-CHR8-or-CHR7-CHR8-O-, wherein R7 and R8 are H, linearity or branching C1-C8 alkyl independently,

R5 and R6 are H, linearity or branching C1-C8 alkyl independently,

N is 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19 or 20,

P1 is 7,8,9,10,11,12,13,14,15,16,17,18,19 or 20,

P2 is 7,8,9,10,11,12,13,14,15,16,17,18,19 or 20,

P3 is 7,8,9,10,11,12,13,14,15,16,17,18,19 or 20,

P4 is 7,8,9,10,11,12,13,14,15,16,17,18,19 or 20,

R1, R2, R3, R4 are H or CH3 independently.

Preferred especially wherein AO be such mixture of EO or PO in each case independently, and wherein EO is O-CH2-CH2-, PO be independently in each case O-CH2-CH (CH3)-or O-CH (CH3)-CH2-and R5 and R6 be H or CH3 independently.Segmented copolymer that preferred especially wherein AO is EO and PO and PO unit be position and by those of acroleic acid esterification endways.

Especially be preferably selected from by the ester of formula Ig, Ih, Ii or Ij representative and select the mixture of the ester of free style Ik, Il, Im or In representative.

Preferably with the component of following other esters: the diacrylate butanediol ester as mixture, butyleneglycol-1EO-diacrylate, butyleneglycol-2EO-diacrylate, butyleneglycol-1EO-1PO-diacrylate, butyleneglycol-2PO-diacrylate, butyleneglycol-3EO-diacrylate, butyleneglycol-2EO-1PO-diacrylate, butyleneglycol-1EO-2PO-diacrylate, butyleneglycol-3PO-diacrylate, Viscoat 295, trimethylolpropane diacrylate, TriMethylolPropane(TMP)-3EO-triacrylate, TriMethylolPropane(TMP)-3EO-diacrylate, TriMethylolPropane(TMP)-2EO-1PO-triacrylate, TriMethylolPropane(TMP)-2EO-1PO-diacrylate, TriMethylolPropane(TMP)-1EO-2PO-triacrylate, TriMethylolPropane(TMP)-1EO-2PO-diacrylate, TriMethylolPropane(TMP)-3PO-triacrylate, TriMethylolPropane(TMP)-3PO-diacrylate, TriMethylolPropane(TMP)-4EO-triacrylate, TriMethylolPropane(TMP)-4EO-diacrylate, TriMethylolPropane(TMP)-1PO-3EO-triacrylate, TriMethylolPropane(TMP)-1PO-3EO-diacrylate, TriMethylolPropane(TMP)-2EO-2PO-triacrylate, TriMethylolPropane(TMP)-2EO-2PO-diacrylate, TriMethylolPropane(TMP)-1EO-2PO-triacrylate, TriMethylolPropane(TMP)-1EO-3PO-diacrylate, TriMethylolPropane(TMP)-4PO-triacrylate, TriMethylolPropane(TMP)-4PO-diacrylate, glycerol tri-acrylate, the glycerine diacrylate, glycerine-3EO-triacrylate, glycerine-3EO-diacrylate, glycerine-2EO-1PO-triacrylate, glycerine-2EO-1PO-diacrylate, glycerine-1EO-2PO-triacrylate, glycerine-1EO-2PO-diacrylate, glycerine-3PO-triacrylate, glycerine-3PO-diacrylate, glycerine-4EO-triacrylate, glycerine-4EO-diacrylate, glycerine-1PO-3EO-triacrylate, glycerine-1PO-3EO-diacrylate, glycerine-2EO-2PO-triacrylate, glycerine-2EO-2PO-diacrylate, glycerine-1EO-2PO-triacrylate, glycerine-1EO-3PO-diacrylate, glycerine-4PO-triacrylate, glycerine-4PO-diacrylate, pentaerythritol triacrylate, pentaerythritol diacrylate, tetramethylolmethane-3EO-triacrylate, tetramethylolmethane-3EO-diacrylate, tetramethylolmethane-2EO-1PO-triacrylate, tetramethylolmethane-2EO-1PO-diacrylate, tetramethylolmethane-1EO-2PO-triacrylate, tetramethylolmethane-1EO-2PO-diacrylate, tetramethylolmethane-3PO-triacrylate, tetramethylolmethane-3PO-diacrylate, tetramethylolmethane-4EO-triacrylate, tetramethylolmethane-4EO-diacrylate, tetramethylolmethane-1PO-3EO-triacrylate, tetramethylolmethane-1PO-3EO-diacrylate, tetramethylolmethane-2EO-2PO-triacrylate, tetramethylolmethane-2EO-2PO-diacrylate, tetramethylolmethane-1EO-2PO-triacrylate, tetramethylolmethane-1EO-3PO-diacrylate, tetramethylolmethane-4PO-triacrylate, tetramethylolmethane-4PO-diacrylate, tetramethylol methane tetraacrylate, tetramethylolmethane-5EO-tetraacrylate, tetramethylolmethane-3EO-tetraacrylate, tetramethylolmethane-4EO-1PO-tetraacrylate, tetramethylolmethane-2EO-1PO-tetraacrylate, tetramethylolmethane-3EO-2PO-tetraacrylate, tetramethylolmethane-1EO-2PO-tetraacrylate, tetramethylolmethane-3PO-2EO-tetraacrylate, tetramethylolmethane-3PO-tetraacrylate, tetramethylolmethane-4EO-tetraacrylate, tetramethylolmethane-1EO-4PO-tetraacrylate, tetramethylolmethane-5PO-tetraacrylate, tetramethylolmethane-1PO-3EO-tetraacrylate, tetramethylolmethane-2EO-2PO-tetraacrylate, tetramethylolmethane-1EO-3PO-tetraacrylate, tetramethylolmethane-4PO-tetraacrylate.

The ester mixture that preferred especially one of them component is represented by one of following compounds: glycerine-3EO-triacrylate (G3EOTA), glycerine-3PO-triacrylate (G3POTA), glycerol tri-acrylate (GTA), TriMethylolPropane(TMP)-3EO-triacrylate (TMP3EOTA), trimethyl propane-3PO-triacrylate (TMP3POTA) and Viscoat 295 (TMPTA).Other components are preferably at first by 5PO, then by the 30EO alkoxylate, then by the trimethyl propane of the complete esterification of vinylformic acid (TMP5PO30EOTA), and at first by 30EO, then by the 5PO alkoxylate, then by the trimethyl propane of the complete esterification of vinylformic acid (TMP30EO5POTA).

Mixture very particularly preferably is:

The mixture of the mixture of the mixture of G3EOTA and TMP30EO5POTA, G3POTA and TMP30EO5POTA, GTA and TMP30EO5POTA.

These linking agents preferred especially with those combinations with formula Im.Further observation is not only applicable to prepare each ester by polyvalent alcohol, and is applicable to by polyol blends and prepares ester mixture.Ester F is hereinafter as representative.

We have found that this purpose further realizes that by a kind of method for preparing polyvalent alcohol A and (methyl) acrylic acid ester F it may further comprise the steps:

A) make the reaction in the presence of at least a esterifying catalyst C and at least a polymerization retarder D and optional water azeotropic solvent E of polyvalent alcohol A and (methyl) vinylformic acid, formation ester F,

B) during a) and/or afterwards, optionally take out the portion water at least that in a), forms by reaction mixture,

F) the described reaction mixture of optional neutralization,

H) when using solvent E, optional by this solvent of distillation taking-up, and/or

I) be used in and be the inert gasses stripping under the reaction conditions.

In preferred embodiments,

-(methyl) vinylformic acid is at least 1.05: 1 to the molar excess for the treatment of each hydroxyl of esterification in A of described polyvalent alcohol A, and

Optional neutral (methyl) vinylformic acid that comprises in-this reaction mixture is in the end still significantly stayed in this reaction mixture after the step.

For the present invention, (methyl) vinylformic acid comprises methacrylic acid, acrylic or methacrylic acid and acrylic acid mixture.Preferred vinylformic acid.

When the pure ester F of needs, it can pass through the known separation method purifying.

(methyl) vinylformic acid is at least 1.05: 1 to the molar excess of A (each hydroxyl for the treatment of esterification among the polyvalent alcohol A), preferably at least 1.1: 1, more preferably at least 1.25: 1, even more preferably at least 1.5: 1, especially at least 2.5: 1.

In preferred embodiments, (methyl) vinylformic acid for example greater than 10: 1, is preferably greater than 20: 1 with excessive use, more preferably greater than 40: 1, even more preferably greater than 100: 1, especially greater than 150: 1, particularly greater than 200: 1.

The esterification products that can obtain thus can be used as free-radical crosslinking agent in hydrogel, and need not be further purified substantially, particularly need not remove excessive (methyl) vinylformic acid and esterifying catalyst C substantially.

Unless mention in addition, used hereinly crosslinkedly be interpreted as group crosslinked (gel is crosslinked; Internal crosslinking; Linearity or low cross-linking polymkeric substance are crosslinked together).This crosslinked can being undertaken by free radical or cationic polymerization mechanism or other mechanism, for example Michael addition, esterification or transesterify mechanism, but preferably undertaken by radical polymerization.

The polymkeric substance that can absorb liquid, aqueous formation hydrogel preferably can absorb at least himself weight, preferred 10 times of himself weight, the more preferably distilled water of 20 times of himself weight, even and they under 0.7psi pressure, also preferably can realize this absorption.

Can be used for polyvalent alcohol of the present invention for having at least 2, preferably at least 3, more preferably 3-10 is individual, even more preferably 3-6 is individual, especially 3-4 the hydroxyl (OH) compound of functional group.

Polyvalent alcohol can be aliphatic series, cyclic aliphatic or aromatics, and preferred aliphatic series or cyclic aliphatic are most preferably aliphatic, straight chain or branching, and choose those that are replaced by functional group wantonly.

Carbonatoms in the polyvalent alcohol is generally 2-50, preferred 3-40.

The reaction of polyvalent alcohol and oxyalkylene itself is that those skilled in the art are known.We are at Houben-Weyl, Methoden der Organischen Chemie, and the 4th edition, 1979, ThiemeVerlag Stuttgart, Heinz Kropf edits, the 6/1a volume, part 1 is found the possible mode of carrying out this reaction in the 373-385 page or leaf.

The example of the mode of preparation polyvalent alcohol A is to make polyvalent alcohol and EO reaction (to obtain required poly-ethylidene polyvalent alcohol), reacts with PO then.

This for example can realize in the following manner.Will about 72g ethylene glycol (examples of polyhydric alcohols) or the polyoxyethylene glycol and the 0.5g KOH of respective amount, the aqueous solution with 45% places autoclave as initial charge, and 80 ℃ and decompression (about 20 millibars) down with this initial charge dehydration.Then, add an amount of propylene oxide down at 145-155 ℃, and it is reacted under this temperature and high pressure.When no longer observing pressure and further change, reaction finishes.Then, with reaction mixture 150 ℃ of following restir 30 minutes.Add an amount of propylene oxide through long-time down at 120-130 ℃ subsequently, and make its reaction equally.With the rare gas element scrubbing and after being cooled to 60 ℃, isolate catalyzer by adding trisodium phosphate and subsequent filtration.

Yet, also can use commercially available alkoxylated diols, for example the triblock polymer of dipropylene glycol and tripropylene glycol and PO-EO-PO type, for example Pluronic of 1720,1740,2035,2510,2520,2525 or 3110 types ^The RPE polymkeric substance.

Viscosity to polyvalent alcohol that can be used according to the invention does not have any particular requirement, but they should easily be pumped to about 80 ℃, and preferably they should have the 1000mPas of being lower than, and preferably are lower than 800mPas, most preferably are lower than the viscosity of 500mPas.

Can be used for esterifying catalyst C of the present invention is sulfuric acid, aryl or alkylsulphonic acid or its mixture.The example of aryl sulfonic acid is Phenylsulfonic acid, tosic acid and Witco 1298 Soft Acid, and the example of alkylsulphonic acid is methylsulfonic acid, ethyl sulfonic acid and trifluoromethanesulfonic acid.Similarly, strongly-acid ion-exchanger or zeolite can be used as esterifying catalyst.Preferably sulfuric acid and ion-exchanger.

Preferred described phenols and quinones, preferred especially quinhydrones, hydroquinone monomethyl ether, the 2-tertiary butyl-4-methylphenol, the 6-tertiary butyl-2,4-xylenol, 2,6 di tert butyl 4 methyl phenol, 2,4-DI-tert-butylphenol compounds, tricresyl phosphite phenylester, Hypophosporous Acid, 50, CuCl ₂And methyl catechol, very particularly preferably quinhydrones and hydroquinone monomethyl ether.

Preferred especially hydroquinone monomethyl ether, quinhydrones and alkylphenol, optional and tricresyl phosphite phenylester and/or Hypophosporous Acid, 50 combination.

Very particularly preferably alpha-tocopherol (vitamin-E), 5,8-dimethyl tocol, Gamma-Tocopherol or Delta-Tocopherol are chosen wantonly and tricresyl phosphite phenylester and/or Hypophosporous Acid, 50 combination.

Very particularly preferably only use sterically hindered phenol as stablizer, it is compared with hydroquinone monomethyl ether, for identical end product acid number, produces the not too dark product mixtures of color during esterification.The example of such most preferred stablizer is an alpha-tocopherol.

Static stabilization can be because of oxygen-containing gas, the existence of the mixture (poor air) of preferred air or air and nitrogen and further being promoted.

In described stablizer, preferably aerobic, promptly need oxygen exist with abundant development its inhibiting those.

Can be used for solvent E of the present invention and particularly be suitable for the solvent that azeotropic takes out reaction water (if words of needs), particularly aliphatic series, cyclic aliphatic and aromatic hydrocarbon or its mixture.

Preferred Skellysolve A, normal hexane, normal heptane, hexanaphthene, methylcyclohexane, benzene, toluene or dimethylbenzene.Preferred especially hexanaphthene, methylcyclohexane and toluene.

This esterification can be undertaken by the routine preparation and/or the treatment process of polyvalent alcohol, mentioned method when this paper begins for example, or in the method described in DE-A 199 41 136, DE-A 38 43 843, DE-A 38 43854, DE-A 199 37 911, DE-A 199 29 258, EP-A 331 845, EP 554 651 or the US 4 187 383.

Usually, this esterification is as described below carries out:

The esterification device comprises stirred reactor, preferably has circulating evaporator and have adding of condenser and phase separation container to distill unitary reactor.

Reactor can be for example for having the reactor of chuck heating and/or inner heating coil.The following reactor of preferred use: have external heat exchanger and nature or, more preferably wherein do not use mechanical assistant promptly to realize the round-robin natural circulation by using the pump circulation of pump.

It should be understood that reaction also can carry out in a plurality of reaction zones, for example at 2-4, the set of reactors of preferred 2-3 reactor.

Suitable circulating evaporator is known by those skilled in the art, and is described in for example R.Billet, Verdampfertechnik, and HTB-Verlag, Bibliographisches InstitutMannheim is in 1965,53.The example of circulating evaporator is pipe bundle heat exchanger, plate-type heat exchanger etc.

It should be understood that circulating system also can comprise a plurality of interchanger.

The distillation unit has conventional design.It can be the simple distillation unit, if suitable words are equipped with the splash protector, or can be rectifying tower.Suitable column internals comprises all internals commonly used, for example tower tray, structured packing and/or dump packing in principle.Preferred tower tray comprises bubble tray, screen tray, valve tray, Thorman tower tray and/or double-pass tray, and preferred dump packing is ring, coil pipe, saddle or cloth.

Usually, 5-20 theoretical stage is just enough.

Condenser and separation vessel have traditional design.

(methyl) vinylformic acid and alkoxylated diols are used for esterification a) with aforesaid molar excess usually.If need, used excessive can be up to about 3000: 1.

Useful esterifying catalyst C comprise mentioned above those.

They usually based on esterification mixture with 0.1-5 weight %, preferred 0.5-5 weight %, more preferably 1-4 weight %, most preferably the amount of 2-4 weight % is used.

If necessary, esterifying catalyst can be removed by reaction mixture by ion-exchanger.Ion-exchanger directly can be added in the reaction mixture and filtering subsequently, maybe can be with reaction mixture by the ion-exchanger bed.

Esterifying catalyst is preferably stayed in the reaction mixture.Yet when catalyzer was ion-exchanger, ion-exchanger was preferably by for example removing by filter.

Static stabilization can pass through oxygen-containing gas, the existence of the mixture (poor air) of preferred air or air and nitrogen and further being supported.

Preferably this oxygen-containing gas is metered into the bottom section of tower, and/or add in the circulating evaporator and/or among the reaction mixture and/or on pass through.

Polymerization retarder (mixture) D (as mentioned above) based on esterification mixture with 0.01-1 weight %, preferred 0.02-0.8 weight %, more preferably the total amount of 0.05-0.5 weight % is used.

Polymerization retarder (mixture) D can for example use with the aqueous solution or the solution in reactant or product.

B) can be during esterification be a) or steam the reaction water that in reaction process, forms afterwards, at this moment, this operation can be supported by the solvent that forms azeotrope with water.

If need, can be used in the solvent E that azeotropic takes out reaction water, comprise above cited compound.

Esterification is preferably carried out in the presence of solvent.

The consumption of solvent is 10-200 weight % based on alkoxylated diols and (methyl) acrylic acid summation, preferred 20-100 weight %, more preferably 30 weight %-100 weight %.

Yet, also can imagine the operation of not using entrainer, for example at DE-A1 38 43 854, the 2nd hurdle the 18th walks to described in the 4th hurdle the 45th row, but offers paired ratio with institute's quoted passage of mentioning the aforementioned stable agent.

When the water in the reaction mixture does not take out via the solvent that forms azeotrope, for example as DE-A3843843 described in, its available rare gas element, preferred oxygen-containing gas, more preferably air or poor air stripping taking-up.

Esterification temperature of reaction a) is generally 40-160 ℃, preferably at 60-140 ℃, and more preferably 80-120 ℃.In reaction process, temperature can keep constant or raise and preferably be raised in reaction process.At this moment, the outlet temperature of esterification is compared with high 5-30 ℃ of beginning temperature.Esterification temperature can be determined by the solvent strength in the reacting condition mixture and control, as described in the German application of DE-A 199 41 136 and document reference number 100 63 175.4.

When using solvent, it can be distilled out by reaction mixture through the distillation unit that is added in reactor head.

Optionally take out distillate, or after condensing, it is infeeded in the phase-separating device.The water that obtains is thus taken out by system usually, and organic phase can be used as reflux and infeeds in the distillation unit and/or directly feed reaction zone and/or infeed in the circulating evaporator, as described in the German patent application of document reference number 100 63 175.4.

When as reflux, organic phase can be used for controlling the temperature in the esterification, as described in DE-A 199 41136.

Esterification a) can be carried out under pressure, superatmospheric pressure or the decompression not having, and preferably carries out under barometric point.

Reaction times is generally 2-20 hour, and preferred 4-15 hour, more preferably 7-12 hour.

The interpolation order of each reactive component is unimportant for the purpose of the present invention.All components can be used as the blended initial charge and introduces and postheating, or one or more components can be omitted or only partly be comprised in the initial charge and only be heated the back interpolation in initial charge.

Operable (methyl) vinylformic acid is not limited on it is formed, and can comprise for example following component:

(methyl) vinylformic acid 90-99.9 weight %

Acetate 0.05-3 weight %

Propionic acid 0.01-1 weight %

Diacrylate 0.01-5 weight %

Water 0.05-5 weight %

Carbonyl compound 0.01-0.3 weight %

Inhibitor 0.01-0.1 weight %

Toxilic acid or acid anhydrides 0.001-0.5 weight %

Used thick (methyl) vinylformic acid is usually with the thiodiphenylamine of 200-600ppm or other stablizer stabilizations of the amount that quite stable turns usefulness into are provided.

Here, carbonyl compound is meant for example acetone and low grade aldehyde, for example formaldehyde, acetaldehyde, crotonic aldehyde, propenal, 2-furfural, 3-furfural and phenyl aldehyde.

Here, slightly (methyl) vinylformic acid is meant (methyl) acrylic acid mixture, its reactant gases in propane/propylene/propenal or Trimethylmethane/iso-butylene/methacrolein oxidation be absorbed in the absorption agent and remove absorption agent subsequently after obtain, or its fractional condensation by reactant gases obtains.

Obviously also can use pure (methyl) vinylformic acid, for example have following purity:

(methyl) vinylformic acid 99.7-99.99 weight %

Acetate 50-1000 ppm by weight

Propionic acid 10-500 ppm by weight

Diacrylate 10-500 ppm by weight

Water 50-1000 ppm by weight

Carbonyl compound 1-500 ppm by weight

Inhibitor 1-300 ppm by weight

Toxilic acid or acid anhydrides 1-200 ppm by weight

Used pure (methyl) vinylformic acid is usually with the 100-300ppm hydroquinone monomethyl ether or other storage stabilizing agent stabilizations of the amount that quite stable turns usefulness into are provided.For example, the also available vitamin-E of pure (methyl) vinylformic acid or other sterically hindered phenol stabilizations.

(methyl) vinylformic acid pure or prepurification typically refers to its purity and is at least 99.5 weight %, and it does not contain (methyl) vinylformic acid of aldehyde component, other carbonyl component and high boiling component substantially.

The water (steaming during esterification) of the condenses that is taken out by additional tower (if the words that exist) may contain 0.1-10 weight % (methyl) vinylformic acid usually, it is separated with system and takes out.(methyl) vinylformic acid that it comprises can preferably extract and return under 10-40 ℃ in the esterification with extraction agent, preferably is used for any solvent of esterification, for example use hexanaphthene, and the ratio of water and extraction agent is 1: 5-30, preferred 1: 10-20.

Can further support circulation in the following manner, with rare gas element, preferred oxygen-containing gas, more preferably the mixture of air or air and nitrogen (poor air) feeds in the circulation, among the reaction mixture or on pass through, speed for example is 0.1-1 based on the volume of reaction mixture, preferred 0.2-0.8, more preferably 0.3-0.7m ³/ m ³H.

Esterification process a) can be monitored by the water yield and/or the concentration reduction of carboxylic acid in reactor that monitoring is taken out of.

Can be for example in 90% of the theory expectation amount of water, preferably at least 95%, more preferably at least 98% finishes reaction when having been taken out of by solvent immediately.

For example can not finish via the phenomenon detection reaction that entrainer takes out by there being further reaction water substantially.When (methyl) vinylformic acid is taken out of with reaction water, its mark can be for example aliquot by the back titration water record.

For example when (methyl) vinylformic acid during with the excessive use of high stoichiometry, for example at least 3: 1, preferably at least 5: 1, most preferably at least 10: 1 o'clock, the taking-up that can omit reaction water.At this moment, the significant quantity that forms water will be stayed in the reaction mixture.Only during reaction or afterwards take out that part of water that determines by the volatility under used temperature, and in addition, do not carry out any measure to take out the reaction water that forms by reaction mixture.For example, at least 10 weight %, preferred at least 20 weight %, more preferably at least 30 weight %, even more preferably at least 40 weight %, most preferably at least 50 weight % gained reaction water can be stayed in the reaction mixture.

C) after the esterification end, can reaction mixture be cooled to 10-30 ℃ in a usual manner, and choose wantonly by adding and with optional solvent phase solvent or the different solvents together that is used for azeotropic taking-up water it to be adjusted to any required target ester concentration.

In another embodiment, available suitable diluent G stopped reaction, and for example in order to reduce viscosity, it is diluted to concentration is for example 10-90 weight %, preferred 20-80 weight %, more preferably 20-60 weight %, even more preferably 30-50 weight %, most preferably from about 40 weight %.

Importantly after dilution, form basic solution uniformly.

This preferably only realized in the short period before being used to produce hydrogel, for example be no more than 24 hours before, preferably be no more than 20 hours before, before 12 hours, even more preferably no more than before 6 hours, be most preferably not exceeding 3 hours before.

Thinner G is selected from for example mixture of methyl alcohol and glycerine of mixture, water and one or more monobasics that water, water and one or more can any ratio organic solvent soluble in water or polyvalent alcohol.Alcohol preferably has 1,2 or 3 hydroxyl, preferably has 1-10, especially at the most 4 carbon atoms.Preferred primary alconol and secondary alcohol.

Preferred alcohol is methyl alcohol, ethanol, Virahol, ethylene glycol, glycerine, 1,2-propylene glycol and 1, ammediol.

D) if necessary words, reaction mixture can be decoloured, for example pass through at for example 10-100 ℃, preferred 20-80 ℃, more preferably under 30-60 ℃ the temperature with activated carbon or metal oxide such as aluminum oxide, silicon-dioxide, magnesium oxide, zirconium white, boron oxide or its mixture process, its amount is for example 0.1-50 weight %, preferred 0.5-25 weight %, more preferably 1-10 weight %.

This can realize in the following manner: powdery or granular discoloring agent is added in the reaction mixture, and subsequent filtration, or make reaction mixture by being the discoloring agent bed of any required suitable moulded product form.

The decolouring of reaction mixture can be carried out in any required stage in treatment process, for example in the crude product mixture stage, or carries out after any pre-wash, neutralization, washing or solvent take out.

Reaction mixture can further carry out pre-wash e) and/or in and f) and/or after scouring g), in preferably only carrying out and f).If need, in and f) and pre-wash e) commutative order.

(methyl) vinylformic acid and/or catalyzer C can by acidifying and with solvent extraction by washing e) and g) and/or in and f) water partially recycled at least and utilize again.

For pre-wash e) or after scouring or g), reaction mixture is handled with washing lotion in washing device, for example water or 5-30 weight %, preferably 5-20 weight %, the more preferably sodium-chlor of 5-15 weight %, Repone K, ammonium chloride, sodium sulfate or ammoniumsulphate soln, preferably water or sodium chloride solution.

The ratio of reaction mixture and washing lotion is generally 1: 0.1-1: 1, preferred 1: 0.2-1: 0.8, more preferably 1: 0.3-1: 0.7.

Washing or neutralization can for example be carried out in stirred vessel or other conventional equipments, for example carry out in tower or mixer-settler device.

With regard to process engineering, any washing in the inventive method or neutralization can use conventional extraction and washing procedure and device to carry out, for example as Ullmann ' s Encyclopedia of IndustrialChemistry (Ullmanns industrial chemistry encyclopaedia), the 6th edition, 1999 electronic publications: described in liquid-liquid extraction device one chapter.For example, can select one or more levels, preferred one-level, and select following current or counter-flow pattern, preferably extract with counter-flow pattern.

The preferred sieve tray column that uses is arranged or random packed tower, stirred vessel or mixer-settler device, and pulse-column or tower with rotation internals.

As long as (following) uses metal-salt, preferably copper or mantoquita then preferably use pre-wash e as inhibitor).

After scouring g) can preferably remove come comfortable f) in the trace alkali or the salt of neutral reaction mixture.

By in and f), may choose wantonly by pre-wash and may still contain the reaction mixture of little amount of catalyst and excessive (methyl) vinylformic acid of main amount can be used 5-25%, preferred 5-20%, the more preferably alkali aqueous solution of 5-15 weight % neutralization, this alkali for example is basic metal or alkaline earth metal oxide, oxyhydroxide, carbonate or supercarbonate, preferred aqueous sodium hydroxide solution, potassium hydroxide aqueous solution, sodium bicarbonate, yellow soda ash, saleratus, calcium hydroxide, milk of lime, ammonia, ammoniacal liquor or salt of wormwood, in this alkali aqueous solution, can choose wantonly and add 5-15 weight % sodium-chlor, Repone K, ammonium chloride or ammonium sulfate more preferably use aqueous sodium hydroxide solution or sodium hydroxide-sodium chloride aqueous solution.Degree of neutralization is preferably 5-60mol% based on sour functional monomer, preferred 10-40mol%, more preferably 20-30mol%.This neutralization can before the polymerization and/or during carry out, preferably before polymerization, carry out.Another preferred degree of neutralization is 50-100mol%, more preferably 55-80mol%, especially 60-75mol%.Preferably just before the polymerization solution and the acrylate solution of linking agent in pure acrylic acid is being mixed together to set degree of neutralization.

The addition manner of alkali should make the temperature in the device can not rise to be higher than 60 ℃, to be preferably 20-35 ℃, and pH is 4-13, preferred 4.5-10.Neutralization heat preferably is removed by cooling vessel by inner spiral coil cooling tube or via the chuck cooling.

The ratio of reaction mixture and neutralizer is generally 1: 0.1-1: 1, preferred 1: 0.2-1: 0.8, more preferably 1: 0.3-1: 0.7.

About this device, above statement is suitable for.

H) when reaction mixture comprises solvent, solvent can take out by distillation substantially.The solvent of any existence is preferably taken out by reaction mixture after washing and/or neutralization, but if need, also can carry out before washing or neutralization.

For this reason, with reaction mixture and a certain amount of storage stabilizing agent, preferred hydroquinone monomethyl ether mixes, and described amount should make after taking out solvent, the 100-500 of described stablizer, and preferred 200-500, more preferably 200-400ppm is present in the target ester (residue).But also can use above-mentioned sterically hindered phenol to replace hydroquinone monomethyl ether, preferably mix use separately or with other stablizers.

The solvent that main amount is taken out in distillation is for example in the stirring tank with chuck heating and/or inner heating coil, and as the 20-700 millibar, preferred 30-500 millibar more preferably carries out under 50-150 millibar and 40-80 ℃ in decompression.

It should be understood that distillation also can realize in falling liquid film or thin-film evaporator.Therefore, in decompression, for example at the 20-700 millibar, preferred 30-500 millibar, more preferably under 50-150 millibar and 40-80 ℃ with reaction mixture recirculation by device, preferably twice or repeatedly.

Can be preferably with rare gas element, preferred oxygen-containing gas, more preferably the mixture of air or air and nitrogen (poor air) is introduced water distilling apparatus, and speed for example is 0.1-1 based on the reaction mixture volume, preferred 0.2-0.8, more preferably 0.3-0.7m ³/ m ³H.

The residual solvent levels of distillation back residue is usually less than 5 weight %, is preferably 0.5-5 weight %, more preferably 1-3 weight %.

The solvent of taking-up is condensed and preferably utilization again.

If necessary, solvent stripping operation i) can additionally or replace distillation to carry out.

Therefore, the target ester that still contains a small amount of solvent is heated to 50-90 ℃, preferred 80-90 ℃, and in suitable device, remove the solvent of residual quantity with suitable gas.Sometimes, if the words that need can apply vacuum to support this operation.

The example of useful device comprises the tower of conventional design, and it contains conventional internals such as tower tray, dump packing or structured packing, preferred dump packing.Useful column internals comprises all internals commonly used in principle, for example tower tray, arrangement filler and/or random packing.Preferred tower tray comprises bubble tray, screen tray, valve tray, Thorman tower tray and/or double-pass tray, and preferred dump packing is ring, coil pipe, saddle, Raschig ring, Intos or Pall ring, cylinder or Ying Teluokesi saddle type filler, Top's Parker (Top-Pak) etc. or cloth.

Here can also use falling liquid film, film or wiped film evaporator, for example Luwa evaporator, Rota-film evaporator or Sambay vaporizer, it can for example protect splash with mist eliminator.

Useful gas is included in and is inert gasses under the stripping condition, preferred oxygen-containing gas, and more preferably mixture of air or air and nitrogen (poor air) or water vapour have been preheated to such gas of 50-100 ℃ especially.

Stripping gas speed for example is 5-20, more preferably 10-20, most preferably 10-15m based on the reaction mixture volume ³/ m ³H.

If necessary, can make ester filter j in any stage of treatment process), preferably after washing/neutralization and any solvent taking-up of carrying out, with any discoloring agent that can remove settled trace salt and exist.

In possible embodiment, in the presence of at least a esterifying catalyst C and at least a polymerization retarder D, alkoxylated diols and (methyl) acrylic acid esterification are a) as mentioned above with at least 10: 1 molar excess carries out, and uses the solvent that can form azeotrope with water.

In preferred embodiments, excessive (methyl) vinylformic acid is not preferably removed substantially, promptly only remove that part of (methyl) vinylformic acid that determines by the volatility under the used temperature by reaction mixture, in addition do not carry out any measure to remove carboxylic acid, for example distill, rectifying, extraction (for example washing), absorb (for example by gac or pass through ion-exchanger) and/or chemical step as removing carboxylic acid with epoxide.

The acrylic acid degree of removing of (methyl) in the reaction mixture preferably is not more than 75 weight % based on (methyl) vinylformic acid that reaction finishes in the afterreaction mixture, more preferably no more than 50 weight %, even more preferably no more than 25 weight %, especially be not more than 10 weight %, most preferably be not more than 5 weight %.In particularly preferred embodiments, can omit b) section, therefore only remove that part of reaction water and (methyl) vinylformic acid that determines by the volatility under the used temperature by reaction mixture.This can preferably prevent by basic total condensation.

In addition, used esterifying catalyst C similarly stays in the reaction mixture substantially.

DIN EN 3682 acid numbers of the reaction mixture that can obtain thus are preferably 25mgKOH/g reaction mixture at least, more preferably 35mg KOH/g reaction mixture at least, even more preferably 45mg KOH/g at least.Acid number is 25-80mg KOH/g more preferably, most preferably 35-50mg KOH/g.

Preferably omit any pre-wash e) or after scouring or g); Filtration step j only) be wise.

Reaction mixture can dilute in step c) subsequently, at this moment, preferably in 6 hours, more preferably converts it into hydrogel in 3 hours.It can preferably neutralize in step f).

Step c), j) and order f) any.

The present invention further provides a kind of composition of matter that comprises following component:

-at least a ester the F that can obtain by one of above-mentioned esterification process,

-(methyl) vinylformic acid and

-thinner G.

Composition of matter of the present invention can further comprise:

-be esterifying catalyst C protonated or not protonated form,

-polymerization retarder D, and

-optional solvents E is if be used for the words of esterification.

This composition of matter can be chosen wantonly and be neutralized and have as at f) described in pH.

When this composition of matter has been neutralized, its water-soluble alkali, alkaline-earth metal or ammonium salt have been converted to small part (methyl) vinylformic acid.

Preferred composition of matter comprises:

-ester F, its weight fraction are 0.1-40%, more preferably 0.5-20%, even more preferably 1-10%, especially 2-5%, particularly 2-4%,

-monomer M, its weight fraction are 0.5-99.9%, more preferably 0.5-50%, even more preferably 1-25%, especially 2-15%, particularly 3-8% or 4-6%,

-esterifying catalyst C, its weight fraction are 0-10%, more preferably 0.02-5%, even more preferably 0.05-2.5%, especially 0.1-1%,

-polymerization retarder D, its weight fraction are 0-5%, more preferably 0.01-1.0%, even more preferably 0.02-0.75%, especially 0.05-0.5%, particularly 0.075-0.25%,

-solvent E, its weight fraction are 0-10%, more preferably 0-5%, even more preferably 0.05-1.5%, especially 0.1-0.5%, and prerequisite is a summation always 100%, and

-optional thinner G supplies 100 weight %.

Can be used as by reaction mixture and the composition of matter according to the present invention that aforesaid method obtains:

The free-radical crosslinking agent of-water-absorbent hydrogel,

The raw material of-production polymeric dispersions,

The raw material of-production polyacrylic ester (except the hydrogel),

The raw material of-paint, or

-cement additire.

The composition of matter of the present invention solubleness in distilled water under 25 ℃ that is particularly useful as the free-radical crosslinking agent of water-absorbent hydrogel is not less than 0.5 weight %, preferably be not less than 1 weight %, more preferably be not less than 2 weight %, even more preferably be not less than 5 weight %, preferably be not less than 10 weight %, even more preferably be not less than 20 weight %, especially be not less than 30 weight %.

K) from esterification, the reaction mixture that comprises its treatment step (if the words of carrying out), for example from f) reaction mixture, or as f) when being omitted, from b), or as b) when being omitted, can choose wantonly with extra monoene ethylenically unsaturated compounds N from reaction mixture a) and (not have acid groups, but can with hydrophilic monomer M copolymerization) mix, and subsequently can polymerization in the presence of at least a radical initiator K and optional at least a grafting base-material L, to prepare the water-absorbent hydrogel.

Can be preferably,

L) make k) reaction mixture after crosslinked.

Can be used for preparing k) the hydrophilic monomer M of these high swelling hydrophilic hydrogel comprises the acid that for example can carry out addition polymerization, as vinylformic acid, methacrylic acid, ethylacrylic acid, α-Lv Bingxisuan, Ba Dousuan, toxilic acid, maleic anhydride, vinyl sulfonic acid, vinyl phosphonate, toxilic acid, maleic anhydride, fumaric acid, methylene-succinic acid, citraconic acid, methylfumaric acid, propene dicarboxylic acid, equisetic acid, allyl sulphonic acid, vinylformic acid sulfo group ethyl ester, methacrylic acid sulfo group ester, vinylformic acid sulfo group propyl ester, methacrylic acid sulfo group propyl ester, 2-hydroxyl-3-acryloxy propyl sulfonic acid, 2-hydroxy-3-methyl acryloxy propyl sulfonic acid, the allyl group phosphonic acids, styrene sulfonic acid, 2-acrylamido-2-methyl propane sulfonic acid, 2-acrylamido-2-methylpropane phosphonic acids and acid amides thereof, hydroxy alkyl ester and the ester and the acid amides that contain amino or ammonium (ammonio).These monomers can use separately or mix mutually and use.In addition, also have water-soluble N-vinylamide and diallyldimethylammonium chloride.Preferred hydrophilic monomer is a formula V compound:

Wherein

R ³Be hydrogen, methyl or ethyl,

R ⁴For-COOR ⁶, alkylsulfonyl, phosphono, (C ₁-C ₄) phosphono or the formula VI group of alkanol esterification:

R ⁵Be hydrogen, methyl, ethyl or carboxyl,

R ⁶Be hydrogen, amino or hydroxyl-(C ₁-C ₄) alkyl and

R ⁷Be alkylsulfonyl, phosphono or carboxyl.

(C ₁-C ₄) example of alkanol is methyl alcohol, ethanol, n-propyl alcohol and propyl carbinol.

Particularly preferred hydrophilic monomer is vinylformic acid and methacrylic acid, especially vinylformic acid.

For optimizing performance, can use advisably not have acidic group, but can with other monoene ethylenically unsaturated compounds N of the monomer copolymerization that has acidic group.This compounds comprises for example acid amides and the nitrile of monoethylenically unsaturated carboxylic acid, for example acrylamide, Methacrylamide and N-vinyl formamide, N-vinyl acetamide, N-ethylene methacrylic yl acetamide, vinyl cyanide and methacrylonitrile.The example of other suitable compound is saturated C ₁-C ₄The vinyl ester of carboxylic acid such as vinyl formate, vinyl-acetic ester or propionate, alkyl contain alkyl vinyl ether such as the ethyl vinyl ether or the butyl vinyl ether of at least 2 carbon atoms, and monoene belongs to unsaturated C ₃-C ₆The ester of carboxylic acid such as monohydroxy C ₁-C ₁₈The ester of alcohol and vinylformic acid, methacrylic acid or toxilic acid, the monoesters of toxilic acid such as toxilic acid hydrogen methyl esters, N-vinyl lactam such as N-vinyl pyrrolidone or N-caprolactam, the vinylformic acid of oxyalkylated monobasic saturated alcohol and methacrylic ester, described alcohol for example for contain 10-25 carbon atom and with alcohol that 2-200mol ethylene oxide and/or propylene oxide/mol alcohol reacts, and the mono acrylic ester of polyoxyethylene glycol or polypropylene glycol and monomethacrylates, the molar mass of polyalkylene glycol (Mn) is for example up to 2000.Other suitable monomers are the vinylbenzene that vinylbenzene and alkyl replace, as ethyl styrene or t-butyl styrene.

These monomers that do not contain acidic group also can mix use with other monomers, for example with vinyl-acetic ester and vinylformic acid 2-hydroxy methacrylate with any mixed.These monomers that do not contain acidic group are with 0-50 weight %, and the amount that preferably is lower than 20 weight % adds in the reaction mixture.

Crosslinked (being total to) polymkeric substance preferably comprises sour official can belong to unsaturated monomer by monoene, its optional alkali metal salts or ammonium salt that before or after polymerization, changed into, and be 0-40 weight % based on the gross weight that the monoene that does not comprise acidic group belongs to unsaturated monomer.

Production, test and the use of (methyl) vinylformic acid (being total to) polymkeric substance, polyacrylic acid and high water absorbent is former so that extensive description and therefore well-known to be arranged, for example referring to " Modern SuperabsorbentPolymer Technology (modern high water absorbency polymer technology) ", F.L. Buchholz and A.T.Graham, Wiley-VCH, 1998 or Markus Frank " high water absorbent ", Ullmann ' sHandbuch der technischen Chemie, the 35th volume, 2003.

Preferably can belong to the crosslinked addition polymerization of unsaturated monomer M or its salt or such hydrogel that copolymerization obtains by monoene by sour official.

Available polymkeric substance merits attention because of its improved saponification index (VSI).

In the cross-linking method of back, with back linking agent processing and preferably during handling or afterwards to carry out the back by elevated temperature crosslinked and dry, linking agent preferably is comprised in the inert solvent with starting polymer.Inert solvent be substantially not with the solvent of starting polymer or back linking agent reaction.Preferably surpass 90%, preferably surpass 95%, more preferably surpass 99%, especially surpass 99.5% not with this kind solvent of starting polymer or back linking agent generation chemical reaction.

The back crosslinked l) and dry m) preferably at 30-250 ℃, especially 50-200 ℃, most preferably under 100-180 ℃, carry out.Preferred crosslinker solution after the application surface by spraying polymkeric substance in suitable spray mixing device.After the spraying, the heated drying polymer powder, and crosslinking reaction not only can be before drying operation, and can during drying carry out.The cross-linking agent solution of preferably in reaction mixer, spraying, or in for example L dige mixing tank, BEPEX mixing tank, NAUTA mixing tank, SHUGGI mixing tank or PROCESSALL, mixing and dry.Can use fluidized bed dryer in addition.

Drying operation can be in mixing tank itself by heating shell or be blown in the warm air and carry out.But also suitable is downstream dryer such as shelf dryer, Rotary pipe type baking oven or heating spiral rod.But for example also can use component distillation as dry technology.Under this temperature, the preferred residence time in reaction mixer or moisture eliminator was lower than 60 minutes, more preferably less than 30 minutes.

Preferably wherein starting polymer is polymkeric substance vinylformic acid or polyacrylic ester, especially uses the polymkeric substance vinylformic acid that the unsaturated free-radical crosslinking agent of multifunctional olefinic obtains by radical polymerization or the aforesaid method of polyacrylic ester.

Preferred these class methods of wherein using the composition of matter that comprises following component: free-radical crosslinking agent, promptly ester F and its ratio are the thinner G (based on the quality of starting polymer) of 0.1-20 weight %, especially 0.5-10 weight %.

Preferred these class methods of wherein using free-radical crosslinking agent, the dosage of described linking agent is 0.01-5.0 weight % based on starting polymer, preferred 0.02-3.0 weight %, more preferably 0.03-2.5 weight %, especially 0.05-1.0 weight %, particularly 0.1 weight %-0.75 weight %.

The present invention also provides the polymkeric substance by the preparation of one of aforesaid method, and the purposes on hygienic articles, wrapping material and non-woven fabric, and the above-mentioned substance composition produce crosslinked or the thermally cross-linkable polymkeric substance in, the purposes in paint and varnish especially.

Stand-by high swelling hydrophilic hydrogel (starting polymer) particularly (is total to) polymkeric substance of polymerization hydrophilic monomer M, grafting (be total to) polymkeric substance of one or more hydrophilic monomers M on suitable grafting base-material L, can be in liquid, aqueous swollen cross-linked cellulose or starch ethers or natural product, for example guar gum derivatives.These hydrogels are that those skilled in the art are known, and are described in for example US-4 286 082, DE-C-27 06 135, US-4 340 706, DE-C-37 13 601, DE-C-28 40 010, DE-A-43 44 548, DE-A-40 20 780, DE-A-40 15 085, DE-A-39 17 846, DE-A-38 07 289, DE-A-35 33 337, DE-A-35 03 458, DE-A-42 44 548, DE-A-42 19 607, DE-A-40 21 847, DE-A-38 31 261, DE-A-35 11 086, DE-A-31 18 172, DE-A-30 28 043, DE-A-44 18 881, EP-A-0 801 483, EP-A-0 455 985, EP-A-0 467 073, EP-A-0 312 952, EP-A-0205 874, EP-A-0 499 774, DE-A-26 12 846, DE-A-40 20 780, EP-A-0 205674, US-5 145 906, EP-A-0 530 438, EP-A-0 670 073, US-4 057 521, US-4062 817, US-4 52 5527, US-4 295 987, US-5 011 892, among US-4 076 663 or the US-4931 497.Also specially suitable is by the high swelling hydrogel as obtaining in production operation described in the WO 01/38402, and as the inorganic/organic mixing water gel at the high swelling described in the DE 198 54 575.With the content of aforementioned patent document, especially the hydrogel that obtains by these methods is hereby incorporated by.

The grafting base-material L that is applicable to the hydrophilic hydrogel that can obtain by the graft copolymerization ethylenic unsaturated acid can be natural or synthetic source.Example is starch, Mierocrystalline cellulose, derivatived cellulose and other polysaccharides and few candy, polyoxyalkylene, especially polyoxyethylene and polyoxytrimethylene, and hydrophilic polyester.

Water-absorbing polymer can be by free radical grafting copolymerization on water-soluble polymer matrix obtains with vinylformic acid or acrylate.The limiting examples of suitable water-soluble polymer matrix is alginate, polyvinyl alcohol and polysaccharide such as starch.For the purpose of the present invention, the unsaturated free-radical crosslinking agent of multifunctional olefinic is used in graft copolymerization.

Water-absorbing polymer can be one side by polymkeric substance vinylformic acid or polyacrylic ester, and the organic/inorganic mixed polymer that forms by silicate, aluminate or silico-aluminate on the other hand.More specifically, used polymkeric substance vinylformic acid or polyacrylic ester can use the unsaturated free-radical crosslinking agent of multifunctional olefinic to obtain and use water-soluble silicate or soluble aluminum hydrochlorate or its mixture to form by radical polymerization.

Preferred hydrogel is polyacrylic ester, polymethacrylate particularly, and US-4931497, US-5 011 892 and US-5 041 496 graftomer.Hydrogel very particularly preferably is at the kneader polymkeric substance described in the WO 01/38402 with at the organic/inorganic mixing water gel based on polyacrylic ester described in the DE 198 545 75.

The material prepared in accordance with the present invention that can be used as free-radical crosslinking agent in hydrogel can use separately or be used in combination with other linking agents, as internal crosslinking agent or surface crosslinking agent, for example:

Other suitable linking agents are methylene-bisacrylamide, methylene-bis Methacrylamide particularly, unsaturated list-or ester such as diacrylate, triacrylate or the tetraacrylate of poly carboxylic acid and polyvalent alcohol, for example diacrylate butanediol ester, tetramethylene dimethacrylate, ethylene glycol diacrylate, Ethylene glycol dimethacrylate, and Viscoat 295 or glycerine diacrylate and glycerol tri-acrylate or tetramethylol methane tetraacrylate; And allylic cpd, as (methyl) vinylformic acid allyl ester, cyanuric acid alkatriene propyl diester, toxilic acid diallyl ester, polyenoid propyl diester, tetraene propoxy-ethane, triallylamine, tetraallyl quadrol, for example at the allyl ester of phosphoric acid described in the EP-A-0 343 427 and vinyl phosphonic acid derivative.Yet, be particularly preferred for being to use the polyenoid propyl ether as other linking agents in the inventive method, and the hydrogel for preparing by acrylic acid acid homopolymerization.Suitable crosslinking agent is pentaerythritol triallyl ether, pentae-rythritol tetraallyl ether, trimethylolpropane allyl ether, polyoxyethylene glycol diallyl ether, monoethylene glycol diallyl ether, glycerine diallyl ether, glycerine triallyl ether, based on the polyenoid propyl ether and the ethoxylation variant thereof of Sorbitol Powder.Particularly preferred linking agent further comprises poly-ethylene glycol diacrylate, the ethoxylated derivative of Viscoat 295, and for example Sartomer SR 9035, and the ethoxylated derivative of glycerine diacrylate and glycerol tri-acrylate.Obviously also can use the mixture of above-mentioned linking agent.

The combination of preferred especially linking agent wherein can be scattered in other linking agents among the linking agent F of the present invention.The example of such linking agent combination is the combination of linking agent F of the present invention and propylene glycol diacrylate or tripropylene glycol diacrylate and propoxylated glycerol triacrylate.Other examples of such linking agent combination are the combination of linking agent of the present invention and diacrylate butanediol ester or Viscoat 295 or pentaerythritol triallyl ether.

Very particularly preferably use ester F prepared in accordance with the present invention as the prepared hydrogel of free-radical crosslinking agent.

Water-absorbing polymer is preferably polymkeric substance vinylformic acid or polyacrylic ester.This water-absorbing polymer can be by known method preparation on the document.The polymkeric substance that preferably comprises cross-linking comonomer (0.001-10mol%), but very particularly preferably by radical polymerization, and the polymkeric substance that uses the unsaturated free-radical crosslinking agent of multifunctional olefinic to obtain.Ester mixture of the present invention preferably allow each ester component Fi based on monomeric total amount being lower than 2 weight %, preferred 1 weight % uses.The summation of all ester components especially preferably is lower than 2 weight %, preferably is lower than 1 weight %.

The high swelling hydrophilic hydrogel can be by known addition polymerization method preparation itself.The preferably addition polymerization of in the aqueous solution, carrying out with gel polymerisation.As mentioned above, it relates to the rare of one or more hydrophilic monomers and the suitable grafting base-material L that chooses wantonly, preferably aqueous, more preferably the aqueous solution of 15-50 weight % utilizes the Trommsdorff-Norrish effect to carry out polymerization (Makromol.Chem.1 in the presence of radical initiator, 169 (1947)), preferably do not use mechanically mixing.This polyreaction can be at 0-150 ℃, under preferred 10 ℃-100 ℃, not only can be under barometric point, and can under superatmospheric pressure or decompression, carry out.Usually, this polyreaction also can preferably be carried out under nitrogen in shielding gas atmosphere.Addition polymerization can use high-energy electromagnetic rays or conventional chemical polymerization starter K to cause, for example organo-peroxide such as benzoyl peroxide, t-butyl hydroperoxide, methyl ethyl ketone peroxide, cumene hydroperoxide, azo-compound such as azobis isobutyronitrile, and inorganic peroxy compounds is as (NH ₄) ₂S ₂O ₈, K ₂S ₂O ₈Or H ₂O ₂

They can be chosen wantonly and reductive agent such as xitix, sodium bisulfite and ferric sulfate (II) or redox system combination, the contained reduction components of wherein said redox system is aliphatic series and aromatic sulfinic acid, as benzene sulfinic acid and toluenesulfinic acid or derivatives thereof, for example at the Mannich affixture of-sulfinic acid, aldehyde and the aminocompound described in the DE-C-1 301 566.Polymer properties can be further by with polymer gel at 50-130 ℃, post-heating a few hours under preferred 70-100 ℃ the temperature and improving.

The gained gel is neutralized to 0-100mol%, preferred 25-100mol%, the more preferably degree of 50-85mol% (based on used monomer), can use conventional neutralizing agent, preferred alkali metal hydroxide, alkalimetal oxide or its corresponding alkali metal carbonate, but more preferably sodium hydroxide, yellow soda ash and sodium bicarbonate.When using sodium hydroxide, the grade that preferred especially use can obtain by the film electrolysis.

Neutralization usually by with neutralizing agent with the aqueous solution or preferably sneak in the gel and realize with solid.To this,,, and with neutralizing agent spraying, scattering or topple over thereon, sneak into carefully then for example by mincer with the gel mechanical disintegration.Then, the gel piece of gained can be repeated by mincer with homogenizing.The neutral gel piece preferably is lower than 10 weight % with belt or pot type moisture eliminator drying up to remaining water content then, especially is lower than till the 5 weight %.

Addition polymerization itself also can be undertaken by any other method described in the document.More specifically, acrylic acid neutralization also can be carried out before polymerization, as preamble described in the step f).No matter neutralization be before the polymerization, during or carry out afterwards, especially preferably use dimer content to be lower than 2000ppm, more preferably less than 1000ppm, most preferably be lower than the vinylformic acid of 500ppm.Very particularly preferably use the sodium hydroxide that obtains by the film electrolysis.Compare with additive method, this method is because of its high purity (for example subchloride content, and do not have Trace Hg) and merit attention.Certainly also can use the sodium hydroxide that obtains by amalgam or barrier film method.Then, polymerization can or be mediated in the reactor and carry out continuously or in batches in conventional belt reactor.When in being aggregated in belt reactor, carrying out,, preferably cause, perhaps especially preferably cause by the redox initiator system by the UV radiation by electromagnetic radiation.The also very particularly preferably combination of two kinds of initiating methods: use electromagnetic radiation and chemistry redox initiator system simultaneously.

N) then, grinding of exsiccant hydrogel and screening at this moment, can be used usually and rolled grinding machine, needle mill or screen mill.The preferred size of screening hydrogel is preferably 45-1000 μ m, more preferably 45-850 μ m, even more preferably 200-850 μ m, most preferably 300-850 μ m.Further particularly preferred scope is 150-850 μ m, especially 150-700 μ m, more preferably 200-600 μ m, most preferably 150-550 μ m.Further special scope is 200-800 μ m, and particularly preferred scope is 250-650 μ m, and scope very particularly preferably is 300-600 μ m.Particularly preferred scope is 200-500 μ m, 100-450 μ m and 150-400 μ m.These scopes are preferred covers 80 weight % particles, especially 90 weight % particles.Size-grade distribution can be used existing method for sieving or preferably use optical means (photograph) to record.

The present invention further provides crosslinked hydrogel, it comprises at least a hydrophilic monomer M that is copolymerized form, and has used polyvalent alcohol and (methyl) acrylic acid ester F crosslinked.This ester can mode of the present invention or is prepared in the mode of prior art, preferably prepares in mode of the present invention.

Useful ester F comprises above-claimed cpd.

The present invention forms the crc value [g/g] of the polymkeric substance of hydrogel and can measure by method shown in the specification sheets part, and preferably be higher than 10, especially 11,12,13,14,15,16,18,20,22,24 or higher, more preferably 25, especially 26,27,28,29, even more preferably 30,31,32,33,34,35,36,37,38,39,40,41,42,43,44,45 or higher.

The present invention forms the AUL 0.7psi value [g/g] of the polymkeric substance of hydrogel and can measure by method shown in the specification sheets part, preferably be higher than 8, especially 9,10,11,12,13,14 or higher, more preferably 15, especially 16,17,18,19 or higher, even more preferably be higher than 20, especially 21,22,23,24,25,26,27,28 or higher.

The present invention forms the AUL 0.5psi value [g/g] of the polymkeric substance of hydrogel and can measure by method shown in the specification sheets part, preferably be higher than 8, especially 9,10,11,12,13,14 or higher, more preferably 15, especially 16,17,18,19 or higher, even more preferably be higher than 20, especially 21,22,23,24,25,26,27,28 or higher.

The saponification index VSI that the present invention forms the polymkeric substance of hydrogel can measure by method method shown in the specification sheets part, preferably be lower than 10, especially 9.5,9 or 8.5 or lower, more preferably less than 8, especially 7.5,7,6.5,6,5.5 or lower, even more preferably less than 5, especially 4.5,4,3.5 or lower.

The present invention forms the residual cross-linker content of the polymkeric substance of hydrogel and can measure by method method shown in the specification sheets part, preferably be lower than 30ppm, more preferably less than 20ppm, most preferably be lower than 10ppm, especially 9.5ppm, 9ppm or 8.5ppm or lower, more preferably less than 8ppm, especially 7.5ppm, 7ppm, 6.5ppm, 6ppm, 5.5ppm or lower, even more preferably less than 5ppm, especially 4.5ppm, 4ppm, 3.5ppm or lower.When using multiple linking agent in mixture, these maximum values relate to each the independent linking agent in the mixture.

The present invention forms the exploitation and the purposes of the polymkeric substance of hydrogel

The invention further relates to the purposes of polymkeric substance in hygienic articles of above-mentioned formation hydrogel, described hygienic articles comprises following structure:

(P) can be through the top thin slice of liquid

(Q) end thin slice of basic impermeable liquid

(R) be positioned at (P) and (Q) between and comprise the core of following composition:

The polymkeric substance of 10-100 weight % the present invention formation hydrogel,

0-90 weight % hydrophilic fiber material,

The polymkeric substance of preferred 20-100 weight % the present invention formation hydrogel, 0-80 weight % hydrophilic fiber material,

The more preferably polymkeric substance of 30-100 weight % the present invention formation hydrogel, 0-70 weight % hydrophilic fiber material,

Even the more preferably polymkeric substance of 40-100 weight % the present invention formation hydrogel, 0-60 weight % hydrophilic fiber material,

Still even the more preferably polymkeric substance of 50-100 weight % the present invention formation hydrogel, 0-50 weight % hydrophilic fiber material,

The polymkeric substance of preferred especially 60-100 weight % the present invention formation hydrogel, 0-40 weight % hydrophilic fiber material,

The polymkeric substance of especially preferred 70-100 weight % the present invention formation hydrogel, 0-30 weight % hydrophilic fiber material,

The polymkeric substance of 80-100 weight % the present invention formation hydrogel very preferably, 0-20 weight % hydrophilic fiber material,

The polymkeric substance of 90-100 weight % the present invention formation hydrogel most preferably, 0-10 weight % hydrophilic fiber material,

(S) be located immediately on the described core (R) and under optional tissue layer and

(T) be positioned at (P) and (R) between optional absorption layer.

Should understand these percentage ratios, under the situation of 10-100 weight %, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% to being possible up to the polymkeric substance of 100 weight % the present invention formation hydrogels under every kind of situation and all intermediate value percentage ratio (for example 12.2%), and 89%, 88%, 87%, 86%, 85%, 83%, 82%, 81 weight %s and the intermediate value percentage ratio (for example 87.8%) of corresponding hydrophilic fiber material under 0% to every kind situation is possible.When having other materials in the core, the percentage ratio of polymkeric substance and fiber can corresponding reduction.Same case is applicable to preferred range, for example under situation very preferably, correspondingly there are 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12%, 11 weight % filamentary materials in the polymkeric substance that can have 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89 weight % the present invention formation hydrogels.Therefore, in preferred range, can have 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, the polymkeric substance of 29%-100 weight % the present invention formation hydrogel, in preferred scope, can have 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, the present invention of 39%-100 weight % forms the polymkeric substance of hydrogel, in addition preferred scope in can have 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, the present invention of 49%-100 weight % forms the polymkeric substance of hydrogel, still even in the preferred scope can have 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, the present invention of 59%-100 weight % forms the polymkeric substance of hydrogel, in particularly preferred scope, can have 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, the present invention of 69%-100 weight % forms the polymkeric substance of hydrogel, especially can have 70% in the preferable range, 71%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, the present invention of 79%-100 weight % forms the polymkeric substance of hydrogel, can have 90% in most preferred scope, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, the present invention of 99% or 100 weight % forms the polymkeric substance of hydrogel.

For the purpose of the present invention, hygienic articles comprises that not only the incontinence of the usefulness of being grown up with pad and incontinence pull-on pant, also comprises hippen.

The top thin slice (P) that can see through liquid is the layer that directly contacts with wearer skin.Its material comprises conventional polyester, polyolefine, regenerated fiber fibrid or film or the natural fiber such as the cotton of synthesizing or making.Under the situation of nonwoven material, fiber is bonded together by tackiness agent such as polyacrylic ester usually.Preferable material is polyester, regenerated fiber and adulterant thereof, polyethylene and polypropylene.The case description of layer that can see through liquid is in WO 99/57355A1, EP 1023883A2.

The layer of impermeable liquid (Q) is generally polyethylene or polypropylene sheet.Yet, can use any other material that can be processed to impermeable liquid thin slice.Thus, impermeable liquid is meant the impermeability of coagulating liq.Yet, but this thin slice can present perviousness to liquid vapour simultaneously, and the modern diaper structure often combines the maximum impermeability of high vapor permeable and its coagulating liq, and described liquid is generally water or urine.

Core (R) not only comprises the polymkeric substance that the present invention forms hydrogel, and comprises hydrophilic fiber material.Wetting ability is meant and liquid, aqueously is diffused on the fiber apace.Filamentary material is generally Mierocrystalline cellulose, modified-cellulose, regenerated fiber, polyester such as polyethylene terephthalate.Special optimum fiber cellulose fiber is as paper pulp.These fibers typically have a diameter from 1-200 μ m, preferred 10-100 μ m, and minimum length is 1mm.

Diaper configurations and be shaped as general knowledge and for example be described in WO and walk to for 95,/26 209 the 66th page the 34th among the 69th page of the 11st row, DE 196 04 601 A1, EP-A-0 316 518 and the EP-A-0 202 127.Diaper and other hygienic articles also are described in WO 00/65084, especially 6-15 page or leaf usually, and WO 00/65348,4-17 page or leaf especially, and WO 00/35502, and 3-9 page or leaf especially is among DE19737434, the WO 98/8439.Feminine care is described in the following document with hygienic articles.Here can use the motif polymerization thing that can absorb liquid, aqueous formation hydrogel.Feminine care is referring to WO95/24173: the absorbent article of control smell; WO 91/11977: the control of body fluid smell; EP 389023: the water-absorbent hygienic articles; WO 94/25077: odour controlling materials; WO 97/01317: the water-absorbent hygienic articles, WO 99/18905, EP 834297, US 5,762,644, US 5,895,381, WO98/57609, WO 2000/065083, WO 2000/069485, WO 2000/069484, WO2000/069481, US 6,123,693, EP 1104666, WO 2001/024755, WO2001/000115, EP 105373, WO 2001/041692, EP 1074233.Tampon is described in the following document: WO 98/48753, WO 98/41179, WO 97/09022, WO 98/46182, WO 98/46181, WO 2001/043679, WO 2001/043680, WO 2000/061052, EP 1108408, WO 2001/033962, DE 200020662, WO 2001/001910, WO2001/001908, WO 2001/001909, WO 2001/001906, WO 2001/001905, WO 2001/24729.Inconvenient article is described in the following document: the personal once-used water-absorption goods of incontinence: EP 311344 specification sheetss, 3-9 page or leaf; Once-used water-absorption goods: EP 850623; Absorbent products: WO 95/26207; Absorbent products: EP 894502; Dry-laying filamentary structure: EP 850616; WO 98/22063; WO 97/49365; EP 903134; EP 887060; EP 887059; EP 887058; EP 887057; EP 887056; EP 931530; WO 99/25284; WO 98/48753.Feminine care and Inconvenient article are described in the following document: sanpro: WO93/22998 specification sheets, 26-33 page or leaf; The water-absorbent member of body fluid: WO 95/26209 specification sheets, 36-69 page or leaf; Once-used water-absorption goods: WO 98/20916 specification sheets, the 13-24 page or leaf; Improved composite water absorbing structure: EP 306262 specification sheetss, 3-14 page or leaf; Bodily waste absorbent products: WO 99/45973.In this is incorporated herein these documents and document wherein clearly.

The polymkeric substance that the present invention forms hydrogel very can be used as water and liquid, aqueous absorption agent, so they can be advantageously used for water-holding agent, flocculating aids, particularly hygienic articles on the gardening market such as the water-absorbent component in diaper, tampon or the cotton wool.

Mix and high swelling hydrogel fixedly of the present invention

Except above-mentioned high swelling hydrogel, water-absorbent compositions of the present invention comprises that it comprises be fixed thereon structure of high swelling hydrogel or hydrogel.Any structure that can regulate the high swelling hydrogel and be integrated in the absorption layer is all suitable.The diversity of this based composition is known and be described in detail in the document.The structure of mounting height swellable hydrogel can be for example fibre substrate, and it comprises the fiber blends of blend of cellulose fibers (air fibre plate, wet laid random web fibre plate) or synthetic polymeric fibers (meltblown fibers sheet, spun-bonded fibre sheet) or cellulose fiber peacekeeping synthon.Possible filamentary material is described in detail in part subsequently.Air fibre plate method for example is described among the WO 98/28478.In addition, open celled foam etc. can be used for mounting height swellable hydrogel.

In addition, this structure can obtain by two individual courses being merged to form one or preferred a plurality of chambers of containing the high swelling hydrogel.Described chamber system is described in detail in EP 0,615 736 A1, the 7th page of the 26th row and subsequently in each row.

At this moment, but one deck should permeate water at least in two-layer.The second layer can see through or impermeable water.Used layer material can be tulle or other fabrics, closed pore or open celled foam, porous-film, elastomerics or the fabric that is made of filamentary material.When water-absorbent compositions comprised layer structure, layer material should have pore structure, and the aperture is enough little of the Bock Altitude swellable hydrogel particles.The example of above-mentioned water-absorbent compositions structure comprises also and comprises two-layer at least laminate that two interlayers are installed and also fixed the high swelling hydrogel.

Usually, hydrogel particle can be fixed in the absorbent core to improve dried wet integrity.Do wet integrity representative and as follows the high swelling hydrogel is installed in ability in the water-absorbent compositions: make hydrogel not only when humidity but also under drying regime, stand external force and high swelling polymkeric substance and can not dislocate or be scattered out.Described power especially as occur in mechanical stress in the moving process when dressing hygienic articles, or the compression weight on the hygienic articles is especially under the situation of incontinence.As for fixing, the known multiple possibility of those skilled in the art.Point out such as walking to for 95,/26 209 the 37th page the 36th in the 41st page of the 14th row at WO by thermal treatment, the fixed example that adds tackiness agent, thermoplastics, adhesive material.Therefore institute's section of drawing is a part of the present invention.The method that strengthens wet tenacity is also referring to WO 2000/36216 A1.

In addition, water-absorbent compositions can comprise base material, for example the polymeric film that is fixed thereon of high swelling hydrogel particle.Fixing not only can be on a side, and can on two sides, realize.But base material permeate water or impermeable water.

The weight fraction of above-mentioned water-absorbent compositions structure introducing high swelling hydrogel is 10-100 weight % based on the gross weight of structure and high swelling hydrogel, preferred 20-100 weight %, more preferably 30-100 weight %, even more preferably 40-100 weight %, more preferably 50-100 weight %, preferred especially 60-100 weight %, especially preferred 70-100 weight %, very preferably 80-100 weight %, most preferably 90-100 weight %.

The filamentary material of water-absorbent compositions

Structure according to water-absorbent compositions of the present invention of the present invention can be based on various filamentary materials as fibre network or matrix.The present invention not only comprises the fiber of natural origin (modification or unmodified) but also comprises synthon.

The detailed summary that can be used for the fiber example among the present invention walks to for 95/26209, the 28 page the 9th in the 36th page of eighth row at WO and provides.Therefore institute's section of drawing is a part of the present invention.

The example of cellulosic fibre comprises the cellulosic fibre that is usually used in the water-absorbent product, as Time of Fluff Slurry and short-staple element.Material (soft or hardwood), production method such as chemical pulping, semichemical pulping, chemi thermo mechanical slurrying (CTMP) and bleaching method are not limited especially.For example, use native cellulose fibre such as cotton, flax, silk, wool, jute, ethyl cellulose and cellulose ethanoate.

Suitable synthon are by polyvinyl chloride, fluorinated ethylene propylene, tetrafluoroethylene, poly(vinylidene chloride), polyacrylic compounds such as ORLON ^, polyvinyl acetate, polyvinyl ethyl acetate, solubility or insoluble polyvinyl alcohol production.The example of synthon comprises TPO fiber such as polyethylene fibre (PULPEX ^), polypropylene fibre and polyethylene-polypropylene conjugate fiber, trevira such as pet fiber (DACRON ^Or KODEL ^), copolyesters, polyvinyl acetate, the polyvinyl ethyl acetate, polyvinyl chloride, poly-inclined to one side 1, the 1-Ethylene Dichloride, polyacrylic, polymeric amide, copolyamide, polystyrene, and the multipolymer of above-mentioned polymkeric substance, also has conjugate fiber by polyethylene terephthalate/the polyethylene glycol isophthalate multipolymer is formed, the conjugate fiber of forming by polyvinyl ethyl acetate/polypropylene, the conjugate fiber of forming by polyethylene/polyester, the conjugate fiber of forming by polypropylene/polyester, the conjugate fiber that copolyesters/polyester is formed, tynex (nylon), polyurethane fiber, styroflex and polyacrylonitrile fibre.Preferred polyolefm fiber, trevira and conjugate fiber thereof.Further preferred heat bonding by core-shell and the conjugate fiber formed of type polyolefine side by side, because it has excellent size stability after liquid-absorbent.

Mentioned synthon preferably are used in combination with thermoplastic fibre.In heat treatment process, therefore latter's creep to a certain degree, and constitutes bonding position to the matrix of the filamentary material that exists, and makes the element sclerosis when cooling again.In addition, the interpolation of thermoplastic fibre is meaning hole dimension present after thermal treatment is carried out increases.This is by adding the feasible ratio that can increase continuously thermoplastic fibre on the web direction of top of thermoplastic fibre continuously during forming at absorption layer, this causes the similar of hole dimension to increase continuously.Thermoplastic fibre can be lower than 190 ℃ by multiple fusing point, is preferably 75 ℃-175 ℃ thermoplastic polymer preparation.These temperature are too low and can not damage cellulosic fibre.

The length of above-mentioned synthon and diameter are not limited especially, and can preferably use length to be 1-200mm and the diameter any fiber as 0.1-100 dawn (g/9000 rice) usually.The length of preferred thermoplastic fibre is 3-50mm, and the length of particularly preferred thermoplastic fibre is 6-12mm.The preferred diameter of thermoplastic fibre is the 1.4-10 dtex, preferred especially 1.7-3.3 dtex (g/10000 rice).The form of fiber can change; Example comprises woven type, narrow cylinder shape, cutting/division yarn type, staple fibre type and continuous filament fibers type.

Fiber in the water-absorbent compositions of the present invention can be wetting ability and/or hydrophobicity.According to the definition of Robert F.Gould in 1964 American Chemical Society's publication " contact angle, wettability and binding property ", when the contact angle between liquid and fiber (or fiber surface) during less than 90 ° or when liquid inclination when spontaneously on similar face, expanding, fiber is called as wetting ability.These two kinds of processes coexist usually.On the contrary, when the contact angle that forms greater than 90 ° and when not observing any expansion, fiber is called as hydrophobicity.

The preferred hydrophilic fiber material that uses.Especially preferably use bodyside as slightly water-wet in the peripheral region of high swelling hydrogel the hydrophilic filamentary material of tool.In process of production, the layer with different hydrophilic is used to produce gradient, and described tonsure is delivered to the liquid of invading in the last hydrogel with its absorption.

The suitable hydrophilic fibre that is used for water-absorbent compositions of the present invention comprises for example cellulosic fibre, modified cellulose fibre, regenerated fiber, trevira such as polyethylene terephthalate (DACRON ^), and wetting ability nylon (HYDROFIL ^).Suitable hydrophilic fibre also can obtain by making the hydrophobic fibre hydrophilization, for example the thermoplastic fibre that is obtained by polyolefine (for example polyethylene or polypropylene, polymeric amide, polystyrene, urethane etc.) with tensio-active agent or treatment of silica.Yet, because of cost reason and be easy to obtain the optimum fiber cellulose fiber.

The high swelling hydrogel particle is embedded in the described filamentary material.But this accomplished in various ways, for example by using hydrogel material and fiber producing the absorption layer of matrix form together, or by the high swelling hydrogel is mixed in the blending in of fibers layer, and be fixed in wherein at last by tackiness agent or the laminated of layer.

The fibre substrate that obtains liquid and distributing liquid can comprise the mixture of synthon or cellulosic fibre or synthon and cellulosic fibre, and wherein, ratio of mixture can be at (100-0) synthon: (0-100) change in the scope of cellulosic fibre.Used cellulosic fibre can be additionally chemicosolidifying, to increase the dimensional stability of hygienic articles.

The chemicosolidifying of cellulosic fibre can provide by different way.Provide Fibrosclerotic first kind of mode by suitable coating is added into filamentary material.Such additive comprises for example polymeric amide-Epicholorohydrin coating (Kymene ^557H, Hercules, Inc., Wilmington, Delaware, USA), polyacrylamide coating (is described in US-A-3, in 556,932 or as American Cyanamid Co., Stamford, CT, the Parez of USA ^The 631NC commodity), melamine-methanal paint and polymine coating.

Cellulosic fibre also can pass through the chemical reaction chemicosolidifying.For example, it is crosslinked with what carry out carrying out in fiber to add the suitable crosslinking agent material.The suitable crosslinking agent material is the typical material that is used for cross-linking monomer, includes but not limited to have acid functionality's C ₂-C ₈Dialdehyde, C ₂-C ₈Single aldehyde, particularly C ₂-C ₉Poly carboxylic acid.The concrete material of this series for glutaraldehyde for example, oxalic dialdehyde, Glyoxylic acid hydrate, formaldehyde and citric acid.Interior or at least 2 hydroxyl reactions of two plain interchain of adjacent fiber of any cellulose chain in these materials and any cellulosic fibre.The crosslinked sclerosis that causes fiber, this processing have been given described vulcanized fiber with bigger dimensional stability.Except its water-wet behavior, these fibers are sclerosis and elastic even combination.Even this physicals make contact with liquid at the same time with force of compression under also can keep capillary structure, and prevent too early collapse.

The cellulosic fibre of chemically crosslinked is known, and is described in WO 91/11162, US 3,224,926, US 3,440,135, US 3,932,209, US 4,035, and 147, US 4,822,453, US 4,888,093, US 4,898,642 and US 5,137,537 in.Chemically crosslinked makes the filamentary material sclerosis, and it is reflected on the improvement dimensional stability of whole hygienic articles at last.Each layer is bonded together by the procedure known to those skilled in the art, for example by thermal treatment, add the mutual fusion of hotmelt, emulsion adhesive etc.

Produce the method for water-absorbent compositions

Water-absorbent compositions is by the structure that contains the high swelling hydrogel and be present in this structure or the high swelling hydrogel that is fixed thereon is formed.

Obtaining comprising high swelling hydrogel for example, to be fixed in the example of method of water-absorbent compositions of the base material on one or two sides known, and comprise in the present invention, but be not subject to this.

(mix proportions is at (100-0) synthon: the preparation method's of water-absorbent compositions (0-100) variation in the scope of cellulosic fibre) example comprises: (1) is wherein with (a) for example to comprise the filamentary material adulterant of the synthon (a) that embed in the high swelling hydrogel (c) and cellulosic fibre (b), (b) and (c) once and the method that mixes simultaneously, (2) wherein (a) and mixture (b) are sneaked into method in (c), (3) wherein with (b) and mixture (c) and (a) blended method, (4) wherein (a) and mixture (c) are sneaked into method in (b), (5) wherein (b) mixed with (c), and continuous measurement adds the method for (a), (6) wherein (a) mixed with (c), and continuous measurement adds the method for (b) and (7) and wherein with (b) and (c) sneaks into method in (a) separately.In these examples, preferred method (1) and (5).The device that is used for this method is not limited especially, and can use the known any conventional equipment of those skilled in the art.

The water-absorbent compositions that obtains in this way can be chosen wantonly and heat-treat, therefore the absorption layer that obtains having excellent in dimension stability under dampness.Heat treating method is not limited especially.Example comprises by infeeding the thermal treatment of warm air or infrared radiation.Heat treated temperature is 60 ℃-230 ℃, preferred 100 ℃-200 ℃, and preferred especially 100 ℃-180 ℃.

The heat treated time length is depended on synthon type, its amount and hygienic articles throughput rate.Usually, the heat treated time length is 0.5 second-3 minutes, preferred 1 second-1 minute.

Water-absorbent compositions for example provides usually can see through the top thin slice of liquid and the end thin slice of impermeable liquid.In addition, flange is connected so that hygienic articles is complete with the adhesion lappet.Can be that those skilled in the art are known through the material and the type of thin slice and flange and adhesion lappet at the bottom of top thin slice and the impermeable, and not limited especially.The example can be referring to WO 95/26209.

The invention has the advantages that after formation can be used as the ester F of linking agent and needn't be purified, and particularly in removing (methyl) vinylformic acid, preferred vinylformic acid is because it typically is the monomer that is used to form hydrogel.

Experimental section

Unless have describedly in addition, otherwise ppm and percentage number average are based on weight.

Embodiment subsequently illustrates the inventive method.

Embodiment

Be used as the production of the crude propylene acid esters of SAP-linking agent

The SAP-linking agent by with acroleic acid esterification polyvalent alcohol or POlol mixture, prepares to take out water in the component distillation in an embodiment.Esterifying catalyst among the embodiment is a sulfuric acid.In an embodiment reactant is introduced in the combination of methylcyclohexane entrainer and the stabilizer blend that comprises hydroquinone monomethyl ether, triphenyl phosphite and Hypophosporous Acid, 50 as initial charge.Then, reaction mixture being heated to about 98 ℃ begins up to component distillation.During component distillation, the temperature in the reaction mixture rises.Measure the water yield of taking out.Promptly end distillation in case taken out at least theoretical water.Subsequently, in vacuum distilling, remove entrainer.Make the product cooling, and in SAP produces, be used as linking agent.

The transformation efficiency of reaction and productive rate are not measured exactly, because the water that takes out in esterification also contains vinylformic acid, and vinylformic acid also is removed during the vacuum distilling of entrainer.Similarly, thick ester still contains free vinylformic acid, with itself and catalyzer titration together (acid number).

Unless have describedly in addition, otherwise umber is all based on weight.

The preparation of ester

Measure acid number according to DIN EN 3682.

Embodiment 1 preparation is as the alkoxylated diols of ester F base-material

A) TriMethylolPropane(TMP)-30EO-5PO

45% aqueous solution of 77g TriMethylolPropane(TMP) and 0.5g KOH is placed autoclave together as initial charge, and 80 ℃ and the decompression (about 20 millibars) under together the dehydration.Then, add the 759g ethylene oxide down at 145-155 ℃, and it is reacted under this temperature and high pressure.When no longer observing the change of pressure, reaction stops.Subsequently, with reaction mixture about 150 ℃ of following restir 30 minutes.Then, under 120-130 ℃ and high pressure, interpolation 167g propylene oxide in long-time, and make its reaction equally.After washing with rare gas element and being cooled to 60 ℃, by adding trisodium phosphate, subsequent filtration is isolated catalyzer.

B) TMP-15-EO prepares in a similar manner.

C) tripropylene glycol is the commercial diol component.

D) glycerine-3EO is similar to embodiment 1a) preparation.

E) TriMethylolPropane(TMP)-3EO is similar to embodiment 1a) preparation.

F) TriMethylolPropane(TMP)-1PO-3EO is similar to embodiment 1a) preparation, but at first add propylene oxide down at 120-130 ℃, under 145-155 ℃, only add ethylene oxide then.

G) glycerine-30EO-5PO is similar to embodiment 1a) preparation.

H) butyleneglycol is commercially available.

The preparation of embodiment 2 acrylate

A) TriMethylolPropane(TMP)-30EO-5PO-triacrylate (TMP30EO5POTA)

With 216 parts of vinylformic acid and 5 parts of sulfuric acid with 1427 parts about 30 heavily ethoxylation and 5 heavy propenoxylated TriMethylolPropane(TMP) (according to embodiment 1a) esterifications in 345 parts of methylcyclohexanes.The auxiliary agent that is added is 2 parts of hydroquinone monomethyl ethers and 2 parts of alpha-tocopherols.Isolate 44 parts of water, remove entrainer by vacuum distilling then.Product is by K300 strainer purifying.Measure acid number.Regulate viscosity by adding 96 parts of vinylformic acid.The viscosity of almost colourless product (iodine number 0-1) is about 330mPas.

B) TMP-15-EO-triacrylate (TMP15EOTA) prepares in a similar manner.

C) tripropylene glycol diacrylate (TPGDA) is can Laromer TPGDA (BASF AG) commercial.But but its also all fours the foregoing description preparation.

D) glycerine-3EO-triacrylate (G3EOTA) prepares in a similar manner.

E) TriMethylolPropane(TMP)-3EO-triacrylate (TMP3EOTA) prepares in a similar manner.

F) TriMethylolPropane(TMP)-1PO-3EO-triacrylate (TMP1PO3EOTA) prepares in a similar manner.

G) glycerine-30EO-5PO-triacrylate (G30EO5POTA) prepares in a similar manner.

H) diacrylate butanediol ester (BDDA) can commercial (BASF AG).

The linking agent mixture that is used for following embodiment can mix simply with described weight ratio by the acrylate that will prepare immediately and prepare.Perhaps, can be with polyethers such as the above-mentioned mixing and the common esterification of subordinate.

Produce hydrogel

For measuring surface-crosslinked quality, can use following Test Research exsiccant hydrogel.Test method

A) centrifugal retention volume (CRC)

This method is measured the hydrogel free swell in tea bag.With 0.2000+/-0.0050g exsiccant hydrogel (granularity grades 106-850 μ m) is weighed in the tea bag that is of a size of 60 * 85mm, subsequently with its sealing.Tea bag was placed 0.9 excessive weight % sodium chloride solution (0.83L sodium chloride solution/1g polymer powder at least) 30 minutes.Make tea bag then under 250g centrifugal 3 minutes.Tea bag after centrifugal records amount of liquid by anti-weighing.

B) water-absorbent (AUL) under load (0.7psi)

The measuring cell that is used to measure AUL 0.7psi is the synthetic glass cylinder of internal diameter 60mm and height 50mm.The mesh size that adhesion is connected at the bottom of the stainless steel sift of its bottom side is 36 μ m.Measuring cell comprises that also diameter is the plastic plate of 59mm and can be placed on weights in the measuring cell with plastic plate.The heavy altogether 1345g of plastic plate and weights.The weight that AUL 0.7psi has machine glass cylinder and plastic plate in vain by mensuration is measured and it is recorded as W0.Then, with 0.900+/-polymkeric substance (size-grade distribution is 150-800 μ m) that 0.005g forms hydrogel weighs in the synthetic glass cylinder, and on being evenly distributed in very much at the bottom of the stainless steel sift.Subsequently, plastic plate is placed in the synthetic glass cylinder carefully, the weighing whole unit, and be Wa with weight record.Then, weights is placed on the plastic plate in the synthetic glass cylinder.Subsequently, with diameter is 120mm, highly be that 10mm and porosity are 0 ceramic filtering plate (Duran, available from Schott) to be placed on diameter be 200mm and highly be the Petri dish central authorities of 30mm, and introduce capacity 0.9 weight % sodium chloride solution so that fluid surface and the filter plate same level in surface and the filter plate surface of can not getting wet.Then, with diameter be the circular filter paper (S﹠amp of 90mm and hole dimension＜20 μ m; S 589Schwarzband is available from Schleicher﹠amp; Schiill) be placed on the ceramic plate.Subsequently, will contain synthetic glass cylinder and the plastic plate and the weights of the polymkeric substance that forms hydrogel, and be placed on the filter paper top, and placed 60 minutes.When finishing during this period of time, whole unit is removed by filter paper and Petri dish, then weights is removed by the synthetic glass cylinder.To contain the synthetic glass cylinder and the plastic plate of swelling hydrogel and weigh together, and be Wb weight record.

AUL calculates by following equation:

AUL 0.7psi[g/g]＝[Wb-Wa]/[Wa-W ₀]

AUL 0.5psi measures under lower pressure in a similar manner.C) 16 hours extractable matter values are similar to EP-A1 811 636, and the 13rd page of the 1st description of walking to the 19th row measured.

Embodiment 3: use acrylate from embodiment 2 and composition thereof preparation high water absorbent.

Embodiment A (Comparative Examples)

In L dige VT 5R-MK colter kneader (volume is 5L), the sodium acrylate solution (100mol% neutralization) and 5.1g (=0.60 weight % is based on Acrylic Acid Monomer) the linking agent TriMethylolPropane(TMP)-15EO-triacrylate that add 180g deionized water, 220g vinylformic acid, 2201g 37.3 weight %.By nitrogen is bubbled by wherein 20 minutes and with the initial charge inerting.Add the dilute aqueous soln of 2.112g Sodium Persulfate, 0.045g xitix and 0.126g hydrogen peroxide, under about 23 ℃, begin reaction.After reaction beginning, the temperature of heating jacket is controlled at temperature of reaction in the reactor.Being aggregated under stirring and the thorough mixing in the kneader carried out.Then, with the fragility gel that obtains at last in the drying by circulating air case, 160 ℃ dry about 3 hours down.Subsequently, with its grinding, and be classified into the 300-850 micron.At last, resulting gel is characterized.

Hereinafter other embodiment similar embodiment 3A is prepared:

Table 1

The embodiment sequence number	The linking agent type	Consumption based on Acrylic Acid Monomer	Consumption (g)
				A	TriMethylolPropane(TMP)-15EO-triacrylate	0.60 weight %	5.1g
B	TriMethylolPropane(TMP)-15EO-triacrylate	2.00 weight %	17.0g
				C	TMP-30EO-5PO-triacrylate (69.3 weight %) Laromer TPGDA (30.7 weight %)	0.60 weight %	5.1g
D	Glycerine-3EO-triacrylate (25.2 weight %) TriMethylolPropane(TMP)-30EO-5PO-triacrylate (74.8 weight %)	0.60 weight %	5.1g
				E	TriMethylolPropane(TMP)-3EO-triacrylate (28.8 weight %) TriMethylolPropane(TMP)-30EO-5PO-triacrylate (71.2 weight %)	2.00 weight %	17.0g
F	TriMethylolPropane(TMP)-1PO-3EO-triacrylate (34.0 weight %) TriMethylolPropane(TMP)-30EO-5PO-triacrylate (66.0 weight %)	0.60 weight %	5.1g
				G	Diacrylate butanediol ester (18.3 weight %) TriMethylolPropane(TMP)-30EO-5PO-triacrylate (81.7 weight %)	0.60 weight %	5.1g

H	Glycerine-30EO-5PO-triacrylate (69.8 weight %) Laromer TPGDA (30.2 weight %)	2.00 weight %	17.0g
				I	TMP-30EO-5PO-triacrylate (7.7 weight %) Laromer TPGDA (92.3 weight %)	0.30 weight %	2.6g

The character of these hydrogels is summarized in the table 2

Embodiment		CRC [g/g]	Extractable matter 16 hours [weight %]	AUL 0.3psi [g/g]
					A	TMP15EOTA 0.6	35.8	9.5％	16.6
B	TMP15EOTA 2.0	26.4	5.1％	25.0
					C	TMP30EO5POTA TPGDA 0.6	36.0	10.1％	16.7
D	TMP30EO5POTA G3EOTA 0.6	36.7	8.6％	17.0
					E	TMP30EO5POTA TMP3EOTA 2.0	27.0	4.3％	25.3
F	TMP30EO5POTA TMP1PO3EOTA 0.6	37.1	8.8％	15.9
					G	TMP30EO5POTA BDDA 0.6	36.6	8.6％	16.2
H	G30EO5POTA TPGDA 2.0	27.6	4.5％	24.7
					I	TMP30EO5POTA TPGDA 0.3	35.0	10.0％	18.0

By table 2 as seen, the character of Comparative Examples linking agent can use multiple other linking agents according to calculated amount of the present invention to obtain in a similar manner.

In addition, embodiment 3I discloses linking agent intensity and can adjust by changing mixture ratio according to the present invention.It can by blending ingredients suitably keep to add the total amount of linking agent constant and only by component ratio and feedback control cross-link intensity and industrial favourable.This represents industrial advantage, can use the constant rate materials flow to adjust with big technical scale optimum ground because linking agent is in this way sneaked into monomer solution.The back is crosslinked:

With 0.12 weight %N-hydroxyethyl-2-oxazolidone, 3.35 weight % water and 1.65 weight %1, the solution of 2-propylene glycol sprays (stirring simultaneously) equably with the common base material polymer powder of exsiccant, and all percentage number averages are based on used polymkeric substance.

Batch sizes is 1.2kg in each case, and spraying is carried out with nitrogen atomization solution by two material nozzles.Use is available from the ploughshear mixer with 5 liters of working volumes of L dige.

Then, with moist powder in loft drier, 180 ℃ of following thermal treatments 60 minutes.Subsequently, under 850 microns sieving once, to remove agglomerate.

The moist polymkeric substance of only about 100g need carry out drying.

Measure the character of this back cross-linked polymer.

Embodiment	Base material polymer	CRC	AUL 0.7psi
				A	3A (Comparative Examples)	29.9	24.0
A1	3B (Comparative Examples)	24.5	21.9
				A2	3C	30.2	24.5
B	3E	25.0	22.4

In other experiments, prepared sizes are the fraction of 300-850 μ m, and back, spent glycol diglycidylether (0.10 weight % is based on polymkeric substance) surface is crosslinked.The consumption of device and all auxiliary agents is all with above-mentioned identical.Yet moist polymkeric substance is in the recirculated air case, and is only following dry 1 hour at 150 ℃.

List various performance datas, so that various linking agent can compare under controlled condition.

Linking agent	Based on acrylic acid linking agent weight percentage	CRC g/g	AUL 0.3psi g/g	AUL 0.7psi g/g	Extractable matter 16 hours
						The TMP-15EO-triacrylate	1.0	30.0	29.0	23.0	9.0
2.0	25.3	26.4	22.6	5.1
					3.0		23.7	25.3	21.6	3.2
TPGDA	1.0	33.8	32.3	24.3							17.3
					2.0	26.6	27.8	23.8	5.0
	3.0	24.8	26.3	22.5						4.4

TMP-30EO-5PO-triacrylate	1.0	32.9	31.8	25.0	13.7
						2.0	32.2	30.0	22.8	11.7
	3.0	29.3	29.1	23.2	8.0
						70 weight % TMP-30EO-5PO-triacrylates, 30 weight %TPGDA	0.25	31.6	30.5	23.6	11.1
0.35	32.1	30.9	23.8	11.4
					0.50		31.2	30.8	24.5	9.1
0.70	29.9	30.2	24.5	6.9
					1.00		28.7	29.5	23.9	5.9
1.50	27.4	28.1	23.6	4.8
					2.00		26.6	27.7	23.4	4.4

It is evident that by last table the mixture of two kinds of linking agents of the present invention is better than the use of each independent linking agent component, also be better than having the unitary class of similar WFR like linking agent.

For example, about 9 extractable matter value realizes when only the linking agent of the present invention of 0.5 weight % makes up, what can compare with it is, is surpassing 1.0 weight % or even is surpassing under the independent component of 2.0 weight % linking agent fractional and realize under similar each linking agent of about 1.0 weight % fractional.For identical extractable matter value, the CRC and the AUL value of linking agent combination are better than similar independent linking agent equally.

In further testing, prepare 6 kinds of different mixtures with explanation the present invention.The polymkeric substance that forms hydrogel is as preparation as described in the embodiment A, and different is replaces used pure linking agent with one of described mixture of equivalent in each case.Then, as mentioned above, it is crosslinked that the ethylene glycol diglycidylether of use 300-850 μ m fraction carries out the back.

Mixture	Linking agent	Weight percentage in mixture	Functionality	M w	M w/F	Molar fraction (α)	Based on acrylic acid consumption	CRC	AUL 0.7psi	Extractable matter 16h
											1	Trimethylolpropane trimethacrylate	21.4％	3	338	113	0.61	0.6 weight %	30.5	24.7	9.0％
The TMP-30EO-5PO-triacrylate	78.6％	3	1906	635	0.39
						2	The glycerine diacrylate	18.6％	2	200		100	0.59	0.6 weight %	31.0	25	8.9％
The TMP-30EO-5PO triacrylate	81.4％	3	1906	635	0.41
							3	Polyoxyethylene glycol-300 diacrylate	47.0％	2	408	204	0.73					0.6 weight %	30.3	24.3	8.2％
The TMP-30EO-5PO triacrylate	53.0％	3	1906	635	0.27
						4		Glycerine-3PO-triacrylate	28.8％	3	428	143	0.64	0.6 weight %	30.1	25.2	7.9％
The TMP-30EO-5PO-triacrylate	71.2％	3	1906	635	0.36
							5	Glycerine-3EO-triacrylate	26.6％	3	386	129	0.66					0.6 weight %	30.8	25.6	9.7％
TMP-40EO-TA	73.4％	3	2056	685	0.34
						6		Glycerine-3EO-triacrylate	26.2％	3	386	129	0.65	0.6 weight %	30.1	24.9	8.0％
Glycerine-40EO-triacrylate	73.8％	3	2014	671	0.35

Claims (30)

1. one kind at least two kinds mixtures that have the compound of at least two two keys separately, the WFR that described mixture has is the two keys of 200-600g/mol, and at least two kinds of described compounds contain at least two (methyl) acrylate separately as two key components, and WFR is provided by following formula:

$\underset{i=1}{\overset{n}{\mathrm{\&Sigma;}}}{\mathrm{\&alpha;}}_i\&times;M{W}_i/Z_i=\mathrm{WFR},$ Wherein

$\underset{i=1}{\overset{n}{\mathrm{\&Sigma;}}}{\mathrm{\&alpha;}}_i=1$

α _iEqual the molar fraction of compound (i) in described mixture,

N equals the compound number in the described mixture, and n 〉=2,

Z _iEqual the double key number order in the described compound (i),

MW _iEqual the molecular weight of described compound (i).

2. according to the mixture of claim 1, its WFR that has is the two keys of 240-400g/mol, and preferred WFR is the two keys of 250-350g/mol.

3. according to the mixture of claim 1 or 2, wherein n is 2,3 or 4, preferred 2.

4. according to each mixture among the claim 1-3, wherein the ratio of the MW/Z of two kinds of compounds differs the two keys of 50g/mol at least at least, preferred two keys of 100g/mol at least, more preferably two keys of 250g/mol at least.

5. according to each mixture among the claim 1-4, wherein the ratio of a kind of MW/Z of compound is lower than the two keys of 400g/mol, preferably is lower than the two keys of 300g/mol, more preferably less than the two keys of 200g/mol, especially is lower than the two keys of 150g/mol.

6. according to each mixture among the claim 1-5, wherein the ratio of a kind of MW/Z of compound is higher than the two keys of 400g/mol and is lower than the two keys of 10000g/mol, preferably is higher than the two keys of 600g/mol and is lower than the two keys of 1000g/mol.

7. according to each mixture among the claim 1-6, wherein the Z of at least a compound is 2-6, preferred 2,3 or 4.

8. according to each mixture among the claim 1-7, wherein said compound is ester Fi, and it can be by obtaining with (methyl) acroleic acid esterification polyvalent alcohol Ai, and each polyvalent alcohol Ai has Zi hydroxy functional group and 2-50 carbon atom.

9. according to each mixture among the claim 1-8, wherein a kind of compound is represented by one of following formula:

Or

Wherein AO be independently in each case-O-CHR7-CHR8-or-CHR7-CHR8-O-, wherein R7 and R8 are H, linearity or branching C1-C8 alkyl independently,

R5 and R6 are H, linearity or branching C1-C8 alkyl independently,

N is 1,2 or 3,

P1 is 0,1 or 2,

P2 is 0,1 or 2,

P3 is 0,1 or 2,

P4 is 0,1 or 2,

R1, R2, R3, R4 are H or CH3 independently.

10. according to each mixture among the claim 1-9, wherein a kind of compound is represented by one of following formula:

Or

Wherein AO be independently in each case-O-CHR7-CHR8-or-CHR7-CHR8-O-, wherein R7 and R8 are H, linearity or branching C1-C8 alkyl independently,

R5 and R6 are H, linearity or branching C1-C8 alkyl independently,

N is 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19 or 20,

P1 is 7,8,9,10,11,12,13,14,15,16,17,18,19 or 20,

P2 is 7,8,9,10,11,12,13,14,15,16,17,18,19 or 20,

P3 is 7,8,9,10,11,12,13,14,15,16,17,18,19 or 20,

P4 is 7,8,9,10,11,12,13,14,15,16,17,18,19 or 20,

R1, R2, R3, R4 are H or CH3 independently.

11. according to the mixture of claim 9 or 10, wherein AO is EO or PO in each case independently,

Wherein EO is O-CH2-CH2-,

PO is O-CH2-CH (CH3)-or O-CH (CH3)-CH2-independently,

R5 and R6 are H or CH3 independently.

12. the alcohol mixture by described polyvalent alcohol Ai begins to prepare the method according to the ester mixture of each described ester Fi among the claim 1-11, may further comprise the steps:

A) described polyvalent alcohol Ai and (methyl) vinylformic acid are reacted in the presence of at least a esterifying catalyst C and at least a polymerization retarder D and optional water azeotropic solvent E, form the ester mixture of described ester Fi,

B) during a) and/or afterwards, optionally take out the some or all of water that in a), form by reaction mixture,

F) the described reaction mixture of optional neutralization,

H) when using solvent E, choose wantonly and remove this solvent by distillation, and/or

I) be used in and be the inert gasses stripping under the reaction conditions.

13. according to the method for claim 12, wherein

The molar excess that-(methyl) vinylformic acid surpasses described polyvalent alcohol Ai for 5*Zi mol% at least and

Optional neutral (methyl) vinylformic acid that comprises in-described the reaction mixture is in the end stayed in the described reaction mixture after the step substantially.

14. according to the method for claim 12 or 13, (methyl) vinylformic acid that wherein is no more than 75 weight % is by removing in the reaction mixture that contains ester mixture that obtains behind described final step.

15. according to each method among the claim 12-14, DIN EN 3682 acid numbers that the reaction mixture that contains ester mixture that wherein obtains behind described final step has are 25mgKOH/g at least.

16. according to each method among the claim 12-15, (methyl) acrylic acid content that the reaction mixture that contains ester mixture that wherein obtains behind described final step has is at least 0.5 weight %.

17. according to each method among the claim 12-16, wherein the mol ratio of (methyl) vinylformic acid in reaction a) and alcohol mixture Ai is 5*Zi at least: 1.

18. a method for preparing cross-linked hydrogel, it may further comprise the steps:

K) make according to the ester mixture of each ester Fi among the claim 1-11 and (methyl) vinylformic acid and optional extra monoene ethylenically unsaturated compounds N, but and optional at least a other copolymerization hydrophilic monomers M, polymerization in the presence of at least a radical initiator K and optional at least a other grafting base-materials L

It is l) optional making) crosslinked behind the reaction mixture that obtains by k,

M) will be by k) or the reaction mixture drying that l) obtains and

N) optional will be by k), l) or the reaction mixture that m) obtains grind and/or sieving.

19. a method for preparing cross-linked hydrogel comprises according to each step a)-i) and extra following steps among the claim 12-17:

K) make if the words of carrying out, reaction mixture of one of step a)-i) and optional extra monoene ethylenically unsaturated compounds N, but and optional at least a other copolymerization hydrophilic monomers M, polymerization in the presence of at least a radical initiator K and optional at least a grafting base-material L

It is l) optional making) crosslinked behind the reaction mixture that obtains by k,

M) will be by k) or the reaction mixture drying that l) obtains and

N) optional will be by k), l) or the reaction mixture that m) obtains grind and/or sieving.

20. the polymkeric substance that can obtain according to the method for claim 18 or 19.

21. comprise the cross-linked hydrogel of the hydrophilic monomer M of at least a copolymerized form, described hydrogel is used according to the ester mixture of each ester Fi among the claim 1-11 crosslinked.

22. comprise the cross-linked hydrogel of the hydrophilic monomer M of at least a copolymerized form, described hydrogel is crosslinked with the reaction mixture that the ester mixture that comprises described ester Fi also can obtain according to the method for claim 12-15.

23. according to each the purposes of polymkeric substance in hygienic articles, wrapping material and non-woven fabric among the claim 20-22.

24. a composition of matter, it comprises following component:

-0.1-40 weight % at least a ester mixture and (methyl) vinylformic acid according to each ester Fi among the claim 1-11,

At least a hydrophilic monomer M of-0.5-99.9 weight %,

At least a esterifying catalyst C of-0-10 weight %,

At least a polymerization retarder D of-0-5 weight % and

At least a solvent E of-0-10 weight %,

Prerequisite is summation 100 weight % always.

25. according to the composition of matter of claim 24, it further comprises following component:

-thinner G supplies 100 weight %.

26. the cross-linked hydrogel that can obtain by composition of matter and extra following steps according to claim 24 or 25:

It is l) optional with crosslinked behind the reaction mixture that obtains,

M) will directly obtain or by l) the reaction mixture drying that obtains and

N) optional will directly obtain or by l) or the reaction mixture that m) obtains grind and/or sieving.

27. can be according to each reaction mixture that obtains among the claim 12-17 or according to the following purposes of the composition of matter of claim 24 or 25:

-as the free-radical crosslinking agent of water-absorbent hydrogel,

-as the raw material for preparing polymeric dispersions,

-as the raw material for preparing polyacrylic ester,

-as paint raw materials, or

-as cement additire.

28. according to each cross-linked hydrogel in the claim 20,21,22 and 26, its residual cross-linker content that has is lower than 10ppm, preferably is lower than 8ppm, more preferably less than 5ppm.

29. the purposes of ester mixture in preparing the polymkeric substance that can absorb liquid, aqueous formation hydrogel according to each ester Fi among the claim 1-11.

30. according to the purposes of the ester mixture of claim 29, wherein to be lower than 2 weight %, preferred 1 weight % exists each ester component Fi based on the monomer total amount.