WO2003104301A1 - (meth)acrylester von polyalkoxyliertem glycerin - Google Patents
(meth)acrylester von polyalkoxyliertem glycerin Download PDFInfo
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- WO2003104301A1 WO2003104301A1 PCT/EP2003/006028 EP0306028W WO03104301A1 WO 2003104301 A1 WO2003104301 A1 WO 2003104301A1 EP 0306028 W EP0306028 W EP 0306028W WO 03104301 A1 WO03104301 A1 WO 03104301A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/58—Ethylene oxide or propylene oxide copolymers, e.g. pluronics
Definitions
- the present invention relates to new (meth) acrylic esters of polyalkoxylated glycerol, a simplified process for the preparation of these esters and use of the reaction mixtures thus obtainable.
- superabsorbents Super Absorbing Polymers, SAP
- SAP Super Absorbing Polymers
- These are networks of flexible hydrophilic polymers, which can be both ionic and nonionic in nature. These are able to absorb and bind aqueous liquids with the formation of a hydrogel and are therefore preferred for the production of tampons, diapers, sanitary napkins, incontinence articles, training underwear for children, shoe insoles and other hygiene articles in the absorption of body fluids.
- Superabsorbents are also used in other areas of technology in which liquids, in particular water or aqueous solutions, are absorbed. These areas are e.g. Storage, packaging, transport (packaging material for water-sensitive items such as flower transport, shock protection); Food sector (transportation of fish, fresh meat;
- the superabsorbers are usually located in the so-called absorbent core, which includes fibers (cellulose fibers), which, as a kind of liquid reservoir, temporarily store the spontaneously applied amounts of liquid and ensure good drainage of body fluids in the absorbent core to ensure superabsorbent.
- absorbent core which includes fibers (cellulose fibers), which, as a kind of liquid reservoir, temporarily store the spontaneously applied amounts of liquid and ensure good drainage of body fluids in the absorbent core to ensure superabsorbent.
- Hydrogels for example, have good transport properties and, when swollen, have a high gel strength. Gels with only low gel strength can be deformed under an applied pressure (body pressure), clog pores in the superabsorbent / cellulose fiber absorbent body and thereby prevent further fluid absorption. Increased gel strength is generally achieved through higher crosslinking, which, however, reduces the retention of the product.
- Surface post-crosslinking is an elegant method of increasing gel strength. In this process, dried superabsorbents with an average crosslinking density are subjected to additional crosslinking. Through the Surface post-crosslinking increases the crosslinking density in the shell of the superabsorbent particles, which increases the absorption under pressure to a higher level.
- the core of the superabsorbent particles has an improved absorption capacity compared to the shell due to the presence of movable polymer chains, so that the shell structure ensures improved liquid transmission without the effect of gel blocking occurring. It is entirely desirable that the total capacity of the superabsorbent is not used spontaneously, but with a time delay. Since the hygiene article is usually exposed to urine several times, the absorption capacity of the superabsorbent does not need to be exhausted after the first disposition.
- Hydrophilic, highly swellable hydrogels are in particular polymers of (co) polymerized hydrophilic monomers, graft (co) polymers of one or more hydrophilic monomers on a suitable graft base, crosslinked cellulose or starch ethers, crosslinked carboxymethyl cellulose, partially crosslinked polyalkylene oxide or natural products swellable in aqueous liquids, such as guar derivatives.
- Such hydrogels are used as aqueous solution-absorbing products for the production of diapers, tampons, sanitary napkins and other types of hygiene, but also as water-retaining agents in agricultural horticulture.
- hydrophilic, highly swellable hydrogels are generally surface or gel cross-linked. This postcrosslinking is known per se to the person skilled in the art and is preferably carried out in the aqueous gel phase or as surface postcrosslinking of the ground and sieved polymer particles.
- EP 238050 discloses, as possible internal crosslinking agents for superabsorbents, addition products of ethylene oxide and / or propylene oxide onto trimethylolpropane esterified two or three times with acrylic acid or methacrylic acid.
- trimethylolpropane triacrylate (SR 351), three times ethoxylated trimethylolpropane triacrylate (SR 454), three times twice ethoxylated trimethylolpropane triacrylate (SR 499), three times triple ethoxylated trimethylolate SR3 ), three times five times ethoxylated trimethylolpropane triacrylate (SR 9035) and a total of 20 times ethoxylated trimethylolpropane triacrylate (SR 415).
- SR 351 trimethylolpropane triacrylate
- SR 454 three times ethoxylated trimethylolpropane triacrylate
- SR 499 three times twice ethoxylated trimethylolpropane triacrylate
- SR 9035 three times five times ethoxylated trimethylolpropane triacrylate
- SR 415 a total of 20 times ethoxylated trimethylolpropane triacrylate
- Propoxylated trimethyl propane triacrylates are available under the trade names SR 492 (three times 1 PO per TMP) and CD 501 (three times 2 PO per TMP).
- glycerol derivatives are under CD 9021 highly propoxylated glycerol triacrylate and commercially available under CD 9020 tripropoxyglycerol triacrylate.
- WO 93/21237 discloses (meth) acrylates of alkoxylated polyvalent C 2 -C 10 hydrocarbons as crosslinking agents. Trimethyl propane crosslinkers corresponding to SR 351, SR 454, SR 502, SR 9035 and SR 415 were used. These crosslinkers have 0, 3, 9, 15 or 20 EO units per TMP. According to WO 93/212373, 2 to 7 EO units per TMP are advantageous, in particular 3 times 4 to 6 EO units per TMP.
- a disadvantage of these compounds is that complex cleaning operations are required for at least partial separation of starting materials and by-products - the crosslinking agents used in the document mentioned have an acrylic acid content of less than 0.1% by weight. ⁇
- Ethoxylated trimethylolpropane tri (meth) acrylates are mentioned again and again in the patent literature as internal crosslinking agents, only the TMP derivatives commercially available from Sartomer being used, e.g. in WO 98/47951 trimethylolpropane triethoxylate triacrylate, in WO 01/41818 Sartomer # 9035 as so-called highly ethoxylated trimethylol propane triacrylate (HeTMPTA) and in WO 01/56625 SR 9035 and
- WO 2001/14438 (Derwent Abstract No. 2001-191644 / 19) and WO 2001/10920 (Chemical Abstracts 134: 163502) describe processes for the esterification of (meth) acrylic acid with polyalkylene glycol monoalkyl ethers in the ratio 3: 1 - 50: 1 in the presence of acids and polymerization inhibitors and, after deactivation of the acid catalyst, copolymerization of the residue from (meth) acrylic acid ester and (meth) acrylic acid at pH 1.5-3.5, and its use as a cement additive.
- a disadvantage of these processes is that it is limited to polyalkylene glycol monoalkyl ethers, that the catalyst has to be deactivated and that such copolymers cannot be used as crosslinking agents for hydrogels since they only have one functionality.
- the object was to provide further compounds which can be used as radical crosslinkers for polymers, in particular for superabsorbers, and to simplify the production process for substances which can be used as radical crosslinkers for superabsorbers.
- PO independently of one another means O-CH2-CH (CH3) - or O-
- p1 + p2 + p3 is 3, 4 or 5, R1, R2, R3 independently of one another H or CH3.
- the EO or PO units are installed in such a way that polyethers and no peroxides are formed.
- esters F are preferred, where AO is EO.
- esters F where at least one AO is PO and at least one further AO is EO.
- ester F of the formula Ib is solved by ester F of the formula Ib:
- PO independently of one another means O-CH2-CH (CH3) - or O- CH (CH3) -CH2-
- n1 + n2 + n3 is 3, 4 or 5
- n1 + m2 + m3 is 1, 2, 3, or 4,
- R1, R2, R3 independently of one another H or CH3.
- PO independently of one another means O-CH2-CH (CH3) - or O- CH (CH3) -CH2-
- n1 + n2 + n3 is 3, 4 or 5
- n1 + m2 + m3 is 1, 2, 3, or 4,
- R1, R2, R3 independently of one another H or CH3.
- esters F Preferred in the above esters are esters F, where m1 + m2 + m3 + n1 + n2 + n3 or p1 + p2 + p3 is 3.
- esters F Preferred in the above esters are esters F, where m1 + m2 + m3 + n1 + n2 + n3 or p1 + p2 + p3 is 5.
- Esters F are particularly preferred, a total of 3 PO being present.
- Esters F are very particularly preferred, with at least 1 PO being present in each of the 3 alkoxy chains of glycerol.
- Esters F in which R1, R2 and R3 are identical are very particularly preferred, in particular when R1, R2 and R3 are H.
- esters F of the abovementioned formula with the meanings given can be used for the preparation of hydrogel-forming polymers which absorb aqueous liquids, in particular as internal crosslinkers.
- the further object is achieved by a process for the preparation of an ester F of alkoxylated glycerol with (meth) acrylic acid, comprising the steps a) reaction of alkoxylated glycerol with (meth) acrylic acid in the presence of at least one esterification catalyst C and at least one polymerization inhibitor D and, if appropriate, a solvent E which forms an azeotrope with water to form an ester F, b) optionally removing at least part of the product formed in a) Water from the reaction mixture, where b) can take place during and / or after a), f) optionally neutralizing the reaction mixture, h) if a solvent E has been used, optionally removing this solvent by distillation and / or i) stripping with a gas inert to the reaction conditions.
- (meth) acrylic acid is understood to mean methacrylic acid, acrylic acid or mixtures of methacrylic acid and acrylic acid. Acrylic acid is preferred.
- ester F is required in its pure form, it can be purified by known separation processes.
- the molar excess of (meth) acrylic acid to alkoxylated glycerol is at least 3.15: 1, preferably at least 3.3: 1, particularly preferably at least 3.75: 1, very particularly preferably at least 4.5: 1 and in particular at least 7, 5: 1.
- (meth) acrylic acid is used in an excess of, for example, greater than 15: 1, preferably greater than 30: 1, particularly preferably greater than 60: 1, very particularly preferably greater than 150: 1, in particular greater than 225: 1 and especially larger than 300: 1 used.
- crosslinking in this document means radical crosslinking (gel crosslinking, internal crosslinking, crosslinking of linear or weakly crosslinked polymer). This crosslinking can take place via radical or cationic polymerization mechanisms or other mechanisms, for example Michael addition, esterification or transesterification mechanisms, preferably by radical polymerization.
- Aqueous liquid-absorbing hydrogel-forming polymers are preferably those with an absorption of distilled water of at least their own weight, preferably 10 times their own weight, in particular 20 times their own weight; this absorption is preferably also achieved under a pressure of 0.7 psi.
- Alkoxylated glycerol which can be used according to the invention have the structure as in formula IIa, Mb or IIc
- Esterification catalysts C which can be used according to the invention are sulfuric acid, aryl or alkylsulfonic acids or mixtures thereof.
- arylsulfonic acids are benzenesulfonic acid, para-toluenesulfonic acid or dodecylbenzenesulfonic acid
- alkylsulfonic acids are methanesulfonic acid, ethanesulfonic acid or trifluoromethanesulfonic acid.
- Strongly acidic ion exchangers or zeolites can also be used as esterification catalysts. Sulfuric acid and ion exchangers are preferred.
- Polymerization inhibitors D which can be used according to the invention are, for example, phenols such as alkylphenols, for example o-, m- or p-cresol (methylphenol), 2-tert-butyl-4-methylphenol, 6-tert.-butyl-2,4-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butylphenol, 4-tert-butylphenol, 2,4-di-tert-butylphenol, 2-methyl-4-tert-
- hydroquinone, hydroquinone monomethyl ether, 2-tert-butyl-4-methylphenol, 6-tert-butyl-2,4-dimethylphenol, 2,6-di-tert.- are particularly preferred.
- Butyl-4-methylphenol, 2,4-di-tert-butylphenol, triphenylphosphite, hypophosphorous acid, CuCl and guaiacol, hydroquinone and hydroquinone monomethyl ether are very particularly preferred.
- an oxygen-containing gas preferably air or a mixture of air and nitrogen (lean air) can be present.
- stabilizers listed preferred are those that are aerobic, i.e. before they require the presence of oxygen to develop their full inhibitory effect.
- Solvents E which can be used according to the invention are, in particular, those which are suitable for azeotropic removal of the water of reaction, if desired, in particular aliphatic, cycloaliphatic and aromatic hydrocarbons or mixtures thereof.
- N-Pentane, n-hexane, n-heptane, cyclohexane, methylcyclohexane, benzene, toluene or xylene are preferably used. Cyclohexane, methylcyclohexane and toluene are particularly preferred.
- the preparation and / or processing methods of polyhydric alcohols known to the person skilled in the art can be used, for example those mentioned at the beginning or those described in DE-A 19941 136, DE-A 3843843, DE-A 3843 854, DE-A 199 37911, DE-A 19929258, EP-A 331 845, EP 554651 or US 4 187 383.
- esterification can be carried out as follows:
- the esterification apparatus consists of a stirred reactor, preferably a reactor with a circulation evaporator and an attached distillation unit with a condenser and phase separation vessel.
- the reactor can be, for example, a reactor with double-wall heating or / and internal heating coils.
- a reactor with an external heat exchanger and natural or forced circulation i.e. using a pump, particularly preferably natural circulation, in which the circulation flow is accomplished without mechanical aids,
- reaction can also be carried out in several reaction zones, for example a reactor cascade consisting of two to four, preferably two to three, reactors.
- Suitable circulation evaporators are known to the person skilled in the art and are described, for example, in R. Billet, Verdampfertechnik, HTB-Verlag, bibliographisches Institut
- circulation evaporators are shell and tube heat exchangers, plate heat exchangers, etc.
- the distillation unit is of a type known per se. This can be a simple distillation, which may be equipped with a splash guard, or a rectification column.
- column internals for example trays, packings and / or fillings.
- trays bubble trays, sieve trays, valve trays, Thormann trays and / or dual-flow trays are preferred; of the fillings, those with rings, spirals, saddle bodies or braids are preferred.
- the condenser and the separation vessel are of conventional construction.
- esterification catalysts C are suitable.
- They are generally used in an amount of 0.1-5% by weight, based on the esterification mixture, preferably 0.5-5%, particularly preferably 1-4% and very particularly preferably 2-4% by weight.
- the esterification catalyst can be removed from the reaction mixture using an ion exchanger.
- the ion exchanger can be added directly to the reaction mixture and then filtered off, or the reaction mixture can be passed over an ion exchange bed.
- the esterification catalyst is preferably left in the reaction mixture. However, if the catalyst is an ion exchanger, this is preferably removed, for example by filtration.
- an oxygen-containing gas preferably air or a mixture of air and nitrogen (lean air) can be present.
- This oxygen-containing gas is preferably metered into the bottom area of a column and / or into a circulation evaporator and / or passed through the reaction mixture and / or through it.
- the polymerization inhibitor (mixture) D (as mentioned above) is used in a total amount of 0.01-1% by weight, based on the esterification mixture, preferably 0.02-0.8, particularly preferably 0.05-0, 5% by weight.
- the polymerization inhibitor (mixture) D can be used, for example, as an aqueous solution or as a solution in a starting material or product.
- the water of reaction formed during the reaction can be distilled off during or after the esterification a), this process being able to be supported by a solvent which forms an azeotrope with water.
- the solvents listed above are suitable as solvent E for azeotropic removal of the water of reaction, if desired.
- the amount of solvent used is 10-200% by weight, preferably 20-100% by weight, particularly preferably 30-100% by weight, based on the sum of alkoxylated glycerol and (meth) acrylic acid.
- the water contained in the reaction mixture is not removed using an azeotroping solvent, it is possible to remove it by stripping with an inert gas, preferably an oxygen-containing gas, particularly preferably with air or lean air, for example as in DE-A 3843843 described.
- an inert gas preferably an oxygen-containing gas, particularly preferably with air or lean air, for example as in DE-A 3843843 described.
- the reaction temperature of the esterification a) is generally 40-160 ° C., preferably 60-140 ° C. and particularly preferably 80-120 ° C.
- the temperature can remain the same or rise in the course of the reaction, but is preferably raised in the course of the reaction. In this case the final temperature of the esterification is 5 - 30 ° C higher than the initial temperature.
- the temperature of the esterification can be determined and regulated by varying the solvent concentration in the reaction mixture, as described in DE-A 19941 136 and the German application with the file number 100 63 175.4.
- a solvent If a solvent is used, it can be distilled off from the reaction mixture via the distillation unit attached to the reactor.
- the distillate can either be removed or, after condensation, fed into a phase separator.
- the aqueous phase obtained in this way is generally discharged, the organic phase can be fed as reflux into the distillation unit and / or can be passed directly into the reaction zone and / or into a circulation evaporator, as in the German patent application with the file number 100 63 175.4.
- the organic phase when used as reflux, can be used to control the temperature in the esterification.
- the esterification a) can be carried out without pressure, but also under overpressure or underpressure, preferably under normal pressure.
- the reaction time is generally 2 to 20 hours, preferably 4 to 15 and particularly preferably 7 to 12 hours.
- reaction components are added is not essential according to the invention. All components can be initially mixed and then heated, or one or more components cannot be initially or only partially and only added after the heating.
- composition of the (meth) acrylic acid which can be used is not restricted and can have, for example, the following components:
- the crude (meth) acrylic acid used is generally stabilized with 200-600 ppm phenothiazine or other stabilizers in amounts which enable comparable stabilization.
- carbonyl-containing includes acetone and lower aldehydes, e.g. Formaldehyde, acetaldehyde, crotonaldehyde, acrolein, 2- and 3-furfural and benazaldehyde, understood.
- Crude (meth) acrylic acid is understood here to mean the (meth) acrylic acid-containing mixture which is obtained after absorption of the reaction gases from propane / propene / acrolein or isobutane / isobutene / methacrolein oxidation in an absorption medium and subsequent separation of the absorption medium or by fractionation Condensation of the reaction gases is obtained.
- pure (meth) acrylic acid can also be used, for example with the following purity: (Meth) acrylic acid 99.7 - 99.99% by weight
- the pure (meth) acrylic acid used is generally stabilized with 100-300 ppm hydroquinone monomethyl ether or other storage stabilizers in amounts which enable comparable stabilization.
- Pure or pre-cleaned (meth) acrylic acid is generally understood to mean (meth) acrylic acid, the purity of which is at least 99.5% by weight and which is essentially free of the aldehydic, other carbonyl-containing and high-boiling components. - ⁇ - - - • • - - - --- -
- the (meth) acrylic acid contained therein can advantageously be extracted with an extracting agent, preferably the solvent which may be used in the esterification, for example with cyclohexane, at a temperature between 10 and 40 ° C. and a ratio of aqueous phase to extracting agent of 1: 5-30, preferably 1:10-20, extracted and returned to the esterification.
- an inert gas preferably an oxygen-containing gas, particularly preferably air or a mixture of air and nitrogen (lean air) can be passed into the circulation, through or over the reaction mixture, for example in amounts of 0.1 1, preferably 0.2-0.8 and particularly preferably 0.3-0.7 m 3 / m 3 h, based on the volume of the reaction mixture.
- the course of the esterification a) can be followed by tracking the amount of water discharged and / or the decrease in the carboxylic acid concentration in the reactor.
- the reaction can be ended, for example, as soon as 90% of the theoretically expected amount of water has been discharged through the solvent, preferably at least 95% and particularly preferably at least 98%.
- the end of the reaction can be determined, for example, by essentially no further water of reaction being removed via the entrainer. If (methacrylic) acid is discharged together with the water of reaction, its proportion can be determined, for example, by back-titrating an aliquot of the aqueous phase.
- Removal of the reaction water can be dispensed with, for example, if the (methacrylic) acid is used in a high stoichiometric excess, for example of at least 4.5: 1, preferably at least 7.5: 1 and very particularly preferably at least 15: 1. In this case, a substantial part of the amount of water formed remains in the reaction mixture. During or after the reaction, only the proportion of water which is determined by the volatility at the temperature applied is removed from the reaction mixture and, in addition, no measures are taken to separate off the water of reaction formed. For example, at least 10% by weight of the water of reaction formed can remain in the reaction mixture, preferably at least 20% by weight, particularly preferably at least 30% by weight, very particularly preferably at least 40 and in particular at least 50% by weight.
- the reactor mixture can be cooled in a customary manner to a temperature of 10 to 30 ° C. and, if appropriate, by adding solvent, which can be the same as or different from the solvent which may be used for the azeotropic removal of water any target ester concentration can be set.
- the reaction can be stopped with a suitable diluent G and to a concentration of, for example, 10-90% by weight, preferably 20-80%, particularly preferably 20 to 60%, very particularly preferably 30 to 50% and in particular diluted approx. 40%, for example to reduce the viscosity.
- the diluent G is selected from the group consisting of water, a mixture of water with one or more water-soluble organic solvents or a mixture of water with one or more single or multi-functional alcohols, for example methanol and glycerol.
- the alcohols preferably carry 1, 2 or 3 hydroxyl groups and preferably have between 1 and 10, in particular up to 4, carbon atoms. Primary and secondary alcohols are preferred.
- Preferred alcohols are methanol, ethanol, isopropanol, ethylene glycol, 1,2-propanediol or 1,3-propanediol.
- the reaction mixture can be decolorized, for example by treatment with activated carbon or metal oxides, e.g. Aluminum oxide, silicon oxide, magnesium oxide, zirconium oxide, boron oxide or mixtures thereof, in amounts of, for example, 0.1-50% by weight, preferably 0.5 to 25% by weight, particularly preferably 1-10% by weight, at temperatures of, for example, 10 to 100 ° C, preferably 20 to 80 ° C and particularly preferably 30 to 60 ° C.
- activated carbon or metal oxides e.g. Aluminum oxide, silicon oxide, magnesium oxide, zirconium oxide, boron oxide or mixtures thereof, in amounts of, for example, 0.1-50% by weight, preferably 0.5 to 25% by weight, particularly preferably 1-10% by weight, at temperatures of, for example, 10 to 100 ° C, preferably 20 to 80 ° C and particularly preferably 30 to 60 ° C.
- the reaction mixture can be decolorized at any point in the work-up process, for example at the stage of the crude reaction mixture or after prewashing, neutralization, washing or solvent removal, if appropriate.
- the reaction mixture can also be subjected to a pre-wash e) and / or a neutralization f) and / or a post-wash g), preferably only a neutralization f). If necessary, neutralization f) and prewash e) can also be interchanged in the order.
- the (meth) acrylic acid and / or catalyst C contained in the aqueous phase of the washes e) and g) and / or neutralization f) can be at least partially recovered by acidification and extraction with a solvent and used again.
- the reaction mixture is washed in a washing apparatus with a washing liquid, for example water or a 5-30% by weight, preferably 5-20, particularly preferably 5-15% by weight sodium chloride, potassium chloride - Ammonium chloride, sodium sulfate or ammonium sulfate solution, preferably water or saline, treated.
- a washing liquid for example water or a 5-30% by weight, preferably 5-20, particularly preferably 5-15% by weight sodium chloride, potassium chloride - Ammonium chloride, sodium sulfate or ammonium sulfate solution, preferably water or saline, treated.
- the quantitative ratio of reaction mixture: washing liquid is generally 1: 0.1-1, preferably 1: 0.2-0.8, particularly preferably 1: 0.3-0.7.
- the washing or neutralization can be carried out, for example, in a stirred tank or in other conventional equipment, e.g. in a column or mixer-settler apparatus.
- Sieve plate or packed or packed columns, stirred tanks or mixer-settlers, and pulsed columns or those with rotating internals are preferably used.
- the prewash e) is preferably used when metal salts, preferably copper or copper salts, are used as inhibitors (with).
- Rinsing g) can be advantageous for removing base or salt traces from the reaction mixture neutralized in f).
- a base such as, for example, alkali metal or alkaline earth metal oxides, hydroxides, carbonates or hydrogen carbonates, preferably sodium hydroxide solution, Potassium hydroxide solution, sodium hydrogen carbonate, sodium carbonate, potassium hydrogen carbonate, calcium hydroxide, lime milk, ammonia
- the degree of neutralization is preferably 5 to 60 mol%, preferably 10 to 40 mol%, particularly preferably 20 to 30 mol%, based on the monomers containing acid groups. This neutralization one can take place before and / or during the polymerization, preferably before the polymerization.
- the base is added in such a way that the temperature in the apparatus does not rise above 60 ° C., is preferably between 20 and 35 ° C. and the pH is 4-13.
- the heat of neutralization is preferably dissipated by cooling the container with the aid of internal cooling coils or via double-wall cooling.
- the ratio of the reaction mixture to the neutralizing liquid is generally 1: 0.1-1, preferably 1: 0.2-0.8, particularly preferably 1: 0.3-0.7.
- a solvent is present in the reaction mixture, this can essentially be removed by distillation. Any solvent present is preferably removed from the reaction mixture after washing and / or neutralization, but if desired this can also be done before washing or neutralization.
- an amount of storage stabilizer preferably hydroquinone monomethyl ether, is added to the reaction mixture such that 100-500, preferably 200-500 and particularly preferably 200-400 ppm thereof are present in the target ester (residue) after removal of the solvent.
- the main amount of solvent is removed by distillation, for example, in a stirred tank with double-wall heating and / or internal heating coils under reduced pressure, for example at 20-700 mbar, preferably 30-500 and particularly preferably 50-150 mbar and a temperature of 40-80 ° C. ,
- the distillation can also be carried out in a falling film or thin film evaporator.
- the reaction mixture is passed through the apparatus, preferably several times in a circuit, under reduced pressure, for example at 20-700 mbar, preferably 30-500 and particularly preferably 50-150 mbar and a temperature of 40-80 ° C.
- An inert gas preferably an oxygen-containing gas, particularly preferably air or a mixture of air and nitrogen (lean air) can advantageously be introduced into the distillation apparatus, for example 0.1-1, preferably 0.2-0.8 and particularly preferably 0, 3 - 0.7 m 3 / m 3 h, based on the volume of the reaction mixture.
- the residual solvent content in the residue after the distillation is generally less than 5% by weight, preferably 0.5-5% and particularly preferably 1 to 3% by weight.
- the separated solvent is condensed and preferably reused.
- solvent stripping i) can be carried out in addition to or instead of the distillation.
- the target ester which still contains small amounts of solvent, is heated to 50-90 ° C., preferably 80-90 ° C., and the remaining amounts of solvent are removed with a suitable gas in a suitable apparatus.
- a vacuum can also be applied to assist.
- Suitable apparatuses are, for example, columns of a type known per se, which have the usual internals, e.g. Bottoms, fillings or directional packs, preferably fillings.
- internals e.g. Bottoms, fillings or directional packs, preferably fillings.
- all common internals come into consideration as column internals, for example trays, packings and / or packing elements.
- Bell bottoms, sieve bottoms, valve bottoms, Thormann bottoms and / or dual-flow bottoms are preferred of the bottoms, of the fillings are those with rings, spirals,
- a falling film, thin film or wiped film evaporator such as e.g. a Luwa, Rotafilm or Sambay evaporator, which can be equipped with a demister as a splash guard, for example.
- gases which are inert under the stripping conditions, preferably oxygen-containing gases, particularly preferably air or mixtures of air and nitrogen (lean air) or water vapor, in particular those which are heated to 50 to 100.degree.
- the amount of stripping gas is, for example, 5-20, particularly preferably 10-20 and very particularly preferably 10 to 15 m 3 / m 3 h, based on the volume of the reaction mixture.
- the ester can be subjected to filtration j) at any stage of the work-up process, preferably after washing / neutralization and, if appropriate, solvent removal, in order to remove traces of salts and any decolorizing agent present.
- the esterification a) of alkoxylated glycerol with the (methacrylic) acid is carried out in a molar excess of at least 15: 1 as mentioned above in the presence of at least one esterification catalyst C and at least one polymerization inhibitor D without a solvent which forms an azeotrope with water ,
- the (methacrylic) acid used in excess is essentially not separated off, ie only the proportion of (methacrylic) acid which is determined by the volatility at the temperature applied is removed from the reaction mixture, and moreover no measures to separate the carboxylic acid have been carried out, such as, for example, distillative, rectificative, extractive, such as, for example, washing, absorptive, such as, for example, passing over activated carbon or via ion exchanger, and / or chemical steps, such as, for example, trapping the carboxylic acid with epoxides.
- the (methacrylic) acid contained in the reaction mixture is preferably not more than 75% by weight, particularly preferably not more than 50% by weight, very particularly preferably
- step b) Adds not more than 25% by weight, in particular not more than 10% by weight and specifically not more than 5% by weight, separated off from the reaction mixture, based on the (methacrylic) acid present in the reaction mixture after the end of the reaction.
- step b) can be dispensed with, so that only the proportion of water of reaction and (methacrylic) acid which is determined by the volatility at the temperature applied is removed from the reaction mixture. This can preferably be prevented by essentially complete condensation.
- esterification catalyst C used essentially remains in the reaction mixture.
- the reaction mixture obtainable in this way preferably has an acid number in accordance with. DIN EN 3682 from at least 25 mg KOH / g reaction mixture, particularly preferably from 25 to 80 and very particularly preferably from 25 to 50 mg KOH / g.
- Prewashing or postwashing e) or g) is preferably dispensed with, only a filtration step j) can be useful.
- the reaction mixture can then be diluted in step c), in which case it is preferably converted to the hydrogel within 6 hours, particularly preferably within 3 hours. It can preferably be neutralized in a step f).
- the sequence of steps c), j) and f) is arbitrary.
- the invention also relates to a mixture of substances
- ester F obtainable by one of the esterification processes described above, (methacrylic) acid and diluent G.
- the mixture of substances can optionally be neutralized and have a pH, as listed under f) above.
- Ester F in the substance mixture 0.1 to 40% by weight, particularly preferably 0.5 to 20, very particularly preferably 1 to 10, in particular 2 to 5 and especially 2 to 4
- Monomer M 0.5-99.9% by weight, particularly preferably 0.5-50% by weight, very particularly preferably 1-25, in particular 2-15 and especially 3 to 5% by weight,
- Esterification catalyst C 0-10% by weight, particularly preferably 0.02-5%, very particularly preferably 0.05-2.5% by weight and in particular 0.1-1% by weight, polymerization inhibitor D 0-5% by weight, particularly preferably 0, 01-1.0, very particularly preferably 0.02-0.75, in particular 0.05-0.5 and especially 0.075-0.25% by weight,
- Solvent E 0-10% by weight, particularly preferably 0-5% by weight, very particularly preferably 0.05-1.5% by weight and in particular 0.1-0.5% by weight, with the proviso that the total is always 100% by weight %, and optionally diluent G ad 100% by weight.
- the reaction mixtures and substance mixtures according to the invention obtainable by the above process can be used
- those mixtures of the invention are particularly suitable which have a water solubility (at 25 ° C. in distilled water) of at least 5% by weight, preferably at least 10% by weight, particularly preferably at least 20% by weight, very particularly preferably at least 30 % By weight and in particular of at least 50% by weight.
- reaction mixture from the esterification including its work-up steps, as far as they are carried out, for example the reaction mixture from f), or, if f) is omitted, from b), or, if b) is dispensed with, the reaction mixture from a ), can optionally be mixed with additional monoethylenically unsaturated compounds N which do not carry any acid groups, but can be copolymerized with the hydrophilic monomers M, then can be polymerized in the presence of at least one radical initiator K and optionally at least one graft base L to prepare water-absorbing hydrogels ,
- Hydrophilic monomers M suitable for producing k) these hydrophilic, highly swellable hydrogels are, for example, polymerizable acids, such as acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, vinylsulfonic acid, vinylphosphonic acid, maleic acid including their anhydride, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, allylsulfonic acid, sulfoethyl acrylate, Sulfomethacrylat, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-acryloxy propyl sulfonic acid, 2-hydroxy-3-methacryl-oxypropylsulfonkla, allylphosphonic acid, styrenesulfonic acid, 2-acrylamido 2methylpropansul
- R 3 is hydrogen, methyl or ethyl
- R 4 is the group -COOR 6 , a sulfonyl group or phosphonyl group, a phosphonyl group esterified with a (CrC- -alkyl alcohol) or a group of
- R 5 is hydrogen, methyl, ethyl or a carboxyl group
- R 6 is hydrogen, amino or hydroxy- (CC 4 ) -alkyl
- R 7 represents a sulfonyl group, a phosphonyl group or a carboxyl group.
- Examples of (CC 4 ) alkyl alcohol are methanol, ethanol, n-propanol or n-butanol.
- hydrophilic monomers are acrylic acid and methacrylic acid, especially acrylic acid.
- additional monoethylenically unsaturated compounds N which do not carry any acid groups but are copolymerizable with the monomers bearing acid groups.
- These include, for example, the amides and nitriles of monoethylenically unsaturated carboxylic acid, e.g. B. acrylamide, methacrylamide and N-vinylformamide, N-vinyl acetamide, N-methyl-vinyl acetamide, acrylonitrile and methacrylonitrile.
- suitable compounds are, for example, vinyl esters of saturated Cp to C carboxylic acids such as vinyl formate, vinyl acetate or vinyl propionate, alkyl vinyl ether with at least 2 C atoms in the alkyl group, such as, for example, B. ethyl vinyl ether or butyl vinyl ether, esters of monoethylenically unsaturated C 3 - to C 6 -carboxylic acids, for. B. esters of monohydric C 1 -C 8 alcohols and acrylic acid, methacrylic acid or maleic acid, half esters of maleic acid, z. B.
- vinyl esters of saturated Cp to C carboxylic acids such as vinyl formate, vinyl acetate or vinyl propionate
- alkyl vinyl ether with at least 2 C atoms in the alkyl group such as, for example, B. ethyl vinyl ether or butyl vinyl ether, esters of monoethylenically unsaturated C 3 - to C 6 -carbox
- N-vinyl lactams such as N-vinyl pyrrolidone or N-vinyl caprolactam
- acrylic acid and methacrylic acid esters of alkoxylated monohydric, saturated alcohols for. B. of alcohols with 10 to 25 carbon atoms which have been reacted with 2 to 200 moles of ethylene oxide and / or propylene oxide per mole of alcohol
- monoacrylic acid esters and monomethacrylic acid esters of polyethylene glycol or polypropylene glycol, the molar masses (M n ) the polyalkylene glycols can be, for example, up to 2000.
- Other suitable monomers are styrene and alkyl-substituted styrenes such as ethylstyrene or tert-butylstyrene.
- These monomers not carrying acid groups can also be used in a mixture with other monomers, e.g. B. Mixtures of vinyl acetate and 2-hydroxyethyl acrylate in any ratio. These monomers not carrying acid groups are added to the reaction mixture in amounts between 0 and 50% by weight, preferably less than 20% by weight.
- the crosslinked (co) polymers preferably consist of monoethylenically unsaturated monomers bearing acid groups, which may or may not be converted into their alkali metal or ammonium salts before or after the polymerization, and from 0-40% by weight, based on their total weight, of no monoethylenically unsaturated monomers bearing acid groups.
- Preferred hydrogels are those obtained by crosslinking polymerization or copolymerization of acid-bearing monoethylenically unsaturated monomers M or their salts.
- the available polymers are characterized by an improved saponification index (VSI).
- the starting polymer is treated with a postcrosslinker and preferably postcrosslinked and dried during or after the treatment by increasing the temperature, the crosslinker preferably being contained in an inert solvent.
- Inert solvents are understood to mean those which, during the reaction, do not essentially react either with the starting polymer or with the postcrosslinker.
- Preferred solvents are those which contain more than 90%, preferably increases more than 95%, particularly preferably more than 99%, in particular more than
- Preferred for post-crosslinking I) and drying m) is the temperature range between 30 and 250 ° C., in particular 50-200 ° C., the range between 100-180 ° C. is very particularly preferred.
- the surface post-crosslinking solution is preferably applied by spraying onto the polymer in suitable spray mixers. Following the spraying, the polymer powder is thermally dried, and the crosslinking reaction can take place both before and during the drying. It is preferred to spray on a solution of the crosslinking agent in reaction mixers or mixing and drying systems such as Lödige mixers, BEPEX mixers, NAUTA mixers, SHUGGI mixers or PROCESSALL. Fluidized bed dryers can also be used.
- Drying can take place in the mixer itself, by heating the jacket or by blowing in warm air.
- a downstream dryer such as e.g. a rack dryer, a rotary kiln, or a heated screw. But it can also e.g. an azeotropic distillation can be used as the drying process.
- the preferred residence time at this temperature in the reaction mixer or dryer is less than 60 min, particularly preferably less than 30 min.
- the starting polymer being a polymeric acrylic acid or a polyacrylate, in particular a polymeric acrylic acid or a polyacrylate, which were obtained via free-radical polymerization and in which a polyfunctional ethylenically unsaturated radical crosslinker was used.
- Such processes are preferred in which the substance mixture containing radical crosslinking agent, ie the ester F, and diluent G in a ratio of 0.1-20% by weight, in particular 0.5-10% by weight, based on the mass of the Starting professors is used.
- radical crosslinker is used in a dosage of 0.01-5.0% by weight, preferably 0.02-3.0% by weight, very particularly preferably 0.03-2.5% by weight. in particular 0.05-1.0 and especially 0.1-0.75% by weight, based on the starting polymer, is used.
- the invention also relates to polymers produced by one of the abovementioned processes and their use in hygiene articles, packaging materials and in nonwovens, and the use of an abovementioned mixture of substances for the production of crosslinked or crosslinkable polymers by heat treatment, in particular in paints and varnishes.
- hydrophilic, highly swellable hydrogels (starting polymers) to be used are, in particular, polymers of (co) polymerized hydrophilic monomers M, graft (co) polymers of one or more hydrophilic monomers M on a suitable graft base L, crosslinked cellulose or starch ethers or in aqueous Liquid-swellable natural products, such as guar derivatives.
- These hydrogels are known to the person skilled in the art and are described, for example, in US Pat. No.
- Particularly suitable are also highly swellable hydrogels a fabrication process like / described in WO 01 38402- r and inorganic-organic hybrid highly swellable hydrogels as described in DE 198 54 575 off.
- the content of the aforementioned patent documents, in particular the hydrogels produced by the processes, are expressly part of the present disclosure.
- Suitable graft bases L for hydrophilic hydrogels which can be obtained by graft copolymerization of olefinically unsaturated acids, can be of natural or synthetic origin. Examples are starch, cellulose or cellulose derivatives and other polysaccharides and oligosaccharides, polyalkylene oxides, in particular polyethylene oxides and polypropylene oxides, and hydrophilic polyesters.
- the water-absorbing polymer can be obtained by radical graft copolymerization of acrylic acid or acrylate onto a water-soluble polymer matrix.
- Suitable water-soluble polymer matrices are, for example, but not exclusively, alginates, polyvinyl alcohol and polysaccharides such as starch.
- a polyfunctional ethylenically unsaturated radical crosslinker is used in the graft copolymerization according to the invention.
- the water-absorbing polymer can be an organic-inorganic hybrid polymer composed of a polymeric acrylic acid or a polyacrylate on the one hand and a silicate, aluminate or aluminosilicate on the other hand.
- polymeric acrylic acid or polyacrylate can be used, which is obtained via radical polymerization. and in which a multifunctional ethylenically unsaturated radical crosslinker was used and in the production process of which a water-soluble silicate or soluble aluminate or mixtures of the two was used.
- Preferred hydrogels are, in particular, polyacrylates, polymethacrylates and the graft polymers described in US Pat. No. 4,931,497, US Pat. No. 5,011,892 and US Pat. No. 5,041,496.
- Very particularly preferred hydrogels are the kneading polymers described in WO 01/38402 and the hybrid organic-inorganic hydrogels based on polyacrylates described in DE 19854575.
- the substances prepared according to the invention and usable as free-radical crosslinkers in hydrogels can be used alone or in combination with other crosslinking agents, for example internal or surface crosslinking agents, for example the following:
- Suitable additional crosslinkers are in particular methylene bisacrylic or
- esters of unsaturated mono- or polycarboxylic acids of polyols such as diacrylate or triacrylate, e.g. B. butanediol or ethylene glycol diacrylate or methacrylate and trimethylolpropane triacrylate and allyl compounds such as allyl (meth) acrylate, triallyl cyanurate, maleic acid diallyl ester, polyallyl ester, tetraallyloxyethane, triallyl amine, tetraallyl ethylenediamine, allyl vinyl ester, such as phosphoric acid such as phosphorus acid, such as phosphorus acid, A-0343427.
- polyols such as diacrylate or triacrylate, e.g. B. butanediol or ethylene glycol diacrylate or methacrylate and trimethylolpropane triacrylate
- allyl compounds such as allyl (meth) acrylate, triallyl cyanurate, male
- hydrogels which are prepared using polyallyl ethers as additional crosslinking agents and by acidic homopolymerization of acrylic acid are particularly preferred in the process according to the invention.
- Suitable crosslinkers are pentaerythritol tri- and tetraallyl ether, polyethylene glycol diallyl ether, monoethylene glycol diallyl ether, glycerol di and triallyl ether, polyallyl ether based on sorbitol, and ethoxylated variants thereof.
- Further particularly preferred crosslinkers are the polyethylene glycol diacrylates, ethoxylated derivatives of trimethylolpropane triacrylate e.g. Sartomer SR 9035, as well as ethoxylated derivatives of glycerol diacrylate and glycerol triacrylate. Mixtures of the above crosslinking agents can of course also be used.
- Hydrogels which are prepared as radical crosslinkers with an ester F prepared according to the invention are very particularly preferred.
- the water-absorbing polymer is preferably a polymeric acrylic acid or a polyacrylate.
- This water-absorbing polymer can be prepared by a process known from the literature. Polymers which contain crosslinking comonomers are preferred (0.001-10 mol%), but polymers which have been obtained by free-radical polymerization and are particularly preferred which a multifunctional ethylenically unsaturated radical crosslinker was used.
- the hydrophilic, highly swellable hydrogels can be produced by known polymerization processes. Polymerization in aqueous solution by the so-called gel polymerization method is preferred. As mentioned above, dilute, preferably aqueous, particularly preferably 15 to 50% by weight aqueous solutions of one or more hydrophilic monomers and, if appropriate, a suitable graft base L in the presence of a radical initiator are preferably used without mechanical mixing using the Trommsdorff.
- the polymerization reaction can be carried out in the temperature range between 0 ° C. and 150 ° C., preferably between 10 ° C. and 100 ° C., both under normal pressure and under elevated or reduced pressure.
- the polymerization can also be carried out in a protective gas atmosphere, preferably under nitrogen.
- high-energy electromagnetic radiation or the usual chemical polymerization initiators K can be used, e.g. B.
- organic peroxides such as benzoyl peroxide, tert-butyl hydroperoxide, methyl ethyl ketone peroxide, gumol hydroperoxide, azo compounds such as azodiisobutyronitrile and inorganic peroxy compounds such as (NH 4 ) 2 S 2 ⁇ 8, K 2 S 2 O 8 or H 2 O 2 .
- reducing agents such as e.g. Ascorbic acid, sodium hydrogen sulfite, and iron (II) sulfate or redox systems which contain an aliphatic and aromatic sulfinic acid, such as benzenesulfinic acid and toluenesulfinic acid or derivatives of these acids, such as, for example, as a reducing component.
- reducing agents such as e.g. Ascorbic acid, sodium hydrogen sulfite, and iron (II) sulfate or redox systems which contain an aliphatic and aromatic sulfinic acid, such as benzenesulfinic acid and toluenesulfinic acid or derivatives of these acids, such as, for example, as a reducing component.
- B. Mannich adducts of sulfinic acids, aldehydes and amino compounds, as described in DE-C-1 301 566, can be used.
- the gels obtained are neutralized to 0-100 mol%, preferably to 25-100 mol%, and particularly preferably to 50-85 mol%, based on the monomer used, it being possible to use the customary neutralizing agents, preferably alkali metal hydroxides, Alkali metal oxides or the corresponding alkali metal carbonates, but particularly preferably sodium hydroxide, sodium carbonate and sodium hydrogen carbonate.
- the customary neutralizing agents preferably alkali metal hydroxides, Alkali metal oxides or the corresponding alkali metal carbonates, but particularly preferably sodium hydroxide, sodium carbonate and sodium hydrogen carbonate.
- the neutralization is usually achieved by mixing in the neutralizing agent as an aqueous solution or preferably also as a solid.
- the gel is mechanically comminuted, for example using a meat grinder, and the neutralizing agent is sprayed on, sprinkled on or poured on, and then carefully mixed in.
- the gel mass obtained can be minced several times for homogenization.
- the neutralized gel mass is then dried with a belt or roller dryer until the residual moisture content is preferably below 10% by weight, in particular below 5% by weight.
- the polymerization itself can also be carried out by any of the other methods described in the literature.
- the neutralization of the acrylic acid can also be carried out before the polymerization, as described in step f) above.
- the polymerization can then be carried out continuously or batchwise in a belt reactor known to the person skilled in the art or in a kneading reactor.
- initiation by means of electromagnetic radiation preferably by means of UV radiation, or alternatively initiation using a redox initiator system is particularly preferred.
- the combination of both initiation methods is also very particularly preferred: electromagnetic radiation and chemical redox initiator system simultaneously.
- the dried hydrogel can then be ground and sieved, - roller mills, pin mills or vibrating mills can usually be used for grinding.
- the preferred particle size of the sieved hydrogel is preferably in the range 45-1000 ⁇ m, preferably 45-850 ⁇ m, particularly preferably 200-850 ⁇ m, and very particularly preferably 300-850 ⁇ m.
- Another particularly preferred range is 150-850 ⁇ m, very particularly preferably 150-700 ⁇ m.
- These areas preferably contain 80% by weight of the particles, in particular 90% by weight of the particles.
- the size distribution can be determined using established laser methods.
- the present invention furthermore relates to crosslinked hydrogels which contain at least one hydrophilic monomer M in copolymerized form and are crosslinked with an ester F of alkoxylated glycerol with (methacrylic) acid.
- the ester can be prepared according to the invention or in a manner known in the art, preferably in a manner according to the invention.
- esters F Compounds as described above can be used as esters F.
- the CRC value [g / g] of the hydrogel-forming polymers according to the invention can be measured by the methods given in the description and is preferably greater than 15, in particular 16, 18, 20, 22, 24 or higher, particularly preferably 25 in particular at 26, 27, 28, 29, particularly preferably at 30, 31, 32, 33, 34, 35, 36, 37 or higher.
- the AUL 0.7 psi value [g / g] of the hydrogel-forming polymers according to the invention can be measured by the methods given in the description and is preferably greater than 8, in particular 9, 10, 11, 12, 13, 14 or higher, particularly preferably at 15, in particular at 16, 17, 18, 19 or higher, particularly preferably greater than 20, in particular 21, 22, 23, 24, 25, 26, 27, 28 or higher.
- the AUL-0.5psi value [g / g] of the hydrogel-forming polymers according to the invention can be measured by the methods given in the description and is preferably greater than 8, in particular 9, 10, 11, 12, 13, 14 or higher, particularly preferably at 15, in particular at 16, 17, 18, 19 or higher, particularly preferably greater than 20, in particular 21, 22, 23, 24, 25, 26, 27, 28 or higher.
- the saponification index VSI of the hydrogel-forming polymers according to the invention can be measured using the methods given in the description and is preferably less than 11, 10.5 or 10, in particular 9.5, 9 or 8.5 or less, particularly preferably less than 8, in particular 7.5, 7, 6.5 , 6, 5.5 or less, particularly preferably less than 5, in particular 4.5, -4, -3: 5 or less.
- the residual crosslinker content of the hydrogel-forming polymers according to the invention can be measured by the methods given in the description and is preferably less than 10 ppm, in particular 9.5 ppm, 9 ppm, or 8.5 ppm or less, particularly preferably less than 8 ppm, in particular 7.5 ppm, 7 ppm , 6.5 ppm, 6 ppm, 5.5 ppm or less, particularly preferably less than 5 ppm, in particular 4.5 ppm, 4 ppm, 3.5 ppm or less.
- the present invention further relates to the use of the above-mentioned hydrogel-forming polymers in hygiene articles, comprising
- hydrophilic fiber material preferably 20 to 100% by weight of the hydrogel-forming polymer according to the invention
- hydrophilic fiber material more preferably 30-100% by weight of the hydrogel-forming polymer according to the invention, 0-70% by weight hydrophilic fiber material even more preferably 40-100% by weight of the hydrogel-forming polymer according to the invention, 0-60% by weight of hydrophilic fiber material, more preferably 50-100% by weight of the hydrogel-forming polymer according to the invention 0-50% by weight of hydrophilic Fiber material particularly preferably 60-100% by weight of the hydrogel-forming polymer according to the invention, 0-40% by weight of hydrophilic fiber material, particularly preferably 70-100% by weight of the hydrogel-forming polymer according to the invention, 0-30% by weight of hydrophilic Fiber material extremely preferred 80-100% by weight of the hydrogel-forming polymer according to the invention, 0-20% by weight of hydrophilic fiber material most preferably 90-100% by weight of the hydrogel-forming polymer according to the invention, 0-10% by weight hydrophilic fiber material
- (S) optionally a tissue layer located immediately above and below the core (R) and (T) optionally a receiving layer located between (P) and (R).
- the percentages are to be understood such that at 10-100% by weight, 11, 12, 13, 14, 15, 16, -17, 18, -1-9 to -100% by weight of hydrogel-forming agents according to the invention Polymer and all intermediate percentages (e.g. 12.2%) are possible and correspondingly hydrophilic fiber material from 0 to 89, 88, 87, 86, 85, 83, 82, 81
- % By weight and percentages in between (for example 87.8%) are possible. If there are other materials in the core, the percentages of polymer and fiber decrease accordingly.
- the analog applies to the preferred ranges, for example 81, 82, 83, 84, 85, 86, 87, 88, 89% by weight can be used for the hydrogel-forming polymer according to the invention and correspondingly 19, 18, 17 , 16, 15, 14, 13, 12, 11% by weight of the fiber material are present. In the preferred range, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 to 100% by weight can be used.
- hydrogel-forming polymer according to the invention in the more preferred range 30, 31, 32, 33, 34, 35, 36, 37, 38, 39 to 100% by weight hydrogel-forming polymer according to the invention, in the even more preferred range 40, 41, 42, 43, 44, 45, 46, 47, 48, 49 to 100% by weight of hydrogel-forming polymer according to the invention, in the more preferred range 50, 51, 52, 53, 54, 55, 56, 57, 58 , 59 to 100% by weight of hydrogel-forming polymer according to the invention, in the particularly preferred range 60, 61, 62, 63, 64, 65, 66, 67, 68, 69 to 100% by weight of hydrogel-forming polymer according to the invention, in particularly preferred range 70, 71, 71, 72, 73, 74, 75, 76, 77, 78, 79 to 100% by weight of hydrogel-forming polymer according to the invention and in the most preferred range 90, 91, 92, 93 , 94, 95, 96,
- the liquid-permeable cover (P) is the layer that has direct skin contact.
- the material for this consists of conventional synthetic or semi-synthetic fibers or films of polyester, polyolefins, rayon or natural fibers such as cotton. In the case of non-woven materials, the fibers are generally to be connected using binders such as polyacrylates. Preferred materials are polyester, rayon and their blends, polyethylene and polypropylene. Examples of liquid-permeable layers are described in WO 99/57355 A1, EP 102 388 3 A2.
- the liquid-impermeable layer (Q) usually consists of a film made of polyethylene or polypropylene.
- the core (R) contains hydrophilic fiber material.
- Hydrophilic is understood to mean that aqueous liquids are rapidly distributed over the fiber.
- the fiber material is usually cellulose, modified cellulose, rayon, polyester such as polyethylene terephthalate. Cellulose fibers such as cellulose are particularly preferred.
- the fibers usually have one
- the fibers have a minimum length of 1 mm.
- diapers The structure and shape of diapers is generally known and is described, for example, in WO 95/26 209 p. 66 line 34 to p. 69 line 11, DE 196 04 601 A1, EP-A-0 316 518 and EP-A-0 202 127.
- diapers and other hygiene articles are also described in WO 00/65084, in particular on pages 6-15, WO 00/65348, in particular on pages 4 - 17, WO 00/35502, in particular pages 3-9, DE 19737434, WO 98/8439 described.
- Hygiene articles for feminine hygiene are described in the following references.
- the hydrogel-forming polymers absorbing aqueous liquids according to the invention can be used there.
- Tampons are described in the following documents: 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, WO 2001/001908, WO 2001/001909, WO 2001/001906, WO 2001/001905, WO 2001/24729.
- Incontinence articles are described in the following documents: Disposable Absorbent Article for Incontinent Individuais: EP 311344 Description pp.
- Disposable absorbent Article EP 850623; Absorbent Article: WO 95/26207; Absorbent Article: EP 894502; Dry Laid Fibrous Structure: EP 850 616; 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 hygiene and incontinence articles are described in the following documents: Catamenial Device: WO 93/22998 Description p.26-33; Absorbent Members for Body Fluids: WO 95/26209 description pp.
- hydrogel-forming polymers according to the invention are outstandingly suitable as absorbents for water and aqueous liquids, so that they are advantageously used as water-retaining agents in agricultural horticulture, as filtration aids and especially as absorbent components in hygiene articles such as diapers, tampons or sanitary napkins can.
- the absorbent composition according to the present invention contains compositions which contain the highly swellable hydrogels or to which they are fixed. Any composition is suitable which can absorb the highly swellable hydrogels and which can also be integrated into the absorption layer. A large number of such compositions are already known and have been described in detail in the literature.
- a composition for incorporating the highly swellable hydrogels can e.g. B. be a fiber matrix, which consists of a cellulose fiber mixture (airlaid web, wet laid web) or synthetic polymer fibers (meltblown web, spunbonded web), or consists of a mixed fiber structure made of cellulose fibers and synthetic fibers. Possible fiber materials are described in detail in the following chapter. The process of an air-laid web is described, for example, in WO 98/28478. Furthermore, open-pore foams or the like can be used for the installation of highly swellable hydrogels.
- such a composition can be created by fusing two individual layers, one or better a plurality of chambers being formed which form the contain highly swellable hydrogels.
- a chamber system is described in detail in EP 0 615736 A1 p. 7 line 26 ff.
- the two layers should be permeable to water.
- the second layer can be either water permeable or water impermeable.
- Tissues or other fabrics, closed or open-cell foams, perforated films, elastomers or fabrics made of fiber material can be used as layer material.
- the absorbent composition consists of a composition of layers, the layer material should have a pore structure whose pore dimensions are small enough to retain the highly swellable hydrogel particles.
- the above examples for the composition of the absorbent composition also include laminates of at least two layers, between which the highly swellable hydrogels are installed and fixed.
- Dry and wet integrity means the ability to incorporate highly swellable hydrogels into the absorbent composition in this way; that they can withstand external forces, both wet and dry, and that there is no displacement or leakage of highly swellable polymer.
- the effects of force are to be understood above all as mechanical loads, such as those that occur in the course of movement when the hygiene article is worn, or the weight load under which the hygiene article is primarily exposed to incontinence.
- the absorbent composition can consist of a carrier material, such as. B. consist of a polymer film on which the highly swellable hydrogel particles are fixed. The fixation can be done on one or both sides.
- the carrier material can be water-permeable or water-impermeable.
- the highly swellable hydrogels are used in a weight fraction of 10 to 100% by weight, preferably 20-100% by weight, more preferably 30-100% by weight, even more preferably 40-100% by weight, more preferably 50-100% by weight, particularly preferably 60-100% by weight, particularly preferably 70-100% by weight, extremely preferably 80-100% by weight and most preferably 90-100% by weight based on the total weight of the composition and the highly swellable hydrogels incorporated.
- the structure of the present absorbent composition according to the invention is based on a variety of fiber materials which are used as fiber networks or matrices. Included in the present invention are both fibers of natural origin (modified or unmodified) and synthetic fibers. .
- Patent WO 95/26209 p. 28 line 9 to p. 36 line 8 gives a detailed overview of examples of fibers which can be used in the present invention. Said passage is therefore part of this invention.
- cellulosic fibers include those commonly used in absorption products such as fleece pulp and cotton type pulp.
- the materials softwood or hardwood
- manufacturing processes such as chemical pulp, semi-chemical pulp, chemothermal mechanical pulp (CTMP) and bleaching processes are not particularly restricted.
- CMP chemothermal mechanical pulp
- natural cellulose fibers such as cotton, flax, silk, wool, jute, ethyl cellulose and cellulose acetate are used.
- Suitable synthetic fibers are made from polyvinyl chloride, polyvinyl fluoride, polytetrafluoroethylene, polyvinylidene chloride, polyacrylics such as ORLON ®, polyvinyl acetate, polyethylvinyl acetate, polyvinyl alcohol soluble or insoluble.
- thermoplastic polyolefin fibers such as polyethylene fibers (PULPEX ® ), polypropylene fibers and polyethylene-polypropylene two-component fibers, polyester fibers such as polyethylene terephthalate fibers (DAC-RON ® or KODEL ® ), copolyesters, polyvinyl acetate, polyethyl vinyl chloride, polyvinyl chloride, polyvinyl chloride , Polyacrylics, polyamides, copolyamides, polystyrene and copolymers of the abovementioned polymers, and also two-component fibers made of polyethylene terephthalate-polyethylene-isophthalate copolymer, polyvinyl vinyl acetate, polypropylene, polyethylene / polyester, polypropylene / polyester, copolyester / polyester, polyamide fibers (Nylon), polyurethane fibers, polystyrene fibers and polyacrylonitrile fibers.
- Polyolefin fibers, polyester fibers and their two-component fibers are preferred. Also preferred are thermally adhesive two-component fibers made of polyolefin of the shell-core type and side-by-side type because of their excellent dimensional stability after the liquid absorption.
- the synthetic fibers mentioned are preferably used in combination with thermoplastic fibers. During heat treatment, the latter partially migrate into the matrix of the existing fiber material and thus represent connection points and renewed stiffening elements when cooling.
- thermoplastic fibers means an extension of the present one
- thermoplastic fibers can be formed from a large number of thermoplastic polymers which have a melting point of less than 190 ° C., preferably between 75 ° C. and 175 ° C. At these temperatures, no damage to the cellulose fibers is yet to be expected.
- the lengths and diameters of the synthetic fibers described above are not particularly limited, and in general, any fiber with a length of 1 to 200 mm and a diameter of 0.1 to 100 denier (grams per 9,000 meters) can be preferably used.
- Preferred thermoplastic fibers have a length of 3 to 50 mm, particularly preferred a length of 6 to 12 mm.
- the preferred diameter of the thermoplastic fiber is between 1, 4 and 10
- Decitex particularly preferably between 1.7 and 3.3 Decitex (grams per 10000 meters).
- the shape is not particularly limited, and examples include fabric-like, narrow cylinder-like, cut / split gauze-like, staple fiber-like and continuous fiber-like.
- the fibers in the absorbent composition of the invention can be hydrophilic, hydrophobic, or a combination of both.
- a fiber is said to be hydrophilic if the contact angle between the liquid and the fiber (or its surface) is less than 90 9 , or when the liquid tends to spontaneously spread on the same surface. As a rule, both processes are coexistent.
- a fiber is said to be hydrophobic if a contact angle of greater than 90 ° is formed and no spreading is observed.
- Hydrophilic fiber material is preferably used. It is particularly preferred to use fiber material that is weakly hydrophilic on the body side and most hydrophilic in the region around the highly swellable hydrogels. In the manufacturing process, layers of different hydrophilicity are used A gradient is created that channels the impinging liquid to the hydrogel, where it is ultimately absorbed.
- Suitable hydrophilic fibers for use in the absorbent composition according to the invention are, for example, cellulose fibers, modified cellulose fibers, rayon, polyester fibers such as, for. B. polyethylene terephthalate (DACRON ® ), and hydrophilic nylon (HYDROFIL ® ).
- Suitable hydrophilic fibers can also be obtained by hydrophilizing hydrophobic fibers, such as treating thermoplastic fibers obtained from polyolefins (such as polyethylene or polypropylene, polyamides, polystyrenes, polyurethanes, etc.) with surfactants or silica.
- polyolefins such as polyethylene or polypropylene, polyamides, polystyrenes, polyurethanes, etc.
- surfactants or silica are preferred for reasons of cost and availability.
- the highly swellable hydrogel particles are embedded in the fiber material described. This can be done in a variety of ways, e.g. B. builds up an absorption layer in the form of a matrix with the hydrogel material and the fibers, or by embedding highly swellable hydrogels in layers of fiber mixture, where they are ultimately fixed, whether by adhesive or lamination of the layers.
- the liquid-absorbing and distributing fiber matrix can consist of synthetic fiber or cellulose fiber or a mixture of synthetic fiber and cellulose fiber, the mixing ratio of (100 to 0) synthetic fiber: (0 to 100) cellulose fiber being able to vary.
- the cellulose fibers used can additionally be chemically stiffened to increase the dimensional stability of the hygiene article.
- fiber stiffening can be achieved in different ways.
- fiber stiffening can be achieved by adding suitable coatings to the fiber material. Include such additions examples play as polyamide-epichlorohydrin coatings (Kymene ® 557H, Hercoles, Inc. Wil- Remington Delaware, USA), polyacrylamide coatings (described in US Patent No. 3,556,932 or as a product of Parez ® 631 NC trademark, American Cyanamid Co., Stamford, CT, USA), melamine-formaldehyde coatings and polyethyleneimine coatings.
- Suitable crosslinking substances are typical substances that are used to crosslink monomers. Included, but not limited to, are C 2 -C 8 dialdehydes, C 2 -C 8 monoalde- hyde with acid functionality, and especially C 2 -C 9 polycarboxylic acids. Specific substances from this series are, for example, glutaraldehyde, glyoxal, glyoxylic acid, formaldehyde and citric acid.
- Chemically crosslinked cellulose fibers are known and are described in WO 91/11162, U.S. Patent 3,224,926, U.S. Patent 3,440,135, U.S. U.S. Patent 3,932,209 Patent 4,035,147, U.S. U.S. Patent 4,822,453, U.S. U.S. Patent 4,888,093, U.S. U.S. Patent 4,898,642 and U.S. Patent 5,137,537.
- the chemical crosslinking stiffens the fiber material, which is ultimately reflected in the improved dimensional stability of the entire hygiene article.
- the individual layers are by methods known to those skilled in the art, such as. B. fused together by heat treatment, adding hot melt adhesives, latex binders, etc.
- the absorbent composition is composed of compositions which contain highly swellable hydrogels and the highly swellable hydrogels which are present in the compositions or are fixed thereto.
- Examples of processes with which an absorbent composition is obtained which consists, for example, of highly swellable hydrogels (c) embedded in a fiber material mixture of synthetic fibers (a) and cellulose fibers (b), the mixing ratio of (100 to 0) synthetic fibers : (0 to 100) cellulose fiber may vary include (1) a process in which (a), (b) and (c) are mixed simultaneously, (2) a process in which a mixture of (a) and ( b) is mixed into (c), (3) a process in which a mixture of (b) and (c) is mixed with (a), (4) a process in which a mixture of (a) and ( c) is mixed into (b), (5) a process in which (b) and (c) are mixed and (a) is metered in continuously, (6) a process in which (a) and (c) are mixed and (b) is metered in continuously, and (7) a method in which (b) and (c) are mixed separately into (a).
- methods (1) and (5) are preferred.
- the correspondingly produced absorbent composition can optionally be subjected to a heat treatment, so that an absorption layer with excellent dimensional stability in the moist state results.
- the heat treatment process is not particularly limited. Examples include heat treatment by supplying hot air or infrared radiation.
- the temperature during the heat treatment is in the range from 60 ° C. to 230 ° C., preferably between 100 ° C. and 200 ° C., particularly preferably between 100 ° C. and 180 ° C.
- the duration of the heat treatment depends on the type of synthetic fiber, its quantity and the speed at which the hygiene article is manufactured. Generally, the duration of the heat treatment is between 0.5 seconds to 3 minutes, preferably 1 second to 1 minute.
- the absorbent composition is generally provided, for example, with a liquid pervious top layer and a liquid impervious bottom layer. Leg cuffs and adhesive tapes are also attached, thus completing the hygiene article.
- the materials and types of the permeable top layer and impermeable bottom layer, as well as the leg ends and adhesive tapes are known to the person skilled in the art and are not particularly restricted. Examples of this can be found in WO 95/26209.
- esters F which can be used as crosslinkers do not have to be purified after their preparation, in particular that the (meth) acrylic acid, preferably acrylic acid, does not have to be separated off, since these are generally a monomer for the preparation which represents hydrogels.
- the superabsorbent crosslinkers are prepared by esterifying alkoxylated glycerol with acrylic acid, the water being separated off in an azeotropic distillation.
- Esterification catalyst in the examples is sulfuric acid.
- the reactants are presented together with a stabilizer mixture consisting of hydroquinone monomethyl ether, triphenyl phosphite and hypophosphorous acid in the examples in methylcyclohexane as an entrainer.
- the reaction mixture is then heated to about 98 ° C until the azeotropic distillation begins. During the azeotropic distillation, the temperature in the reaction mixture rises. The amount of water separated off is determined. The distillation is stopped when at least the theoretical amount of water has been removed.
- the entrainer is then removed in a vacuum distillation.
- the product is cooled and used as a crosslinker in the production of superabsorbents.
- glycerol 77 g of glycerol are placed in an autoclave with 0.5 g of KOH, 45% in water and dewatered together at 80 ° C. and reduced pressure (approx. 20 mbar). Then 184 g of ethylene oxide are added at 145 to 155 ° C. and allowed to react at this temperature under increased pressure. The reaction is complete when no change in pressure is observed. The mixture is then stirred at about 150 ° C for 30 minutes. After purging with inert gas and cooling to 60 ° C., the catalyst is separated off by adding sodium pyrophosphate and subsequent filtration.
- 77 g of glycerol are placed in an autoclave with 0.5 g of KOH, 45% in water and dewatered together at 80 ° C. and reduced pressure (approx. 20 mbar). Then 146 g of propylene oxide are added at 120 to 130 ° C. and allowed to react at this temperature under increased pressure. The reaction is complete when no change in pressure is observed. The mixture is then stirred at 120 ° C. for a further 30 min. Subsequently, 74 g of ethylene oxide are metered in at 145 to 155 ° C. over a prolonged period at elevated pressure and are also allowed to react. After purging with inert gas and cooling to 60 ° C., the catalyst is separated off by adding sodium pyrophosphate and subsequent filtration.
- 77 g of glycerol are placed in an autoclave with 0.5 g of KOH, 45% in water 5 and dewatered together at 80 ° C. and reduced pressure (approx. 20 mbar). Then 74 g of ethylene oxide and 146 g of propylene oxide are added at 120 to 130 ° C. and the temperature is slowly increased to approximately 150 ° C. It is allowed to react under increased pressure. The reaction is complete when there is no more pressure change. is considered. The mixture is then stirred at about 150 ° C for 30 minutes. After purging with 0 inert gas and cooling to 60 ° C., the catalyst is separated off by adding sodium pyrophosphate and subsequent filtration.
- 77 g of trimethylolpropane are placed in an autoclave with 0.5 g of KOH, 45% in water and dewatered together at 80 ° C. and reduced pressure (approx. 20 mbar). Then 76 g of ethylene oxide are added at 145 to 155 ° C. and allowed to react at this temperature under increased pressure. The reaction is complete when no change in pressure is observed. The mixture is then stirred at about 150 ° C for 30 minutes. After purging with inert gas and cooling to 60 ° C., the catalyst is separated off by adding sodium pyrophosphate and subsequent filtration.
- 183 parts of approximately 3-fold ethoxylated glycerol are esterified with 216 parts of acrylic acid and 5 parts of sulfuric acid in 345 parts of methylcyclohexane.
- 3 parts of hydroquinone monomethyl ether, 1 part of triphenyl phosphite and 1 part of hypophosphorous acid are added as auxiliaries.
- 44 parts of water are separated off before the entrainer is removed by vacuum distillation.
- the product is cleaned using K300 filters.
- the acid number is determined.
- the viscosity is adjusted by adding 96 parts of acrylic acid.
- the viscosity of the almost colorless product is approx. 330 mPas.
- 255 parts of about 5-fold ethoxylated glycerol are esterified with 216 parts of acrylic acid and 5 parts of sulfuric acid in 345 parts of methylcyclohexane. -3 parts of hydroquinone monomethyl ether, 1 part of triphenyl phosphite and 1 part of hypophosphorous acid are added as auxiliaries. 44 parts of water are separated off before the entrainer is removed by vacuum distillation. The product is cleaned using K300 filters. The acid number is determined. The viscosity is adjusted by adding 96 parts of acrylic acid. The viscosity of the almost colorless product (iodine color number 0-1) is approx. 320 mPas.
- test methods To determine the quality of the surface crosslinking, the dried hydrogel can be examined using the following test methods. test methods
- This method determines the free swellability of the hydrogel in the tea bag.
- 0.2000 +/- 0.0050 g of dried hydrogel (grain fraction 106 - 850 ⁇ m) is weighed into a 60 x 85 mm tea bag, which is then sealed.
- the tea bag is placed in an excess of 0.9% by weight saline solution (at least 0.831 saline solution / 1 g polymer powder) for 30 minutes.
- the tea bag is then centrifuged at 250 g for 3 minutes. The amount of liquid is determined by weighing the centrifuged tea bag.
- the measuring cell for determining the AUL 0.7 psi is a plexiglass cylinder with an inner diameter of 60 mm and a height of 50 mm, which has a glued-on stainless steel sieve bottom with a mesh size of 36 ⁇ rrL on the underside furthermore a plastic plate with a diameter of 59 mm and a weight that can be placed together with the plastic plate in the measuring cell.
- the weight of the plastic plate and the total weight are 1345 g.
- the weight of the empty plexiglass cylinder and the plastic plate is determined and noted as W 0 .
- the absorption under pressure (AUL) is calculated as follows:
- the AUL 0.5psi is measured analogously with lower pressure.
- this residual crosslinker is first extracted from the dried hydrogel by means of a double extraction. For this, 0.400 g of dry hydrogel and 40 g of 0.9% by weight saline solution are weighed into a closable and centrifugable ampoule. To do this, add 8 ml dichloromethane, close the ampoule and then shake for 60 min. The ampoule is then immediately centrifuged at 1500 rpm for 5 minutes, so that the organic phase is clearly separated from the aqueous phase.
- the sample obtained in this way is separated by means of liquid phase chromatography and analyzed by mass spectrometry.
- the quantification is carried out against a dilution series of the same crosslinking agent used.
- a Zorbax Eclipse XDB C-8 (150 x 4.6 mm - 5 ⁇ m) is used as the chromatography column and a Zorbax Eclipse XDB C-8 (12.5 x 4.6 mm - 5 ⁇ m) as the precolumn.
- a methanol / water mixture (75/25) is used as the eluent.
- the gradient course is as follows:
- Flow is 1 ml / min at 1600 psi pressure.
- the injection volume is 20 ⁇ l.
- Typical analysis time is 14 minutes for the samples.
- the detection is done by mass spectrometry e.g. in the range 800 - 1300 m / z (fill scan, positive).
- the device works with APCI (Atmospheric Pressure Chemical Ionization, positive ionization).
- APCI atmospheric Pressure Chemical Ionization, positive ionization
- the capillary temperature is set to 180 ° C
- the APCI vaporizer temperature to 450 ° C
- source current to 5.0 ⁇ A
- the gas flow 80 ml / min.
- the individual settings must be made specifically for each networker.
- the characteristic peaks that are later relevant for the evaluation are determined using a suitable calibration solution of the crosslinking agent. As a rule, the main peak is selected.
- CONC Probe A Pr0 b e x CONCstd X VF / A : Std
- CONCp robe is the desired residual crosslinker concentration in the dry hydrogel in mg / kg
- CONCs td is the desired cross-linker concentration in the calibration solution in mg / kg
- Ap r obe is the peak area of the extract sample of the dried hydrogel
- VF is the dilution factor
- VF M DC M solv / (Mp r0 be XM E ⁇ tract)
- M DCM is a weight of dichloromethane for extraction
- M r o be is a sample of dry hydrogel
- M E ⁇ tract is a weight of dichloromethane extract
- the crushed gel is then processed in two different ways:
- the comminuted gel is homogeneously distributed in a thin layer on a sheet metal sieve tray and then dried in vacuo at 80 g C for 24 h. This drying is very gentle on the product and is therefore the optimal standard of comparison.
- the dried hydrogel is then milled and the 300-600 micron sieve fraction is isolated.
- the crushed gel is first annealed in a sealed plastic bag at 90 S C for 24 h. Then it is distributed homogeneously in a thin layer on sheets with sieve trays and dried in vacuo at 80 ° C. for 24 h. This drying simulates the drying conditions that occur in typical production plants, which usually limit the drying performance and throughput due to the associated decrease in quality.
- the dried hydrogel is ground and the sieve fraction of 300 - 600 micrometers is isolated.
- the hydrogels obtained by the two working-up methods are characterized by determining the teabag capacity (CRC) and the content of extractables after 16 h and in terms of the content of unreacted residual crosslinking agent.
- CRC teabag capacity
- the moisture content is determined and if this is over 1% by weight it is taken into account arithmetically when determining these properties.
- the moisture content is typically about 5% by weight.
- the saponification index (VSI) of the crosslinking agent in the gel is then determined from the measured values, which is calculated as follows:
- the subscripts here indicate the processing method 1 or 2.
- the saponification index is therefore greater, the more the teabag capacity increases due to the drying process and the more the extractables increase. Both contributions are weighted equally.
- crosslinkers whose saponification index is as small as possible.
- the ideal networker has a VSI of zero.
- the use of such crosslinkers makes it possible to increase the performance of the operational dryer without sacrificing quality up to the technically achievable maximum. The reason for this is that the wetting set during the polymerization - and thus the properties of the end product - no longer changes due to hydrolysis during drying.
- the crushed gel is then processed in two different ways:
- the crushed gel is homogeneously distributed in a thin layer on sheets with sieve trays and then dried in vacuo at 80 g C for 24 h. This drying is very gentle on the product and is therefore the optimal standard of comparison.
- the dried hydrogel is then milled and the 300-600 micron sieve fraction is isolated.
- the crushed gel is first annealed in a sealed plastic bag at 90 S C for 24 h. Then it is distributed homogeneously in a thin layer on sheets with sieve trays and dried in vacuo at 80 S C for 24 h. This drying simulates the drying conditions that occur in typical production plants, which usually limit the drying performance and throughput due to the associated drop in quality.
- the dried hydrogel is ground and the sieve fraction of 300 - 600 micrometers is isolated.
- the dry normal base polymer powder is mixed with a solution of 0.06% by weight of ethylene glycol diglycidyl ether (Nagase, Japan), 3.43% by weight of water and 1.47 Wt.%) Propanediol-1, 2, each based on polymer used, homogeneously sprayed with stirring.
- the moist powder is then heated in a drying cabinet at 150 ° C. for 60 min. Then sieve again at 850 micrometers to remove agglomerates. The properties of this post-crosslinked polymer are determined.
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Abstract
Description
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Priority Applications (18)
Application Number | Priority Date | Filing Date | Title |
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CA002487030A CA2487030A1 (en) | 2002-06-11 | 2003-06-10 | (meth)acrylic esters of polyalkoxylated glycerine |
JP2004511367A JP4373328B2 (ja) | 2002-06-11 | 2003-06-10 | ポリアルコキシル化されたグリセリンの(メタ)アクリルエステル |
CNB038136686A CN100349958C (zh) | 2002-06-11 | 2003-06-10 | 聚烷氧基化甘油的(甲基)丙烯酸酯 |
US10/516,702 US20050165208A1 (en) | 2002-06-11 | 2003-06-10 | (Meth)acrylic esters of polyalkoxylated glycerine |
MXPA04012180A MXPA04012180A (es) | 2002-06-11 | 2003-06-10 | Esteres (met) acrilicos de glicerina polialcoxilada. |
AU2003274698A AU2003274698A1 (en) | 2002-06-11 | 2003-06-10 | (meth)acrylic esters of polyalkoxylated glycerine |
DE50303213T DE50303213D1 (de) | 2002-06-11 | 2003-06-10 | (meth)acrylester von polyalkoxyliertem glycerin |
BR0311498-8A BR0311498A (pt) | 2002-06-11 | 2003-06-10 | éster f, processos para preparar o mesmo e um hidrogel reticulado, polìmero, hidrogel reticulado, uso de um polìmero, composição de matéria, e usos de uma mistura da reação, e de um éster f |
EP03740207A EP1517942B1 (de) | 2002-06-11 | 2003-06-10 | (meth)acrylester von polyalkoxyliertem glycerin |
DE10358372A DE10358372A1 (de) | 2003-04-03 | 2003-12-11 | Gemische von Verbindungen mit mindestens zwei Doppelbindungen und deren Verwendung |
AT04724254T ATE520643T1 (de) | 2003-04-03 | 2004-03-30 | Gemische von verbindungen mit mindestens zwei doppelbindungen und deren verwendung |
EP04724254A EP1613583B1 (de) | 2003-04-03 | 2004-03-30 | Gemische von verbindungen mit mindestens zwei doppelbindungen und deren verwendung |
KR1020057018679A KR20050120690A (ko) | 2003-04-03 | 2004-03-30 | 2개 이상의 이중 결합을 포함하는 화합물들의 혼합물 및그의 용도 |
US10/551,605 US7420013B2 (en) | 2003-04-03 | 2004-03-30 | Mixtures of compounds comprising at least two double bonds and use thereof |
BRPI0408969-3A BRPI0408969A (pt) | 2003-04-03 | 2004-03-30 | misturas de pelo menos dois composto, processos para preparar uma mistura de éster e um hidrogel reticulado, polìmero, hidrogel reticulado, composição de matéria e usos de um polìmero e de uma mistura de reação e de ésteres |
PCT/EP2004/003348 WO2004087635A2 (de) | 2003-04-03 | 2004-03-30 | Gemische von verbindungen mit mindestens zwei doppelbindungen und deren verwendung |
JP2006504915A JP2006522047A (ja) | 2003-04-03 | 2004-03-30 | 少なくとも2つの二重結合を備える化合物の混合物およびその使用 |
TW093109276A TW200500383A (en) | 2003-04-03 | 2004-04-02 | Mixtures of compounds having two or more double bonds and use thereof |
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DE10225943A DE10225943A1 (de) | 2002-06-11 | 2002-06-11 | Verfahren zur Herstellung von Estern von Polyalkoholen |
DE10225943.7 | 2002-06-11 | ||
DE10319462.2 | 2003-04-29 | ||
DE10319462 | 2003-04-29 |
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PCT/EP2003/006028 WO2003104301A1 (de) | 2002-06-11 | 2003-06-10 | (meth)acrylester von polyalkoxyliertem glycerin |
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US (1) | US20050165208A1 (de) |
EP (1) | EP1517942B1 (de) |
JP (1) | JP4373328B2 (de) |
CN (1) | CN100349958C (de) |
AT (1) | ATE325150T1 (de) |
AU (1) | AU2003274698A1 (de) |
BR (1) | BR0311498A (de) |
CA (1) | CA2487030A1 (de) |
DE (1) | DE50303213D1 (de) |
ES (1) | ES2263988T3 (de) |
MX (1) | MXPA04012180A (de) |
PL (1) | PL374404A1 (de) |
RU (1) | RU2005100765A (de) |
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WO2009000852A1 (en) * | 2007-06-27 | 2008-12-31 | Shell Internationale Research Maatschappij B.V. | An alkoxylate composition and a process for preparing the same |
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US7772420B2 (en) * | 2003-07-10 | 2010-08-10 | Basf Aktiengesellschaft | (Meth)acrylic esters of monoalkoxylated polyols, and production thereof |
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Publication number | Publication date |
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EP1517942B1 (de) | 2006-05-03 |
JP4373328B2 (ja) | 2009-11-25 |
RU2005100765A (ru) | 2005-09-10 |
US20050165208A1 (en) | 2005-07-28 |
ES2263988T3 (es) | 2006-12-16 |
EP1517942A1 (de) | 2005-03-30 |
PL374404A1 (en) | 2005-10-17 |
MXPA04012180A (es) | 2005-02-25 |
CA2487030A1 (en) | 2003-12-18 |
CN1659213A (zh) | 2005-08-24 |
AU2003274698A1 (en) | 2003-12-22 |
JP2005532431A (ja) | 2005-10-27 |
CN100349958C (zh) | 2007-11-21 |
ATE325150T1 (de) | 2006-06-15 |
DE50303213D1 (de) | 2006-06-08 |
BR0311498A (pt) | 2005-03-15 |
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