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EP1056789A1 - Vernetzte quellfähige polymere - Google Patents

Vernetzte quellfähige polymere

Info

Publication number
EP1056789A1
EP1056789A1 EP99934290A EP99934290A EP1056789A1 EP 1056789 A1 EP1056789 A1 EP 1056789A1 EP 99934290 A EP99934290 A EP 99934290A EP 99934290 A EP99934290 A EP 99934290A EP 1056789 A1 EP1056789 A1 EP 1056789A1
Authority
EP
European Patent Office
Prior art keywords
crosslinking
compounds
weight
formula
polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP99934290A
Other languages
German (de)
English (en)
French (fr)
Inventor
Rüdiger Funk
Volker Frenz
Uwe Stüven
Fritz Engelhardt
Thomas Daniel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1056789A1 publication Critical patent/EP1056789A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/245—Differential crosslinking of one polymer with one crosslinking type, e.g. surface crosslinking
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/14—Water soluble or water swellable polymers, e.g. aqueous gels

Definitions

  • the present invention relates to the use of diglycol silicates as crosslinking agents in the production of hydrogels containing carboxyl groups with improved properties, and to the use of the hydrogels thus produced as so-called superabsorbers for absorbing aqueous liquids.
  • Superabsorbers are water-insoluble, crosslinked, carboxyl group-containing polymers which are capable of swelling and forming hydrogels in aqueous liquids and body fluids, e.g. Take up urine or blood and keep the amount of fluid absorbed under a certain pressure. They are also called superabsorbent polymers or SAP.
  • Polyglycidyl ethers, haloepoxy compounds, polyols, polyamines or polyisocyanates can be used as crosslinking agents.
  • the previously known systems for surface post-crosslinking can be divided into four groups with different mechanisms of action:
  • EP-A-0 317 106 teaches a typical example of crosslinking with a reactive ring-opening compound through the use of polyglycidyl ethers, such as e.g. Ethylene glycol diglycidyl ether and EP-A-0 618 005 with the use of polyazetidinium salts.
  • polyglycidyl ethers such as e.g. Ethylene glycol diglycidyl ether and EP-A-0 618 005 with the use of polyazetidinium salts.
  • DE-A-4 020 780 improved absorption under pressure is achieved by surface-crosslinking treatment of a polymer with 0.1 to 5% by weight alkylene carbonate.
  • US-A-4 666 983 teaches the use of diisocyanates and polyisocyanates as possible compounds for the post-crosslinking of SAP surfaces.
  • the reaction with hydroxyl groups creates carbamate structures.
  • cross-linking consists in the formation of ionic instead of covalent cross-linking points.
  • polyvalent metal ions such as e.g. Aluminum is suitable for ionic crosslinking of the carboxyl functions.
  • WO-A-94/09043 describes the use of polyhydroxy compounds, in particular organic polyhydroxy compounds such as e.g. Diethylene glycol or trimethylolpropane at elevated temperature with ester formation.
  • EP-A-0 610 013 describes organic esters of carboxyl compounds of a polyfunctional organic alcohol, wherein an only partial esterification of the hydroxyl groups is also described.
  • the esters can also be applied to the SA surface in a mixture with water or an organic solvent.
  • EP-A-0 644 207 describes the surface crosslinking of (by using a blowing agent) porous SAP with polyhydroxy compounds.
  • the crosslinking reaction is completely analogous to WO-A-94/09043, the difference lies exclusively in the base polymer before the surface postcrosslinking.
  • EP-A-0 509 708 teaches the use of mixtures of a polyhydroxy compound with a surfactant, characterized by an HLB value between 3 and 10.
  • the surfactant does not contribute to the reaction but rather facilitates the distribution of the polyhydroxy component on the surface .
  • Crosslinking with certain polyfunctional organic alcohols is also disclosed by EP-A-0 450 924.
  • the methods according to items 1-3 have some disadvantages.
  • the crosslinking agents selected from these groups show a very high reactivity and they react directly to the polymer to be crosslinked. This high reactivity is very disadvantageous for an even distribution on the surface. This disadvantage cannot be compensated for by an increased mixing time. The application properties are not optimal due to this lack of distribution on the surface.
  • alkylene carbonates or poorly reactive polyols has the disadvantage that it is necessary to crosslink at very high temperatures in order to obtain sufficient reactivity. At such high temperatures, a thermal post-crosslinking of the entire polymers can be determined, the centrifuge retention being adversely affected. The high temperatures can also lead to an undesirable thermal decomposition of the product, which leads to discoloration of the product.
  • a method of crosslinking the surface of a superabsorbent polymer by a silane coupling reaction e.g. EP-A-0 195 406 teaches gamma-glycidoxypropyltrimethoxysilanes.
  • the primary binding takes place through the reactive group X, the hydrolyzable group being converted to the silanol group in the presence of water, which in turn can form a Si-O-Si bond in a further step by dehydration.
  • the hydrolyzable group being converted to the silanol group in the presence of water, which in turn can form a Si-O-Si bond in a further step by dehydration.
  • no compounds are disclosed which consist only of hydrolyzable groups.
  • the object of the present invention is to provide a new method for surface crosslinking, by means of which hydrogels with improved properties with regard to gel strength and water retention are obtained.
  • the crosslinkers should have a medium reactivity which allows the system used to be distributed over the surface without the disadvantage of crosslinking only at very high temperatures.
  • the invention therefore relates to a process for the surface crosslinking of particles of superabsorbent polymers, characterized by the use of compounds of the formula 1 as crosslinking agents
  • R and R ' are independent of one another or identical and denote hydrogen or Ci-Cg-alkyl.
  • R and R ' preferably have the same meaning and in particular each represent H or CH 3 .
  • the invention furthermore relates to water-swellable hydrogels based on (co) polymerized, hydrophilic monomers or based on natural hydrophilic polymers, a mixture of these two polymers or a copolymer which contains carboxyl groups, characterized in that they contain a compound of Formula 1 were superficially networked. 5
  • the crosslinking reaction generally takes place by transesterification in the range of higher temperatures.
  • the crosslinking reaction can be accelerated by a catalyst, which means that it can be carried out at a lower temperature. Temperatures of 120 to 220 ° C are preferred for the process according to the invention.
  • the crosslinking is preferably carried out by transesterification of the compounds of formula 1 with ring opening with the reactive carboxyl groups of the monomers or the (co) poly eren.
  • the compounds of formula 1 are preferably used in amounts of 0.05 to 10% by weight, based on the total monomer weight or the total polymer weight. They are preferably used in the form of aqueous, alcoholic or aqueous-alcoholic mixtures.
  • Suitable natural polymers which can be crosslinked with compounds of the formula 1 to give hydrogels according to the invention can be used both in unrefined and in refined form.
  • Carboxymethylpolysaccharides such as carboxymethylhydroxypropyl guar, carboxymethyl starch and alginates, are particularly suitable.
  • Particularly suitable copolymerizable hydrophilic monomers are acrylic acid, methacrylic acid, crotonic acid, 2-acrylamido-2-methylpropanesulfonic acid and phosphonic acid, vinylphosphonic acid, vinylphosphonic acid half-esters, their salts, acrylamide, N-vinylamides, vinyl acetate or mixtures thereof.
  • acrylic acid and its salts e.g. Na, K and / or ammonium acrylate.
  • the polymerization can be carried out by any known reaction, radical polymerization in a homogeneous phase, e.g. in aqueous solution, a so-called gel polymerization.
  • the precipitation polymerization from organic solvents, such as from alcohols, preferably tert offers further possibilities for the synthesis of the hydrogels according to the invention.
  • -Butanol or hydrocarbons such as hexane or cyclohexane, or suspension, dispersion, emulsion or microemulsion polymerization, but also ionic polymerization.
  • radical polymerization can be triggered by radical formers such as organic or inorganic peroxides and azo compounds.
  • radical formers such as organic or inorganic peroxides and azo compounds. Examples are benzoyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, (NH 4 ) 2 S 0 8 , KS 0s, 6
  • the polymerization can also be triggered by high-energy radiation.
  • the compounds of formula 1 can be used for crosslinking during the polymerization reaction and / or only after the polymerization reaction for subsequent crosslinking of the polymer. If the compound of formula 1 is first added to an uncrosslinked pr (co) polymer, this is usually done before drying by homogeneous mixing, for example by kneading an aqueous polymer gel in a kneader. Spraying from dilute solution onto a polymer powder or a polymer granulate is also possible. In this case, a suitable crosslinking of the polymers in the vicinity of the particle surface can be carried out by a suitable choice of the solvent system.
  • hydrogels according to the invention are outstandingly suitable as absorbents for aqueous liquids, for the formulation of cosmetic preparations, as consolidators and / or binders of fibrous sheet-like structures containing reactive groups, as polymeric additives for aqueous drilling fluids and cement additives in petroleum production, and for use in hygiene articles , Packaging materials and nonwovens.
  • SAP super absorbent polymers
  • acrylic acid For use as so-called “super absorbent polymers” (SAP) for use in hygiene articles such as diapers, tampons or sanitary napkins, hydrogels according to the invention based on acrylic acid are particularly suitable, some of which may be present as alkali or ammonium salts.
  • the neutralization can take place both before and after the polymerization.
  • the hydrophilic monomers are polymerized to produce SAP, preferably in the presence of conventional crosslinkers containing at least two ethylenically unsaturated double bonds, e.g. N, N '-methylene bisacrylamide, triallylamine, 1,4-butanediol diacrylate, pentaerythritol trialkyl ether and / or tetraalkyl oxyethane.
  • Hydrogels according to the invention based on polysaccharides containing carboxyl groups are also outstandingly suitable for use as SAP.
  • the addition of acidic catalysts can accelerate the crosslinking reaction and / or lower the reaction temperature.
  • inorganic oxo acids such as, for example, phosphoric acid, sulfuric acid, boric acid, polyphosphates, polyborates, polyphosphonates, phosphonic acid anhydrides, and also hydrogen sulfates, hydrogen phosphates .
  • acids of the general formula HX where X can be a halogen and all known Lewis acids, such as, for example, BF etherate or sulfonic acids, in particular organic sulfonic acid, such as, for example, p-toluenesulfonic acid.
  • Hydrogen phosphates, boric acid and their anhydrides, esters or partial esters, and p-toluenesulfonic acid and BF 3 etherate are particularly suitable.
  • test methods are used to characterize superabsorbent polymers, including the measurement of the extractable fractions after n hours and the absorption of 0.9% by weight NaCl solution with and without weight loading.
  • the supernatant solution is filtered and the polyacrylic acid or the polyacrylate is titrated.
  • the pH electrode for the titration is calibrated at pH 2, 7 and 10. It is first titrated to a pH of 10 with approximately 0.1 N NaOH.
  • the amount of NaOH consumed is called Va (in ml), the normality of the base is Na (n meq / ml).
  • the solution titrated in this way is then adjusted to pH 2.7 with approximately 0.1 N HCl.
  • the amount of HC1 consumed is called Vb, the normality of the acid is Nb (in meq / ml).
  • Vab denotes the amount of base required
  • Vbb the amount of acid required to titrate the pure salt solution.
  • the extractable parts are calculated according to: 8th
  • Ea the equivalent mass of an unneutralized monomer in the polymer chain (72 daltons)
  • Eb the equivalent mass of a neutralized monomer in the polymer chain (94 daltons)
  • the free water absorption of the SAP is measured using the teabag method.
  • Approx. 0.2 g SAP are welded into a tea bag and immersed in a 0.9% by weight NaCl solution for 20 minutes.
  • the tea bag is then spun in a centrifuge for 5 minutes with a centrifugal force of 250 -G.
  • a tea bag without SAP determines the blank value of the measurement:
  • 0.9 g SAP When absorbed under pressure, 0.9 g SAP are evenly distributed on the bottom of a plexiglass cylinder.
  • the cylinder has a height of 50 mm and an inner diameter of 60 mm.
  • On the bottom of the cylinder is a wire mesh with a mesh size of 36 ⁇ m (400 mesh).
  • a cover plate is placed over the super absorber and the sample is loaded with an appropriate weight (20, 40, 60 g / cm 2 ). The superabsorbent is then allowed to swell under the appropriate pressure for 60 minutes.
  • the AUL (Absorbency under Load) under a pressure load is calculated according to:
  • AUL (g / g) [(Wb-Wa) / Ws]
  • Wa is the mass of the apparatus
  • Wb is the mass of the apparatus after water has been absorbed by the SAP
  • Ws is the mass of the SAP.
  • the shear modulus is measured using a Carri-Med controlled stress rheometer. A 6 cm plate-plate geometry is used for the measurement. To determine the shear modulus, 2.5 g of SAP in 100 g of 0.9% by weight NaCl are allowed to swell for 24 hours and the shear modulus is then measured as a function of the frequency. The value at 10 Hz is given as a memory module.
  • the initiators a redox system consisting of 2.2 g of 2, 2'-azobisamidinopropane dihydrochloride, dissolved in 20 g of demineralized water, 4 g of potassium peroxodisulfate, dissolved in 150 g of demineralized water and 0 , 4 g of ascorbic acid, dissolved in 20 g of demineralized water, added in succession and stirred.
  • the reaction solution is then left to stand without stirring, a solid gel being formed by the onset of polymerization, in the course of which the temperature rises to approximately 89 ° C. This is then crushed mechanically, dried at temperatures above 150 ° C and ground.
  • the product produced in this way was worked into a baby diaper in a conventional manner and was distinguished here by particularly good fluid retention. 10
  • 25 gels are mixed with 56.5 g of sodium hydroxide solution (50%) (degree of neutralization of acrylic acid 74 mol%), kneaded twice, mixed with 25 g of a 1% solution of compound 2, again kneaded twice, then at temperatures above 150 ° C dried, ground and sieved in a thin layer.
  • sodium hydroxide solution 50%) (degree of neutralization of acrylic acid 74 mol%)
  • the gel obtained in this way is referred to as example 4b after surface postcrosslinking.
  • Examples 11 to 15 describe the preparation of water-swellable products with good absorbency by crosslinking polymers of various origins with compounds according to the invention, which is done in such a way that mixtures of polyacrylates and carboxymethylpolysaccharides or alginates are pasted in water with compounds of the formula 1 mixed, kneaded homogeneously, dried in an air stream at 180 ° C., ground and sieved.
  • compounds of the general formula 1 are added as aqueous or aqueous-alcoholic mixtures with the addition of 0.1 to 0.6% by weight, based on polymer, of acidic catalysts and at 120 ° C treated to 180 ° C. After cooling to room temperature, the following values, which are listed in Table IV, were found compared to the starting product.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epidemiology (AREA)
  • Veterinary Medicine (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Hematology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Absorbent Articles And Supports Therefor (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Materials For Medical Uses (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
EP99934290A 1998-02-21 1999-02-18 Vernetzte quellfähige polymere Withdrawn EP1056789A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE1998107504 DE19807504A1 (de) 1998-02-21 1998-02-21 Vernetzte quellfähige Polymere
DE19807504 1998-02-21
PCT/EP1999/001065 WO1999042496A1 (de) 1998-02-21 1999-02-18 Vernetzte quellfähige polymere

Publications (1)

Publication Number Publication Date
EP1056789A1 true EP1056789A1 (de) 2000-12-06

Family

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Application Number Title Priority Date Filing Date
EP99934290A Withdrawn EP1056789A1 (de) 1998-02-21 1999-02-18 Vernetzte quellfähige polymere

Country Status (9)

Country Link
EP (1) EP1056789A1 (id)
JP (1) JP2002504568A (id)
CN (1) CN1291203A (id)
AU (1) AU3253199A (id)
BR (1) BR9908078A (id)
CA (1) CA2319786A1 (id)
DE (1) DE19807504A1 (id)
ID (1) ID28466A (id)
WO (1) WO1999042496A1 (id)

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EP1130045B2 (en) 2000-02-29 2015-10-28 Nippon Shokubai Co., Ltd. Process for producing a water-absorbent resin powder
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US7193006B2 (en) 2002-12-06 2007-03-20 Nippon Shokubai Co., Ltd. Process for continuous production of water-absorbent resin product
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EP2431349B1 (en) 2009-05-15 2017-03-29 Nippon Shokubai Co., Ltd. Method for producing (meth)acrylic acid
WO2011025013A1 (ja) 2009-08-28 2011-03-03 株式会社日本触媒 吸水性樹脂の製造方法
JP2013504674A (ja) * 2009-09-16 2013-02-07 ビーエーエスエフ ソシエタス・ヨーロピア 色安定性の超吸収剤
CN102549028B (zh) 2009-09-30 2016-03-02 株式会社日本触媒 聚丙烯酸(盐)系吸水树脂及其制造方法
CN102712763B (zh) 2010-01-20 2014-07-30 株式会社日本触媒 吸水性树脂的制造方法
EP2527391B1 (en) 2010-01-20 2023-08-09 Nippon Shokubai Co., Ltd. Method for producing water absorbent resin
EP2535369B1 (en) 2010-02-10 2021-03-24 Nippon Shokubai Co., Ltd. Process for producing water-absorbing resin powder
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Also Published As

Publication number Publication date
CN1291203A (zh) 2001-04-11
JP2002504568A (ja) 2002-02-12
CA2319786A1 (en) 1999-08-26
DE19807504A1 (de) 1999-08-26
ID28466A (id) 2001-05-24
AU3253199A (en) 1999-09-06
BR9908078A (pt) 2000-10-24
WO1999042496A1 (de) 1999-08-26

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