WO2011141526A1 - Matière hybride biodégradable gonflant au contact de l'eau - Google Patents

Matière hybride biodégradable gonflant au contact de l'eau Download PDF

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Publication number
WO2011141526A1
WO2011141526A1 PCT/EP2011/057647 EP2011057647W WO2011141526A1 WO 2011141526 A1 WO2011141526 A1 WO 2011141526A1 EP 2011057647 W EP2011057647 W EP 2011057647W WO 2011141526 A1 WO2011141526 A1 WO 2011141526A1
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Prior art keywords
water
hybrid material
polymer matrix
methylene
unit
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PCT/EP2011/057647
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German (de)
English (en)
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Holger Behrens
Wulf Bentlage
Jürgen Kunstmann
Beate Mondrzik
Zahra Rezaie
Helmut Ritter
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Geohumus International Research & Development Gmbh
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Publication of WO2011141526A1 publication Critical patent/WO2011141526A1/fr

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    • 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
    • C08F224/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00—Soil-conditioning materials or soil-stabilising materials
    • C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds

Definitions

  • the invention relates to a water-swellable hybrid material comprising a structure-crosslinked polymer matrix and inorganic compounds bound therein
  • Solid particles having improved biodegradability and a process for its preparation.
  • Water-swellable hybrid materials having a polymer matrix with inorganic particulate matter bound therein are known in the art and are described, for example, in WO 03/000621. Such water-swellable hybrid materials can be used as a soil additive, inter alia in agriculture to improve water storage and soil structure.
  • the polymer component of these hybrid materials is usually based on
  • Acrylate (co) polymers which can absorb many times their own weight of water or aqueous liquids to form hydrogels. Such polymers are also referred to as superabsorbents. Although polyacrylic-based superabsorbents are toxicologically and ecotoxicologically largely harmless, they are practically difficult to biodegrade and can remain in the soil for several decades, depending on the site conditions.
  • Polysaccharide content is not incorporated into the main chain, since in aqueous solution saccharides can not be converted into acrylic acid ester with acrylic acid. However, since only the saccharide portion is biodegradable, the hard-biodegradable polyacrylic acid backbones are retained in these hybrid materials.
  • Superab sorbern by polymerization of modified natural substances such as starch, cellulose or protein molecules to improve. Although these polymers can be completely biodegraded, but their preparation is very expensive.
  • the object of the present invention is to provide a water-swellable hybrid material which is stable during use and biodegradable after fulfilling its task.
  • Another object of the present invention is to provide a water-swellable hybrid material that can be degraded in a controlled manner. It is desirable to be able to control the biodegradation of the water-swellable hybrid material in a targeted manner.
  • Another object of the present invention is to provide a water-swellable hybrid material whose degradation products are non-toxic to the environment. Furthermore, it is desirable that the water-swellable
  • Hybrid material is mainly degraded to inorganic particulate matter, carbon dioxide and water.
  • Another object of the present invention is to provide a water-swellable hybrid material which, in addition to being biodegradable, has excellent swellability. It is also desirable to have the water-swellable hybrid material in terms of its physical properties, eg its water absorption capacity, to be able to adapt to the appropriate application.
  • Hybrid material is not affected.
  • a solution according to the invention consists of a water-swellable hybrid material comprising a biodegradable, crosslinked polymer matrix and inorganic solid particles bound therein, wherein the crosslinked polymer matrix comprises at least one constitutive unit A, wherein the unit A is of one olefinic
  • unsaturated carboxylic acid is derived, and at least one further constitutive unit B, wherein the unit B is adapted to insert at least one biodegradable predetermined breaking point in the crosslinked polymer matrix, and wherein the crosslinked polymer matrix at least one biologically cleavable predetermined breaking point in the
  • Main chain of the polymer matrix has.
  • Biologically fissile predetermined breaking points represent weak points in the
  • Polymer structure can be cleaved under the influence of environmental influences.
  • the invention makes it possible to insert specifically such predetermined breaking points in the polymer matrix.
  • the type of constitutive unit used the
  • Predetermined breaking points in the main chain of the structure-crosslinked polymer matrix and / or in the crosslinking bridges of the structure-crosslinked polymer matrix are inserted.
  • Preferably, both in the main chain and in the crosslinking bridges Predetermined breaking points available.
  • These predetermined breaking points may be, for example, a functional group which is sensitive to hydrolysis or oxidatively degradable.
  • the oxidative degradation can be caused by ozone, for example, by
  • predetermined breaking points are functional groups in which the structure-crosslinked polymer matrix can be cleaved enzymatically by microorganisms or photochemically under the influence of sunlight.
  • the rate of degradation of the hybrid material can be adjusted as desired by the number and type of predetermined breaking points inserted into the polymer matrix.
  • the biodegradable, structurally crosslinked polymer matrix can be cleaved enzymatically by microorganisms or photochemically under the influence of sunlight.
  • the rate of degradation of the hybrid material can be adjusted as desired by the number and type of predetermined breaking points inserted into the polymer matrix.
  • Polymer matrix made entirely from synthetic monomers.
  • An advantage of completely synthetic materials over polymers containing natural products such as starch or cellulose is that they can be produced with a defined, constant quality, and thus always the same chemical
  • composition and rate of degradation have the same physical properties.
  • use of synthetic monomers allows a wide variation of the polymer structure and thus a targeted adaptation to the desired application.
  • FIG. 1 shows examples of predetermined breaking points in polymer systems and the biodegradation of such polymer systems.
  • Fig. 2 shows an example of ring opening upon copolymerization of a compound of the formula (I) and an acrylic acid monomer.
  • water-swellable is understood as meaning a material which, on contact with water or aqueous liquids, such as, for example, Salt solutions, body fluids, etc., or other protic-polar
  • the swelling behavior of the hybrid material may be e.g. can be determined by contacting the dry or wet hybrid material with a sufficient amount, e.g. demineralized water, typically at room temperature of about 20-23 ° C, preferably 20 ° C, and weighing the drained material after certain
  • structure-crosslinked polymer matrix or “crosslinked polymer matrix” refers in the present case to a three-dimensionally crosslinked homo- or copolymer with open and / or closed pore structure, which comprises the inorganic compounds
  • structure-crosslinked polymer matrix and “crosslinked polymer matrix” are used synonymously.
  • the structure-crosslinked polymer matrix is composed of two or more different monomer units, wherein at least one chain-shaped polymer or copolymer, referred to in the context of the present invention as a "main chain", by monomer or oligomer units, which in the context of the present invention as
  • Network bridges are referred to each other.
  • the structure-crosslinked polymer matrix or the hybrid material essentially retains its structure in the water-saturated state.
  • the structurally crosslinked polymer matrix or material can preferably absorb water to the saturation limit without altering its original structure, i. the polymer matrix or the hybrid material forms under
  • inorganic solid particles means in
  • the inorganic solid particles are bound or incorporated chemically and / or physically in the structure-crosslinked polymer matrix.
  • the inorganic solid particles bound in the structure-crosslinked polymer matrix according to the invention can not be washed out of the polymer matrix.
  • constitutive unit X is derived from a compound of the formula Y
  • a compound of the formula Y is used to obtain a polymer having a constitutive unit X.
  • Constutive unit and unit are used interchangeably under a “biologically fissile breaking point” is used in the context of
  • the present invention is understood to mean a functional group in which the
  • structure-crosslinked polymer matrix can be degraded hydrolytically, oxidatively or enzymatically under the influence of environmental influences.
  • biologically cleavable predetermined breaking points are ether, ester, thioester, carbonyl, peroxy, hydrazo or ureylene groups and electron-rich centers such. Double or triple bonds.
  • environmental influences include exposure to moisture, sunlight, ozone or enzymes released by
  • Microorganisms are produced.
  • Biologically splittable predetermined breaking points can be located in the main chain of the polymer matrix and / or in the crosslinking bridges of the polymer matrix.
  • the biologically cleavable breaking point is a functional group which can be degraded hydrolytically or ozonolytically, especially preferably hydrolytic.
  • the polymer chain is first broken down into shorter fragments and finally degraded under environmental conditions to final degradation products, which may consist of carbon dioxide, methane, water or other non-toxic compounds.
  • final degradation products which may consist of carbon dioxide, methane, water or other non-toxic compounds.
  • Polymer matrix can be done, for example, that first the
  • Polymer chains are cleaved under environmental conditions, preferably by hydrolysis, at the predetermined breaking points into shorter chains, and then the shorter chains of microorganisms are converted to C0 2 , water and / or biomass.
  • straight-chain, branched or cyclic, optionally substituted alkyl, alkenyl, alkynyl or acyl having 1 to 20 carbon atoms may comprise the following radicals:
  • Alkyl radicals may comprise straight-chain, branched or cyclic, optionally substituted radicals having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms and in particular lower alkyl radicals having 1 to 6, preferably 1 to 4 carbon atoms. Specific examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, n-hexyl, dodecyl, octadecyl and cyclohexyl.
  • the alkyl radicals may have one or more substituents from the group of halogens such as F, Cl and Br or acryloxy, amino, amide, aldehyde, alkoxy, alkoxycarbonyl, alkylcarbonyl, carboxy, cyano, epoxy, hydroxy , Keto, methacryloxy, mercapto, phosphoric acid, sulfonic acid or vinyl groups.
  • halogens such as F, Cl and Br or acryloxy, amino, amide, aldehyde, alkoxy, alkoxycarbonyl, alkylcarbonyl, carboxy, cyano, epoxy, hydroxy , Keto, methacryloxy, mercapto, phosphoric acid, sulfonic acid or vinyl groups.
  • Alkenyl and alkynyl radicals may include straight-chain, branched or cyclic, optionally substituted radicals having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and especially lower alkyl radicals having 1 to 6, preferably 1 to 4 carbon atoms. Special examples for
  • Alkenyl radicals are allyl, 1-methylprop-2-en-1-yl, 2-methyl-prop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-methylbut-3-en-1-yl and 1-methylbut-2-en-1-yl.
  • alkynyl radicals are propynyl, but-2-yn-1-yl, but-3-yn-1-yl and 1-methyl-but-3-yn-1-yl.
  • Acyl radicals may optionally comprise substituted radicals of organic acids which formally arise by cleavage of an OH group from the organic acid, for example radicals of a carboxylic acid or radicals derived therefrom such as thiocarboxylic acid, optionally N-substituted imino carboxylic acids or the radicals of carbonic acid monoesters, optionally N -substituted carbamic acids, sulfonic acids, sulfinic acids, phosphonic acids, phosphinic acids.
  • the acyl radicals may contain one or more substituents from the group of halogens such as F, Cl and Br or acryloxy, amino, amide, aldehyde, alkoxy, alkoxycarbonyl,
  • radicals named thereafter may be optionally mono- or polysubstituted Suitable substituents are, for example, methyl, ethyl, propyl, butyl, hydroxy or halogens, such as, for example, F, Cl, Br or I.
  • Weight percentages are based on the total weight of the dry hybrid material, i. for example, at one
  • the water-swellable hybrid material comprises a biodegradable, structurally crosslinked polymer matrix and inorganic particulate matter bound therein, wherein the structurally crosslinked polymer matrix comprises at least one constitutive moiety A, wherein the moiety A is derived from an olefinically unsaturated carboxylic acid, and at least one further constitutive unit B, wherein the unit B is adapted to insert at least one biologically cleavable predetermined breaking point in the structure-crosslinked polymer matrix.
  • the structure-crosslinked polymer matrix may comprise an additional, optional constitutive unit C.
  • the constitutive unit A is derived from an olefinically unsaturated carboxylic acid.
  • Suitable carboxylic acid monomers for preparing the crosslinked copolymer according to the invention are carboxylic acids having at least one
  • Carboxyl group and at least one olefinic double bond Preferably, a double bond in the olefinically unsaturated carboxylic acid is in the ⁇ -position to a carboxyl group.
  • the double bond is activated and can be polymerized easier.
  • the polymerizability of a double bond can also be facilitated by an end position in the molecule.
  • double bond can also be located at any other position in the olefinically unsaturated carboxylic acid monomer.
  • the olefinically unsaturated carboxylic acid monomer may comprise further double bonds, which may optionally also be polymerizable.
  • Suitable olefinically unsaturated carboxylic acids are, for example, acrylic acid, methacrylic acid, ethylacrylic acid, cc-chloroacrylic acid, cyanoacrylic acid, .beta.-methylacrylic acid (crotonic acid), .alpha.-phenylacrylic acid, .beta.-acryloxypropionic acid,
  • the olefinically unsaturated carboxylic acid monomer is selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid and fumaric acid, particularly preferred is acrylic acid. It can also be mixtures of several olefinically unsaturated
  • the olefinically unsaturated carboxylic acid monomers may be used in an amount of from 10 to 99.99 mol% based on the total content of the monomers used, e.g. in an amount of 50 to 99 mol%, 60 to 98 mol% or from 70 to 97 mol%.
  • the olefinically unsaturated carboxylic acid monomers are used in an amount of 80 to 96 mol% or 88 to 99 mol%, based on the total content of the monomers used.
  • the crosslinked copolymer contains 10 to 99 mol% of the constituent unit A based on
  • Total amount of constitutive units of the crosslinked copolymer preferably 50 to 99 mol%, 60 to 98 mol% or 70 to 97 mol%, and particularly preferably 80 to 96 mol%.
  • the olefinically unsaturated carboxylic acid monomers can be used in the
  • Reaction mixture are at least partially neutralized, and thus the pH, the polymerization and ultimately the structure of the hybrid material according to the invention are suitably modified.
  • a maximum of about 80%, for example about 60 to 80%, and in exemplary embodiments, a maximum of 40% of the acid groups of the monomers are neutralized.
  • the (partial) neutralization can be carried out by basic solid particles and / or by addition of at least one basic substance, for example an alkaline earth and / or alkali metal hydroxide, lime, alkylamines, or ammonium hydroxide.
  • KOH or NaOH can be used.
  • the (partial) neutralization with KOH is carried out by basic solid particles and / or by addition of at least one basic substance, for example an alkaline earth and / or alkali metal hydroxide, lime, alkylamines, or ammonium hydroxide.
  • R 1 is selected from the group comprising hydrogen and straight-chain, branched or cyclic, optionally substituted alkyl, alkenyl, alkynyl or acyl having 1 to 20 carbon atoms,
  • R 4 is either absent, in which case R 2 and R 3 are linked via a single or double bond, or selected from the group comprising straight-chain or branched optionally substituted alkylene, alkenylene or alkynylene having 1 to 20 carbon atoms, these being CO-, -COO-, -O-CO-O-, -CONR d , -SiH 2 -, -O-, -S-, -SO- or -SO 2 - groups may be interrupted, where R d is hydrogen or straight-chain, branched or cyclic,
  • alkyl optionally substituted alkyl, alkenyl, alkynyl or acyl with 1 to 20
  • Suitable compounds of the formula (I) are, for example, 2-methylene-1,3-dioxalane, 2-methylene-1,3-dioxepane, 2-methylene-4,7-dihydro-1,3-dioxepin, 6-methylene-1 , 1-dioxa-5,7-diazacyclohexadecane-12,16-dione, 2-methylene-1,3,6-triazocane, 2-methylene-1,3,3,7-dioxadiazocane, 2-methylene-1, 3-dioxacycloundecane-4,11-dione, 2-methylene-1, 3,8,11-tetraazacyclopentadecane-9,10-dione, 3-methylene-1, 2,4,5-tetrazecane-6,10-dione, 2-methylene-l, 3,6-dioxathiocane-6,6-dioxide, (Z) 2-methylene-1, 3-dioxepin-4,7-d
  • the compound of the formula (I) is preferably 2-methylene-1,3-dioxalane, 2-methylene-1,3-dioxepan or 2-methylene-4,7-dihydro-1,3-dioxepin or mixtures thereof.
  • X can have a single or
  • Double bond to be linked to the C atom An example of one Ring opening in the copolymerization of acrylic acid and 2-methylene-l, 3-dioxalane is shown in Fig. 2.
  • the compound according to formula (I) can be further polymerisable
  • structurally crosslinked polymer matrix 0.1 to 50 mol% of constitutive unit B derived from a compound of formula (I), based on the total amount of constitutive units of the structurally crosslinked polymer matrix, preferably 0.5 to 40 mol%, 1 to 30 mol% or from 2 to 20 mol%, and more preferably 5 to 15 mol%.
  • the constitutive unit B is derived from a compound according to formula (II),
  • R 5 to R 10 are each independently selected from the group comprising hydrogen, halogen and straight-chain, branched or cyclic, optionally substituted alkyl, alkenyl, alkynyl or acyl having 1 to 20
  • n is an integer between 1 and 10 or between 1 and 8.
  • m is an integer between 2 and 6.
  • Suitable compounds of the formula (II) are, for example, alkene compounds having 2 to 6 conjugated double bonds.
  • Specific examples of compounds of the formula (II) are isoprene, dimethylbutadiene, butadiene, chloroprene, cyclohexadiene, butadienecarboxylic acid or butadiene dicarboxylic acid.
  • Hybrid material according to the invention can be used.
  • the compounds of the formula (I) or (II) can be used in an amount of 0.01 to 50 mol%, based on the total content of the monomers used, e.g. in an amount of 0.1 to 40 mol%, 1 to 30 mol% or from 2 to 20 mol%.
  • the compounds of the formula (I) or (II) are preferably used in an amount of 5 to 1 mol% or else 1 to 12 mol%, based on the total content of the monomers used.
  • Structurally crosslinked polymer matrix 0.1 to 50 mol% of constitutive unit B derived from a compound of formula (II), based on the total amount of constitutive units of the structurally crosslinked polymer matrix, preferably 0.5 to 40 mol%, 1 to 30 mol% or from 2 to 20 mol%, and more preferably 5 to 15 mol%.
  • Predetermined breaking points are generated, which can be decomposed ozonolytically.
  • the ratio between the at least one constitutive unit A and the at least one constitutive unit B which is suitable for inserting predetermined breaking points into the main chain of the polymer matrix is between 100: 1 and 2: 1, preferably between 50: 1 and 3: 1, more preferably between 35: 1 and 5: 1, even more preferably between 15: 1 and 5: 1, and most preferably about 10: 1.
  • the main chains of the structure-crosslinked polymer matrix are decomposed under the action of environmental influences, preferably hydrolytically, into fragments having preferably such chain lengths, which can be metabolized particularly well by microorganisms.
  • the ratio between the at least one unit A and the at least one unit B which is suitable to insert predetermined breaking points in the main chain of the polymer matrix, so selected that the main chains of the structure-crosslinked polymer matrix under the influence of environmental influences, preferably hydrolytically, in fragments with a molecular weight between 500 and 6000, preferably between 600 and 3000, more preferably between 700 and 1500 and more preferably between 800 and 1000 cleaved.
  • the structure-crosslinked polymer matrix comprises at least two units B, wherein the first unit B is suitable for inserting at least one biologically cleavable predetermined breaking point into the main chain of the structure-crosslinked polymer matrix, and the second unit B is suitable, at least one biologically cleavable predetermined breaking point into the crosslinking bridges of the structure-crosslinked polymer matrix.
  • Crosslinking bridges of the structure-crosslinked polymer matrix may be the polymer matrix at least one second constitutive unit B, which is derived from a compound according to formula (III)
  • Each R 1 1 is independently selected from radicals of the formula (IV)
  • n is an integer> 0,
  • Z is selected from the group comprising -O- and -NH-,
  • R 12 is selected from the group comprising straight-chain or branched optionally substituted alkylene, alkenylene, alkynylene or arylene having 1 to 20 carbon atoms and R 13 is hydrogen or methyl.
  • x is equal to 2.
  • n is an integer between 1 and 10 or between 1 and 8.
  • n is an integer between 2 and 4.
  • Suitable compounds of the formula (III) are adipic acid bis [2- (2-methylacryloxy) ethyl] esters, fumaric acid bis [2- (2-methylacryloxy) ethyl] esters, Itaconic acid bis [2- (2-methylacryloxy) ethyl] ester and maleic bis [2- (2-methylacryloxy) ethyl] ester.
  • Structure-crosslinked polymer matrix may alternatively or additionally be produced by at least one second constitutive unit B, which is derived from a compound according to formula (V)
  • each R is independently selected from residues of
  • n is an integer> 0,
  • Z is selected from the group comprising -O- and -NH-,
  • R is selected from the group comprising straight-chain or branched optionally substituted alkylene, alkenylene, alkynylene or arylene having 1 to 20 carbon atoms and
  • R 13 is hydrogen or methyl.
  • n is an integer between 1 and 10 or between 1 and 8, Preferably, n is an integer between 2 and 4.
  • compounds of the formula (V) are zo-phthalic acid bis [2- (2-methylacryloxy) ethyl] esters, isophthalic acid bis [2- (2-methylacryloxy) ethyl] esters or terephthalic acid bis- [2- (2-methylacryloxy) ethyl] ester.
  • the second constitutive unit B is derived from the compound terephthalic acid bis [2- (2-methylacryloxy) ethyl] ester.
  • the compounds of the formula (III) and / or (V) may be used in an amount of 0.0001 to 10 mol%, based on the total amount of the monomers used, e.g. in an amount of 0.001 to 8 mol%, 0.01 to 5 mol% or from 0.1 to 5 mol%.
  • the compounds of the formula (III) and / or (V) are preferably used in an amount of from 0.1 to 2 mol%, based on the total content of the monomers used.
  • the crosslinked copolymer contains 0.0001 to 10 mol% of the second unit B, based on the
  • Total amount of constituent units of the crosslinked copolymer preferably 0.001 to 8 mol%, 0.01 to 5 mol% or from 0.1 to 5 mol%, and particularly preferably 0.1 to 2 mol%.
  • Polymer matrix additional predetermined breaking points are generated, which can be hydrolytically degraded.
  • the structure-crosslinked polymer matrix comprises at least two units B, wherein the first unit B is derived from a compound of the formula (I) and the second unit B is derived from a compound of the formula (III) and / or (V). According to a further embodiment, the structure-crosslinked polymer matrix comprises at least two units B, wherein the first
  • Unit B is derived from a compound of formula (II) and the second unit B is derived from a compound of formula (III) and / or (V).
  • the structure-crosslinked polymer matrix comprises at least three units B, wherein the first unit B is derived from a compound of formula (I), the second unit B of a compound of formula (II) and the third unit B of a compound of Formula (III) and / or (V) is derived.
  • the crosslinking bridges can be generated by suitable crosslinkers.
  • Suitable crosslinkers are compounds having at least two polymerizable double bonds or compounds having at least one polymerizable double bond and at least one further functional group which is reactive with acid groups.
  • Suitable examples are mono-, di- and polyesters of acrylic acid, methacrylic acid, itaconic acid and maleic acid, mono-, di- and polyesters of polyhydric alcohols such as butanediol, hexanediol,
  • Butanediol diacrylate as well as the esters of these acids with allyl alcohol and its alkoxylated homologues. Further examples are N-diallylacrylamide,
  • diamines and their salts with at least two ethylenically unsaturated substituents such as di- and triallylamine and tetraallylammonium chloride.
  • Particularly suitable are 1, 4-butanediol diacrylate (BDDA), methylenebisacrylamide and allyl methacrylate (ALMA).
  • the structure-crosslinked polymer matrix is selected from the group consisting of 1, 4-butanediol acrylate with a crosslinker.
  • Methylenbisacrylamid and allyl methacrylate crosslinked Methylenbisacrylamid and allyl methacrylate crosslinked.
  • the crosslinker can be used in an amount of 0.00001 to 10 mol%, based on the total content of the monomers used, e.g. in an amount of 0.0001 to 8 mol%, 0.001 to 5 mol% or from 0.01 to 3 mol%, it is preferably used in an amount of 0.1 to 2 mol%.
  • Polymer matrix preferably 0.0001 to 8 mol%, 0.001 to 5 mol% or from 0.01 to 3 mol%, and particularly preferably 0.1 to 2 mol%.
  • biodegradable, crosslinked copolymer may comprise at least one further optional constitutive unit C.
  • the additional, optional constitutive unit C can be located, for example, in the main chain of the crosslinked polymer matrix and derived from compounds such as acrylonitriles or acrylamides.
  • Suitable acrylonitriles are, for example, acrylonitrile, methacrylonitrile, ethylacrylonitrile or chloroacrylonitrile.
  • Acrylic amides are, for example, acrylamide, methacrylamide, N-methacrylamide, Nt-butylacrylamide, N-cyclohexylacrylamide and N-ethylacrylamide.
  • Other suitable optional constitutive units can be derived, for example, from compounds such as styrene, ethene, propene, butene or methyl (meth) acrylate. Preference is given to substituted N-acrylamides or N, N-di-substituted acrylamides.
  • the compound from which the constitutive unit C is derived can be used in an amount of 0 to 20 mol%, based on the total content of the monomers used, for example in an amount of 0.0001 to 8 mol%, 0.001 to 5 mol%, or 0.01 to 3 mol%, it is preferably used in an amount of 0.1 to 2 mol%.
  • the crosslinked copolymer contains 0 to 20 mol% of constitutive unit C, based on the
  • Total amount of constitutive units of the crosslinked copolymer preferably 0.0001 to 8 mol%, 0.001 to 5 mol%, or 0.01 to 3 mol%, and particularly preferably 0.1 to 2 mol%.
  • the ratio of the sum of the at least one constitutive unit A and the at least one constitutive unit C to the at least one constitutive unit B is suitable
  • the ratio between the sum of the at least one unit A and the at least one unit C is compared to at least one constitutive unit B which is suitable for inserting predetermined breaking points into the main chain of the polymer matrix, selected such that the main chains of the structurally crosslinked polymer matrix are oxidized, preferably hydrolytically, into fragments having a molecular weight between 500 and 6000, preferably between 600 and 3000, more preferably between 700 and 1500 and more preferably between 800 and 1000 are cleaved.
  • the structure-crosslinked polymer matrix of the present invention may comprise 10 to 99.99 mol% of the compound from which a constituent unit A is derived and 0.01 to 50 mol% of the compound from which a constitutive unit B is derived, respectively based on the total content of the used
  • the structure-crosslinked polymer matrix of the present invention comprises 80 to 99.9 mol% of the compound from which a constituent unit A is derived and 0.1 to 40 mol% of the compound from which a constitutive unit B is derived, respectively based on the total content of the monomers used.
  • the structure-crosslinked polymer matrix of the present invention comprises 80 to 99.9 mol% of the compound from which a constituent unit A is derived and 0.1 to 40 mol% of the compound from which a constitutive unit B is derived, respectively based on the total content of the monomers used.
  • the structure-crosslinked polymer matrix of the present invention comprises 80 to 99.9 mol% of the compound from which a constituent unit A is derived and 0.1 to 40 mol% of the compound from which a constitutive unit B is derived, respectively based on the total content of the monomers used.
  • compositions comprise, for example, 88 to 99 mol% of the compound from which a constituent unit A is derived, 1 to 12 mol% of the compound from which a constitutive unit B is derived, and 0.1 to 5 mol% of the compound Compound from which a constitutive unit C is derived, based on the total content of the monomers used.
  • compositions comprise, for example, from 88 to 99 mole% of the compound from which a constituent unit A is derived, from 1 to 12 mole% of the compound from which a constitutive unit B is derived, from 0.1 to 5 mole% of the compound Compound from which a constitutive unit C is derived, and 0.00001 to 10 mol%, preferably 0.1 to 1 mol% of crosslinking agent. based on the total content of the used Monomers.
  • the amounts of the above-mentioned compounds are selected so that the total amount is 100 mol%.
  • the structurally crosslinked polymer matrix of the present invention contains from 10 to 99.99 mole percent of unit A, and from 0.01 to 50 mole percent of unit B, each based on the total content of constitutive units of the structure-crosslinked polymer matrix.
  • the structure-crosslinked polymer matrix of the present invention comprises from 80 to 99.9 mole% of unit A, and from 0.1 to 40 mole% of unit B, each based on the total content of constitutive units of the structure-crosslinked polymer matrix.
  • the structurally crosslinked polymer matrix additionally comprises from 0.001 to 5 mol% of the unit C, based on the total content of the constitutive units of
  • compositions comprise, for example, 88 to 99 mol% of the unit A, 1 to 12 mol% of the unit B derived, and 0.1 to 5 mol% of the unit C, in each case based on the total content of constitutive units of the structure-crosslinked polymer matrix.
  • Further preferred compositions comprise, for example, 88 to 99 mol% of the unit A, 1 to 12 mol% of the unit B derived, 0.1 to 5 mol% of the unit C, and 0.00001 to 10 mol%, preferably 0.1 to 1 mol%, the constitutive unit, the
  • the amounts of the constitutive units mentioned above are selected so that the total amount is 100 mol%.
  • the inorganic particulate solids are chemically and / or physically (a) bound into the structurally crosslinked polymer matrix, e.g. permanently occluded in the pore structure, i. essentially not completely washable.
  • the weight ratio of polymer matrix to inorganic particulate solids may be between 99: 1 and 1:99, preferably between about 90:10 to 10:90, or between about 70:30 to about 30:70.
  • the level of inorganic particulate matter is at least about 30% by weight or 50% by weight, preferably at least about 60% by weight, and more preferably at least about 70 or even at least 80% by weight.
  • the amount of polymer may be at least about 5 weight percent, preferably at least about 10 weight percent, or at least about 20 weight percent, or at least about 30 weight percent.
  • the inorganic particulates may suitably comprise minced minerals or slags or minerals.
  • Suitable inorganic solid particles are, for example, selected from basalt, bentonite, pumice, calcite,
  • the water-absorbing hybrid material may be only one kind of inorganic solid particles or mixtures of several kinds of inorganic ones
  • the water-absorbing material Contain solid particles.
  • the water-absorbing material Contain solid particles.
  • Hybrid material at least two or at least three types of inorganic particulate matter.
  • the hybrid water-absorbing material contains a mixture of sand, bentonite and Eifelgold as inorganic particulates.
  • the particle size of the inorganic solid particles may be the
  • the freeness can be selected so that the inorganic solid particles used have a particle size of greater than 2000 ⁇ , e.g. a particle size greater than 1000 ⁇ , preferably greater than 500 ⁇ and more preferably greater than 250 ⁇ on.
  • the particles are large of the inorganic filler particles in the range of 10 ⁇ to 2000 ⁇ , in particular 10 ⁇ to 1000 ⁇ , preferably 20 ⁇ to 500 ⁇ , more preferably 50 ⁇ to 250 ⁇ ).
  • at least 90%, preferably at least 95%, preferably at least 99%, of the inorganic filler particles are within the aforementioned value ranges.
  • the freeness can be selected such that the particle size of the inorganic solid particles is less than 200 ⁇ m, preferably less than 100 ⁇ m.
  • the hybrid material may be inorganic solid particles such as clay materials such as bentonite,
  • Montmorillonite, phyllosilicates, zeolites, etc. These clay materials may for example have the property to absorb even small amounts of liquid and To bind cations. They can therefore contribute to the strength and swelling behavior of the hybrid material.
  • Their particle sizes may be, for example, between about 100 to 8000 ⁇ , preferably between 300 and 5000 ⁇ . Their proportion may for example be between about 5 wt .-% and 60 wt .-%, based on the total weight of the hybrid material in the dry state.
  • inorganic solids such as feldspar or sand, which are preferably added in the hybrid material according to the invention, are effective above all else
  • this can prevent flooding of the hybrid material according to the invention from the substrate.
  • hybrid material according to the invention may additionally contain, in a minor amount, further solid, optionally finely ground, inorganic or organic
  • the inventive hybrid material water-soluble and / or dissolved in water inorganic additives selected from at least one of alkali metal, potassium silicate, sodium water, alkali metal hydroxide, potassium hydroxide, sodium hydroxide, silica, alkali metal phosphate, alkali nitrate,
  • fertilizers from the group of conventional K, N, P fertilizers and / or trace elements such as iron, zinc, etc. are added to the hybrid material according to the invention, which represent an optimal source of nutrients for plants, and so for example in agricultural or botanical applications can significantly improve the soil structure and soil climate.
  • the properties of the hybrid material according to the invention can be further modified or improved if it additionally water-soluble or dissolved in water, or solid, optionally finely divided, water-insoluble organic additives are added.
  • Suitable organic additives are, for example, urea, uric acid, for example for C0 2 evolution during the polymerization and / or as a fertilizing nitrogen source, guanidine, for example as fertilizer,
  • Microorganisms such as algae, bacteria, yeasts, fungi, fungal spores and the like, e.g. for nutrient supply. Also dyes,
  • Odors may be added, e.g. to improve the sensory properties. It is also possible to add fungicides, pesticides, herbicides and the like to the hybrid material, e.g. an aerosol free, environmentally friendly introduction of the active ingredients close to the roots, possibly with depot effect, or to realize a slow, optionally controlled release.
  • the water-swellable hybrid material of the present invention can be prepared by known polymerization methods.
  • the polymerization in aqueous solution can be carried out as a gel polymerization.
  • the polymerization can be carried out as a radical polymerization initiated by a free radical generator.
  • Suitable free-radical formers are, for example, peroxide compounds, organic peroxides, redox systems, azo initiators or photoinitiators.
  • peroxide compounds are potassium peroxomonosulfate, potassium peroxodisulfate or hydrogen peroxide.
  • organic peroxides are benzoyl peroxide or tert-butyl hydroperoxide.
  • azo initiators are 2,2'-azobis [2- (2-imidazoHn-2-yl) propane] dihydrochloride (VA-044) or azobisisobutyronitrile (AIBN).
  • photoinitiators are benzoin, benzoin ethers, benzil,
  • Acetophenone derivatives and mixtures thereof are Kaliump eroxo di sul fat Natriumdisul fid or
  • Hydrogen peroxide / hydroxylamine chloride this is preferably the
  • AIBN Azobisisobutyronitrile
  • the radical generator can be used in an amount of 0.001 to 5 mol%, based on the total content of monomers.
  • the polymerization reaction can be carried out in a solvent.
  • suitable solvents are, for example, protic-polar solvents, such as water, aqueous solutions, alcohols, such as methanol, ethanol, alkylamines,
  • Tetrahydrofuran, dioxane, and any mixtures thereof Preferably, water is used. Furthermore, these protic-polar solvents
  • Solvents may be used, optionally with the addition of surfactants, emulsifiers or other amphiphilic substances in order to obtain a homogeneous reaction mixture as possible.
  • the reaction solution in addition to the monomers and the radical generator optionally further additives, such as surfactants, are added.
  • additional cyclodextrins can be used in the gel polymerization in aqueous solution.
  • Suitable cyclodextrins are, for example, ⁇ -, ⁇ - or ⁇ -cyclodextrins or cyclodextrin derivatives, such as
  • CAVASOL ® or C AVAMAX ® Particularly suitable are ⁇ -cyclodextrins such as HPBCD (hydroxypropyl- ⁇ -cyclodextrin), HEBCD (hydroxyethyl- ⁇ -cyclodextrin), DIMEB (heptakis (2,6-dimethyl) - ⁇ -cyclodextrin), TRIMEB
  • methylated ⁇ -cyclodextrin or methylated cyclodextrins such as TRIMEB, DIMEB, RAMEB are used.
  • RAMEB randomly methylated RAMEB cyclodextrin (randomly methylated beta cyclodextrin).
  • the cyclodextrins can be used in an amount of 0.001 to 15 mol%, 0.01 to 12 mol% or 0.1 to 10 mol%, based on the total content of monomers, preferably in an amount of 0.4 to 8 mol%.
  • the polymerization temperature depends on the nature of the radical generator used and may for example be between 4 and 150 ° C.
  • the average reaction temperature of the polymerization reaction is maintained between about 50 ° C and 130 ° C, preferably from about 60 to 110 ° C, especially from about 70 to 100 ° C.
  • the starting temperature of the reaction mixture may be adjusted to between about 4 ° C and about 40 ° C, preferably about 10 ° C to about 25 ° C, more preferably 8 to 12 ° C.
  • the polymerization can be carried out in a protective gas atmosphere.
  • Suitable shielding gases are nitrogen or argon.
  • the polymerization can also be carried out under ambient air.
  • the starting compounds can be reacted by various methods. For example, the inorganic solid particles may be initially charged and then the monomers and / or polymerizable components may be added.
  • the method for producing a biodegradable, water-swellable hybrid material comprises the following steps: a) providing an aqueous, alkaline earth carbonate and / or carbon dioxide-containing slurry of inorganic solid particles, the pH of the reaction mixture being equal to or greater than 7, b) addition of at least one olefinically unsaturated carboxylic acid monomer, from which a constitutive unit A is derived, and at least one further monomer, from which a constitutive unit B is derived, into which
  • step a) the slurry is oxidized in addition to avoid lumps
  • the method for producing a biodegradable, water-swellable hybrid material comprises the following steps: a) providing an aqueous slurry of inorganic
  • Solid particles and acid-neutralizing alkali substances the pH of the reaction mixture being equal to or greater than 7, b) addition of at least one olefinically unsaturated carboxylic acid monomer, from which a constitutive unit A is derived, and at least one further monomer, from which a constitutive unit B is derived, into which
  • the method for producing a biodegradable, water-swellable hybrid material comprises the following steps: a) providing a reaction mixture comprising at least one olefinically unsaturated carboxylic acid monomer from which a constitutive unit A is derived, at least one further monomer, of which a constituent unit B is derived, and at least one suitable solvent, wherein the pH of the reaction mixture is less than 7, b) adding inorganic solid particles to the reaction mixture, c) and starting the polymerization reaction.
  • a crosslinker is added after step b) and before starting the polymerization reaction according to step c).
  • suitable Crosslinkers are, for example, compounds of the formula (III) or (V) or
  • crosslinker may also be added before or together with the inorganic solid particles.
  • Heat of reaction is removed continuously to keep the temperature as low as possible.
  • at least partial evaporation of the solvent can be effected so as to increase the volume relative to the volume of the reaction mixture
  • this hybrid material comprises a structure-crosslinked polymer matrix and inorganic solid particles bound therein.
  • this hybrid material has an excellent swelling behavior in particular a significantly faster initial water absorption with excellent mechanical stability in the saturated state.
  • Reaction mixture containing the monomers and / or polymerizable components be less than 7 before adding the inorganic solid particles.
  • the pH is below 6.8, more preferably below 6.5, in particular below pH 6 or below pH 5.
  • the pH of the reaction mixture containing the monomers and / or polymerizable components, prior to the addition of the inorganic Particles between about pH 0 and pH 6, between pH 1 and 5 or between pH 2 and 4.
  • the water-absorbability of the structure-crosslinked polymer matrix is not only greatly affected by the compounds selected, their composition or degree of crosslinking, but also by the degree of neutralization of the polymer. The degree of neutralization indicates how many of those in the polymer
  • Particulate matter may optionally have partial neutralization or pH
  • Adjustment by addition of at least one basic substance e.g. an alkaline earth and / or alkali hydroxide, lime, alkylamines, or ammonia.
  • at least one basic substance e.g. an alkaline earth and / or alkali hydroxide, lime, alkylamines, or ammonia.
  • KOH is used.
  • the solid particles are distributed substantially uniformly in the reaction mixture, wherein the stirring is preferably also continued during the polymerization.
  • the polymerization reaction can be controlled, for example, as described in EP 2168990, so that the hybrid material forms under volume increase relative to the volume of the reaction mixture.
  • the heat of reaction is preferably controlled by suitable measures. For example, by controlling the polymerization reaction, an increase in volume relative to the volume of the reaction mixture prior to onset of the polymerization reaction of at least 10%, preferably at least 20%, more preferably at least 50%, and most preferably at least 100% may be effected.
  • Solid particles as listed above are mixed into the reaction mixture, whereby they are also bound in the polymer matrix.
  • Preferred examples for this purpose, at least one organic substance from the group of
  • Microorganisms bacteria fungi, algae, yeasts, fungicides, pesticides, herbicides, cellulose, starch, derivatives of starches, plastics or polysaccharides, wood, straw, peat, waste paper, chromium-free leather and recycled granules, plastic granules, fibers or nonwovens or mixtures thereof ,
  • At least one water-soluble, water-swellable and / or water-soluble additive as listed above may be added to the reaction mixture.
  • Preferred examples of this may be alkali silicate,
  • Neutralizing agents may be, for example, alkaline earth and / or alkali metal hydroxide, lime, alkylamines, or ammonia, preferably KOH.
  • post-crosslinking may be necessary.
  • the resulting product may be sprayed in a mixer with a post-crosslinking agent.
  • Suitable postcrosslinkers are, for example, solutions of Al 3+ compounds in water or of long-chain diols or long-chain diamines in organic solvents. Examples of postcrosslinkers are
  • Diethylene glycol triethylene glycol, polyethylene glycol, glycerol, polyglycerol, propylene glycol, diethanolamine, triethanolamine or polyoxypropylene.
  • Postcrosslinkers may be present in an amount in the range of 0.001 to 20 mol%, 0.01 to 10 mol% or 0.1 to 5 mol% based on the total content of the monomers used.
  • the postcrosslinking reaction can be carried out at elevated temperature, e.g. at 40, 60, 80 or 100 ° C. Following the postcrosslinking reaction, the product obtained can be dried again and sieved.
  • an after-treatment such as e.g. post-crosslinking, neutralization and the like, usually not required, i. that after this acidic
  • Production method obtained hybrid material can be obtained in a form which is directly suitable for the applications described below.
  • the water-swellable hybrid material according to the present invention may be obtained by suitable selection of the ingredients and / or appropriate process control substantially free of monomer residues, but this need not always be the case.
  • the polymers can be subjected to intensive drying after production to remove monomer residues.
  • a cleaning method as described in EP 2168990 can be used to reduce or remove the residual monomer content in the hybrid material.
  • the hybrid material may be thermally or chemically post-treated, such as by heating the hybrid material in a convection oven, or, more preferably, with superheated steam at temperatures of about 100 to about 150 ° C, optionally under pressure.
  • the water-swellable hybrid material is in
  • the term "substantially free of residual monomers” means a material which has a residual monomer content of less than 2000 ppm, eg less than 1000 ppm, preferably less than 500 ppm and more preferably less than 300 ppm, optionally even less than 100 ppm or less than 50 ppm.
  • hybrid material may alternatively or additionally also be used for postcrosslinking, for partial hydrolysis and / or simply for drying or for setting a defined residual moisture content of the hybrid material.
  • the hybrid material after its preparation in an aqueous medium a residual moisture content at 20 ° C of at least about 0.1 wt .-%, based on the total weight of the residual wet material, preferably up to about 60 wt .-%, more preferably about 20 to 40 Wt .-%, in particular about 35 wt .-% exhibit. This can be adjusted by partial drying according to the desired requirements.
  • Hybrid material according to the invention for a variety of applications advantageous mechanical properties.
  • the thermoplastic material for a variety of applications advantageous mechanical properties.
  • Hybrid material after one hour of air drying of the hybrid material at 40 ° C a Shore A hardness (according to DIN 53505) of at least about 25, preferably about 30 to 50, have.
  • a Shore A hardness according to DIN 53505
  • the hybrid material may additionally or alternatively have a Shore A hardness (DIN 53505) of at least about 15, preferably about 20 to 30, have. Furthermore, in the saturated state after storage of the material for 24 hours in demineralized water, the hybrid material may additionally or alternatively still have a Shore A hardness (DIN 53505) of at least about 1, preferably about 2 to 10.
  • the specific gravity of the hybrid material is, depending on the solid particles and / or polymeric constituents used, at least 0.3 g cm 3 , preferably between about 0.3 and 0.9 g cm 3 , preferably between about 0.4 and 0 , 7 g / cm 3 .
  • the water-swellable hybrid material according to the invention differs from conventional materials in its production and composition.
  • it has a high swellability and is directly comparable in the undried, residual moist state, for example, with humus.
  • a suction effect may occur which may cause liquid absorption beyond the absorbency of the polymer matrix.
  • the hybrid material according to the invention has according to an exemplary
  • Embodiment of the invention at a time-dependent swelling behavior Room temperature, ie, about 20 to 22 ° C, which corresponds to a water absorption of at least 7.5 times the intrinsic weight of the dry hybrid material within one hour, preferably at least 10 times, preferably 12.5 times, more preferably at least 15 times the net weight of the dry hybrid material within the first hour.
  • the water uptake of the hybrid material may be at least 10 times the net weight of the dry hybrid material, preferably at least 12.5 times, preferably 15 times, more preferably at least 17.5 times the weight of the dry hybrid material .
  • the water uptake of the hybrid material may be at least 12.5 times the net weight of the dry hybrid material, preferably at least 15 times, preferably 17.5 times, more preferably at least 20 times the net weight of the dry hybrid material .
  • the water absorption of the hybrid material after 24 h is at least 15 times, preferably 20 times, preferably at least 25 times, more preferably at least 30 times the intrinsic weight of the dry
  • Hybrid material and may be more than 50 times, the
  • Hybrid material does not assume gel consistency.
  • the water-swellable hybrid material produced according to the invention is usually in the form of blocks or larger pieces and may be in front of the other
  • the blocks or large pieces may be cut to form slices, mats, or smaller blocks.
  • a variety of shapes can be obtained from the mats thus obtained by further cutting or punching.
  • square sticks can be produced, which later add the plant roots for growth supply the necessary mineral and fertilizer requirements when they are put into their food area.
  • a shredder which the production of earthy crumbs arbitrarily adjustable particle size is directly possible, which may be adapted in appearance and texture of humus. In the fresh state production can still be a certain stickiness, which can be used to mix more solids and the
  • the hybrid material according to the invention can be used in a variety of ways as a soil additive, for example in granule or crumb form.
  • a soil additive for example in granule or crumb form.
  • it can in a suitable amount in soil, sand, humus, peat and the like mixed by its water absorption and storage capacity to promote the germination, growth and cultivation of plants, and so even when admixed with unfavorable soils in poor weather conditions good planting results ,
  • the porous, sponge-like structure of the hybrid material of the present invention can improve soil capillarity while positively affecting soil quality by the presence of finely ground minerals, especially finely ground sand.
  • the mineral content of the hybrid materials is a weighting of the product such that e.g. one
  • hybrid material according to the invention is in the admixture in soils in arid regions for water storage. It is possible to use the hybrid material of the invention alone
  • a special embodiment for this is the use of products in plant containers, which are connected to a water reservoir, for example, by capillary rods that make up the
  • Product sponges bring the water taken from them through the plant roots.
  • the hybrid material according to the invention can serve as a carrier material for a wide variety of solid and liquid products. So it can not only be used as a water reservoir and
  • Nutrient source but also as a depot material for the environmentally friendly introduction of fungicides, herbicides, pesticides, etc. are used by being charged before use in the soil with the appropriate substances.
  • the crumbs of the hybrid material according to the invention with its pores and pockets are excellently suitable as a carrier for a wide variety of solids.
  • the hybrid material can be subsequently mixed with castor meal, which is obtained in the production of castor oil and is one of the solid fertilizers.
  • castor meal which is obtained in the production of castor oil and is one of the solid fertilizers.
  • rapeseed meal a residual product of rapeseed oil production, may be used instead of castor meal. Mixtures of these and other Ol allungsschrot Wegnecknote are of course also usable.
  • the hybrid material according to the invention can also be used as slurry slurry or
  • the hybrid material can be combined with wood flour or wood shavings, which can then be used dried as "animal litter" for animal husbandry, for example in ungulates.
  • Fabrics or nonwovens can be equipped free of crystals and used wherever water-absorbent products need to be bound and / or fixed. These include slope greenery, supplements for the transport of goods and contributions in kind.
  • crumb-containing fabrics and nonwovens can additionally be provided with floatable natural and synthetic materials, such as in
  • hybrid material according to the invention can also be used in the hygiene sector, for example in the cosmetics or wellness sector, wherein e.g. the
  • Hybrid material can be used as a component of fango packs, moor or mud baths, or for mineral packs such as mineral-based facial or body masks. Moreover, due to its high specific gravity and its water absorption and swelling capacity, the water-swellable hybrid material can be incorporated into
  • Sealing applications can be used, such as as an additive in systems for well sealing e.g. in oil wells, as a component in sandbags for dyke repair or elevation, as a cable protection agent to destroy the destructive
  • the swellability of the copolymers produced is defined as the uptake of liquid in grams per gram weight of the hybrid material in the
  • Demineralized water was used as the test solution.
  • the tea bag test is carried out as follows: 1 g of the sample (original state) is placed in a tea bag with a size of 80x120 mm and the teabag sealed. Then it is completely immersed in a beaker filled with demineralised water. After the scheduled time, e.g. after 24 hours, the tea bag is removed, drained on a glass rod for 30 minutes and weighed. The amount of water absorbed by the product then results as the difference between the weight of the tea bag before and after the swelling process, whereby the water taken up by the pure tea bag must be taken into account. Taking into account the water content of the product used, the swellability of the dry product can be determined. The specified
  • the residual monomer content is determined by HPLC and always refers to the dry product.
  • the viscosity was determined using a HAAKE MARS II Rheometer (Thermo Fisher Scientific Inc.) at a temperature of 23 ° C.
  • PP35 Ti Cone -Platte- structure
  • Betspiel 1 Polymerization of acrylic acid with adipic acid bis [2- (2-methyl-acryloyloxy) ethyl] ester
  • Neutralization degree is 40%.
  • the reaction mixture is stirred and cooled to 10 ° C.
  • the reaction is started by adding 1.3 g of sodium peroxodisulfate dissolved in 10 ml of water and 0.1 g of sodium disulphite dissolved in 2 ml of demineralized water. The maximum temperature of the reaction is reached after about 5 min. After this
  • the residual monomer content is below 1000 ppm.
  • the swellability of the dry product in demineralized water, measured after 24 hours of swelling, is 49 g / g.
  • Example 2 Polymerization of acrylic acid with adipic acid bis [2- (2-methyl-acryloyloxy) ethyl] ester
  • Neutralization degree is 30%.
  • the reaction mixture is purged with argon for 15 minutes.
  • 1.3 g of sodium peroxodisulfate dissolved in 10 ml of deionized water and 0.1 g of sodium disulfite dissolved in 2 ml of deionized water the reaction is started. After 30 minutes, the reaction is already over, as the reaction mixture becomes highly viscous. The product obtained is crushed and dried.
  • the swellability of the dry product in demineralized water, measured after 24 hours of swelling, is 105 g.
  • Example 3 Polymerization of acrylic acid with adipic acid bis [2- (2-methyl-acryloyloxy) ethyl] ester
  • Adipic acid bis [2- (2-methyl-acryloyloxy) ethyl] ester (1 mmol) was added and stirred. Then, 72 g of acrylic acid (1.0 mol) are added.
  • the residual monomer content is below 1000 ppm.
  • the swellability of the dry product in demineralized water, measured after 24 hours of swelling, is 79 g / g.
  • Example 4 Polymerization of acrylic acid with adipic acid bis [2- (2-methyl-acryloyloxy) ethyl] ester and 2-methylene-1,3-dioxalane
  • the swellability of the dry product in deionized water, measured after 24 hours of swelling, is 20.4 g / g.
  • Example 5 Polymerization of acrylic acid with adipic acid bis [2- (2-methyl-acryloyloxy) ethyl] ester, 2-methylene-1,3-dioxalane and buntandioldiacrylate
  • Adipic acid bis [2- (2-methyl-acryloyloxy) ethyl] ester (1 mmol)
  • 12 g of 2-methylene-1,3-dioxalane 140 mmol
  • 0.15 g of buntandioldiacrylate 0.15 mmol
  • the swellability of the dry product in deionized water is 66 g / g. Hydro lyric degradation
  • Example 6 Polymerization of acrylic acid with adipic acid bis [2- (2-methyl-acryloyloxy) ethyl] ester, 2-methylene-1,3-dioxalane and buntandioldiacrylate
  • Adipic acid bis [2- (2-methyl-acryloyloxy) ethyl] ester (1 mmol), 24 g 2-methylene-1,3-dioxalane (280 mmol) and 0.15 g of buntandioldiacrylate (0.8 mmol) added and stirred.
  • the swellability of the dry product in deionized water, measured after 24 hours of swelling, is 76 g. Hydrolytic degradation
  • Example 7 Comparison of the hydrolytic degradability of the hybrid material according to the invention and a comparison hybrid material
  • Sample A (prior art): Commercially available hybrid material from butanediol acrylate-crosslinked acrylic acid and rock flour
  • Sample B (according to the invention): Hybrid material according to Example 6 Hydrolytic degradation
  • the hybrid material of the invention exhibits a significantly lower viscosity compared to the prior art hybrid material (Sample A) which does not have a biodegradable polymer matrix.
  • the lower viscosity of the sample B compared to the sample A shows that the hybrid material according to the invention is readily hydrolytically degradable.

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Abstract

La présente invention concerne une matière hybride gonflant au contact de l'eau et comprenant une matrice polymère réticulée biodégradable à l'intérieur de laquelle sont liées des particules minérales solides, la matrice polymère réticulée présentant au moins une zone de rupture apte au craquage biologique dans la chaîne principale de la matrice polymère. La matrice polymère réticulée comprend au moins une unité constitutive A, l'unité A étant dérivée d'un acide carboxylique oléfiniquement insaturé, et au moins une autre unité constitutive B, l'unité B convenant pour introduire au moins une zone de rupture apte au craquage biologique dans la matrice polymère réticulée.
PCT/EP2011/057647 2010-05-11 2011-05-11 Matière hybride biodégradable gonflant au contact de l'eau WO2011141526A1 (fr)

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CN103922434A (zh) * 2014-04-10 2014-07-16 北京工业大学 一种天然多孔基材的吸附-絮凝剂制备方法
CN104788604A (zh) * 2014-01-22 2015-07-22 亿利资源集团有限公司 一种生态保湿蓄水复合材料及其制备方法
EP3228679A1 (fr) * 2016-04-04 2017-10-11 Geohumus GmbH Matériau hybride
WO2020102227A1 (fr) * 2018-11-13 2020-05-22 Green Polymers Ltd. Composition polymère destinée à être utilisée en tant qu'amendement de sol présentant une capacité d'absorption d'eau améliorée pendant l'arrosage des cultures agricoles
CN112175173A (zh) * 2020-10-09 2021-01-05 中国科学技术大学 一种烯烃插入率可控的可降解聚α-烯烃材料的制备方法
CN117447649A (zh) * 2023-12-06 2024-01-26 成都理工大学 一种凝胶颗粒封堵剂体系及制备方法

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CN104788604A (zh) * 2014-01-22 2015-07-22 亿利资源集团有限公司 一种生态保湿蓄水复合材料及其制备方法
CN104788604B (zh) * 2014-01-22 2017-01-25 亿利资源集团有限公司 一种生态保湿蓄水复合材料及其制备方法
CN103922434A (zh) * 2014-04-10 2014-07-16 北京工业大学 一种天然多孔基材的吸附-絮凝剂制备方法
EP3228679A1 (fr) * 2016-04-04 2017-10-11 Geohumus GmbH Matériau hybride
WO2020102227A1 (fr) * 2018-11-13 2020-05-22 Green Polymers Ltd. Composition polymère destinée à être utilisée en tant qu'amendement de sol présentant une capacité d'absorption d'eau améliorée pendant l'arrosage des cultures agricoles
CN113272406A (zh) * 2018-11-13 2021-08-17 聚合物绿色有限责任公司 在农作物浇水期间吸水性提高的用作土壤改良剂的聚合物组合物
CN112175173A (zh) * 2020-10-09 2021-01-05 中国科学技术大学 一种烯烃插入率可控的可降解聚α-烯烃材料的制备方法
CN112175173B (zh) * 2020-10-09 2022-04-19 中国科学技术大学 一种烯烃插入率可控的可降解聚α-烯烃材料的制备方法
CN117447649A (zh) * 2023-12-06 2024-01-26 成都理工大学 一种凝胶颗粒封堵剂体系及制备方法
CN117447649B (zh) * 2023-12-06 2024-04-02 成都理工大学 一种凝胶颗粒封堵剂及制备方法

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