WO2010037631A1 - Réduction de l'évapotranspiration de plantes soumises à un stress hydrique au moyen d'agents superabsorbants - Google Patents

Réduction de l'évapotranspiration de plantes soumises à un stress hydrique au moyen d'agents superabsorbants Download PDF

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Publication number
WO2010037631A1
WO2010037631A1 PCT/EP2009/061910 EP2009061910W WO2010037631A1 WO 2010037631 A1 WO2010037631 A1 WO 2010037631A1 EP 2009061910 W EP2009061910 W EP 2009061910W WO 2010037631 A1 WO2010037631 A1 WO 2010037631A1
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Prior art keywords
superabsorbent
water
medium
polymerization
plants
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PCT/EP2009/061910
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German (de)
English (en)
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Aloys HÜTTERMANN
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Basf Se
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    • 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
    • C09K17/14—Soil-conditioning materials or soil-stabilising materials containing organic compounds only
    • C09K17/18—Prepolymers; Macromolecular compounds
    • C09K17/20—Vinyl polymers
    • C09K17/22—Polyacrylates; Polymethacrylates
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G7/00—Botany in general
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G24/00—Growth substrates; Culture media; Apparatus or methods therefor
    • A01G24/30—Growth substrates; Culture media; Apparatus or methods therefor based on or containing synthetic organic compounds
    • A01G24/35—Growth substrates; Culture media; Apparatus or methods therefor based on or containing synthetic organic compounds containing water-absorbing polymers

Definitions

  • the present invention relates to the field of plant cultivation, in particular under arid, semi-arid or other low-water conditions.
  • the survival of plants in semi-arid areas depends on the plants surviving the dry phases between precipitation.
  • the rate of evapotranspiration - the water loss of the plant-soil system to the surrounding air - is crucial, the higher the likelihood that the plant will survive the dry period.
  • the task is thus to create a possibility of reducing evapotranspiration in the cultivation of plants.
  • the superabsorbent is added to a growth medium or the growth medium comprises the superabsorber.
  • superabsorbent in the sense of the present invention means or comprises in particular optionally water-containing, but water-insoluble polymers whose molecules are chemically bonded, for example by covalent or ionic bonds, or physically, eg by looping of the polymer chains Three-dimensional network are linked and which are able to swell with the addition of water or aqueous solutions under volume increase.
  • promotion of drought resistance includes in particular the reduction / reduction of the evapotranspiration of the system "plant soil”.
  • lowering of evapotranspiration is understood in particular to mean a reduction in evapotranspiration (in g / d) of> 5%, preferably> 10%, more preferably> 20% and most preferably> 30% compared to a control.
  • the evapotranspiration can be measured, for example gravimetrically or by other methods known in the art.
  • survival rate under dry conditions includes in particular an increase in the survival rate (in days) without water supply by> 20%, preferably> 40%, more preferably> 80% and most preferably> 100% compared to a control.
  • growing medium includes and / or in the simplest case includes, but is not limited to, the soil in which the respective plants are reared,
  • the growing medium may also be, for example, a hydroponic or a soil-free growing medium.
  • Preferred as rearing medium are mixtures of sand, silt and clay in the fine soil with different Bodenskelettan worrying the total soil.
  • plants includes and / or includes in particular and insofar preferably also all the shoot plants, furthermore in particular and insofar also preferably all useful and ornamental plants, cereals, grasses and trees.
  • Preferred shoot plants are those from the classes of Pinopsida, Dicotyledoneae and Monocotyledoneae. This concerns in particular trees from the class of the Pinopsida, subclass Coniferae; Trees and ornamental plants of the genus Dicotyledoneae, subclasses Hamamelidae, Rosidae, Dilleniidae, Lamiidae, ornamentals and cereals of the genus Monocotyledonae, subclass Liliidae and Arecidae.
  • the most preferred grasses are the species and varieties: Lolium perenne Poa pratensis L. Varieties 'Award,' 'Liberator,' 'Chicago II,' 'Rambo,' 'NuBlue' Poa annua var. Reptans Hausskn. Festuca arundinacea L. 'Barlexus'
  • Vegetative cultivars included TiftNo.3 ', Tift No, 4', Tifway, Midlawn 1 , Tifsport, MS-Choice, Aussie Green, GN-1, Premier, Ashmore, Patriot, OKC 70-18, and Celebration .'Transcontinental '. Aussie Green, MS-Choice, Princess 77, SWI-045, SWI-1041, and SWI-1012. SWI-1014, Arizona Common, Sundevil, SR9554, GN-1, and Patriot. Zoysia japonica cv. Lanyin 'Manila', ⁇ 'Crowne', Z. japonica Steud., 'EIToro', Z.
  • japonica Steud. 'Meyer', 'Cavalier' [Z. matrella (L.) Merr.], Hemar thria compressa (L. f) R. Br. Dactylis glomerata L. Agrostis stolonifera L. 'Penn A-4';"Penncross", Agrostis canina L. 'Vesper', '7001', and 'Penn A-4', Agrostis capillaris' Leikvin ','Nor'Lolitan perenne Microlaena stipoides (Labill.) R.Br var. Stipoides.
  • the superabsorbent is in the culture medium, i. In most cases, this is incorporated into the soil before the plants are grown. However, during the actual rearing, apart from thorough irrigation prior to planting, most of the applications of the present invention usually require no special steps or precautions. Thus, promotion of water use efficiency and / or drought resistance and / or survival through efficient and straightforward measures is possible.
  • the use or the method is suitable for automation as well as for use on a large scale, even if in principle the use and / or the method is not limited thereto.
  • the present invention does not affect significantly, in particular no damage to the environment.
  • the increased growth occurs after a short time, i. after one or two months is detectable.
  • an advantageous and insofar preferred embodiment of the present method involves that the superabsorbent is present in the growth medium in a concentration of> 0.1% to ⁇ 1% (dry matter / weight of the dry medium). This has proven particularly useful in practice. Particularly preferred is the range of> 0.2% to ⁇ 0.8%, more preferably> 0.3% to ⁇ 0.7%, and most preferably> 0.4% to ⁇ 0.6%.
  • > 90% of the superabsorber is at a depth of> 0 to ⁇ 50 cm.
  • the superabsorber which is used in the form of a dry powder, transforms into a gel when it absorbs liquid, with the usual absorption of water corresponding to a superabsorber.
  • Crosslinking is essential for synthetic superabsorbents and an important difference to conventional pure thickeners, as it leads to the insolubility of the polymers in water. Soluble substances would not be useful as superabsorbent.
  • superabsorbents are used, for example, in infant diapers, adult incontinence products or feminine hygiene products.
  • Other fields of application are, for example, those used as water-retaining agents in agricultural horticulture, as water storage for protection against fire, for liquid absorption in food packaging or, more generally, for the absorption of moisture.
  • Superabsorbents can absorb a multiple of their own weight of water and retain it under some pressure.
  • such a superabsorbent has a CRC ("Centrifuge Retention Capacity", measuring method see below) of at least 5 g / g, preferably at least 10 g / g and in a particularly preferred form at least 15 g / g. may also be a mixture of materially different individual superabsorber or a mixture of components that show superabsorbent properties only in combination, it comes here less on the material composition than on the superabsorbent properties.
  • Swollen gel can hinder liquid transport to superabsorbers that have not yet swollen ("gel blocking")
  • Good transport properties for liquids are possessed, for example, by superabsorbents which have a high gel strength in the quenched state
  • Gels with only low gel strength are under an applied pressure ( Increased gel strength is usually achieved by a higher degree of cross-linking, which however reduces the absorption capacity of the product
  • An elegant method for increasing the gel strength is to increase the degree of cross-linking in the gel Surface of the superabsorbent particles in relation to the interior of the particles.
  • dried superabsorber particles having an average crosslinking density are usually additionally crosslinked in a thin top layer surface layer of their particles subjected.
  • crosslinked hydrophilic polymers in particular polymers of (co) polymerized hydrophilic monomers, graft (co) polymers of one or more hydrophilic monomers on a suitable graft, crosslinked cellulose or starch ethers, crosslinked carboxymethylcellulose, partially crosslinked polyalkylene oxide or swellable in aqueous liquids natural products, such as guar derivatives understood.
  • the at least one superabsorbent has a swelling capacity in distilled water of at least> 80 g / g, preferably at least> 120 g / g and in a particularly preferred form at least> 180 g / g and a CRC ("Centrifuge Retention Capacity") of at least> 40 g / g, preferably at least> 80 g / g and in a particularly preferred form at least> 100 g / g.
  • a swelling capacity in distilled water of at least> 80 g / g, preferably at least> 120 g / g and in a particularly preferred form at least> 180 g / g and a CRC ("Centrifuge Retention Capacity") of at least> 40 g / g, preferably at least> 80 g / g and in a particularly preferred form at least> 100 g / g.
  • the at least one superabsorber is preferably obtained by polymerization of a monomer solution containing
  • Suitable monomers a) are, for example, ethylenically unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, or derivatives thereof, such as acrylamide, methacrylamide, acrylic esters and methacrylic acid esters. Particularly preferred monomers are acrylic acid and methacrylic acid. Very particular preference is given to acrylic acid.
  • Preferred hydroquinone half ethers are hydroquinone monomethyl ether (MEHQ) and / or tocopherols.
  • MEHQ hydroquinone monomethyl ether
  • Tocopherol is understood in particular to mean compounds of the following formula
  • R 3 is hydrogen or methyl
  • R 4 is hydrogen or methyl
  • R 5 is hydrogen or methyl
  • R 4 is hydrogen or an acid radical having 1 to 20 carbon atoms.
  • Preferred radicals for R 6 are acetyl, ascorbyl, succinyl, nicotinyl and other physiologically acceptable carboxylic acids.
  • the carboxylic acids can be mono-, di- or tricarboxylic acids.
  • R 6 is particularly preferably hydrogen or acetyl. Especially preferred is RRR-alpha-tocopherol.
  • the monomer solution preferably contains at most 130 ppm by weight, more preferably at most 70 ppm by weight, preferably at least 10 ppm by weight, more preferably at least 30 ppm by weight, in particular by 50 ppm by weight, hydroquinone, in each case based on Acrylic acid, wherein acrylic acid salts are taken into account as acrylic acid.
  • an acrylic acid having a corresponding content of hydroquinone half-ether can be used.
  • the crosslinkers b) are compounds having at least two polymerizable groups which can be incorporated in the polymer network by free-radical polymerization.
  • Suitable crosslinkers b) are, for example, ethylene glycol dimethacrylate, diethylene glycol diacrylate, allyl methacrylate, trimethylolpropane triacrylate, triallylamine, tetraallyloxyethane, di- and triacrylates, mixed acrylates which, in addition to acrylate groups, contain further ethylenically unsaturated groups, or crosslinker mixtures.
  • Suitable crosslinkers b) are especially N, N'-methylenebisacrylamide and N thylenbismethacrylamid 1 NT-Me, esters of unsaturated mono- or polycarboxylic acids of poly- ols, such as diacrylate or triacrylate, for example butanediol or Ethylenglykoldiacry- lat and also trimethylolpropane triacrylate and allyl compounds, such as allyl (meth) acrylate, triallyl cyanurate, maleic acid diallyl esters, polyallyl esters, tetraallyloxyethane, triallylamine, tetraallylethylenediamine, allyl esters of phosphoric acid and vinylphosphonic acid derivatives, as described, for example, in EP 343 427 A2.
  • crosslinkers b) are pentaerythritol di-, pentaerythritol tri- and pentaerythritol tetraallyl ethers, polyethylene glycol diallyl ether, ethylene glycol diallyl ether, glycol. cerindi- and glycerol triallyl ethers, polyallyl ethers based on sorbitol, and ethoxylated variants thereof.
  • Useful in the process according to the invention are di (meth) acrylates of polyethylene glycols, wherein the polyethylene glycol used has a molecular weight between 300 and 1000.
  • crosslinkers b) are di- and triacrylates of 3 to 15 times ethoxylated glycerol, of 3 to 15 times ethoxylated trimethylolpropane, of 3 to 15 times ethoxylated trimethylolethane, especially di- and triacrylates of 2 to 6-times ethoxylated glycerol or trimethylolpropane, the 3-fold propoxylated glycerol or trimethylolpropane, and the 3-fold mixed ethoxylated or propoxylated glycerol or trimethylolpropane, the 15-fold ethoxylated glycerol or trimethylolpropane, and the 40-times ethoxylated glycerol, trimethylolethane or trimethylolpropane.
  • Very particularly preferred crosslinkers b) are polyethoxylated and / or propoxylated glycerols which have been esterified with acrylic acid or methacrylic acid to give di- or triacrylates.
  • Particularly advantageous are di- and / or triacrylates of 3- to 10-fold ethoxylated glycerol.
  • diacrylates or triacrylates of 1 to 5 times ethoxylated and / or propoxylated glycerol.
  • Most preferred are the triacrylates of 3 to 5 times ethoxylated and / or propoxylated glycerol.
  • acrylamide, methacrylamide, crotonamide, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminopropyl acrylate, diethylaminopropyl acrylate, dimethylaminobutyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoneopentyl acrylate and dimethylaminoneopentyl methacrylate are monomers which can be copolymerized with the monomers a).
  • polyvinyl alcohol polyvinylpyrrolidone
  • starch starch derivatives
  • polyglycols polymers fully or partially formulated from vinylamine monomers, such as partially or completely hydrolyzed polyvinylamide (so-called "polyvinylamine”) or polyacrylic acids, preferably polyvinyl alcohol and starch.
  • Suitable polymerization regulators are, for example, thio compounds, such as thioglycolic acid, mercaptoalcohols, for.
  • the monomers (a), (b) and optionally (c) are, optionally in the presence of water-soluble polymers d), in 20 to 80, preferably 20 to 50, in particular 30 to 45 wt .-% aqueous solution in the presence of polymerization initiators (co) polymerized with each other.
  • polymerization initiators it is possible to use all compounds which decompose into free radicals under the polymerization conditions, eg. As peroxides, hydroperoxides, hydrogen peroxide, persulfates, azo compounds and the so-called redox initiators. Preference is given to the use of water-soluble initiators. In some cases, it is advantageous to use mixtures of different polymerization initiators, eg. B.
  • Suitable organic peroxides are, for example, acetylacetone peroxide, methyl ethyl ketone peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-amyl perpivalate, tert-butyl perpivalate, tert-butyl perohexanoate, tert-butyl perisobutyrate, tert-butyl per-2-ethylhexanoate tert-butyl perisononanoate, tert-butyl permaleate, tert-butyl perbenzoate, tert-butyl per 3,5,5-tri-methylhexanoate and tert-amylperneodecanoate.
  • Suitable polymerization initiators are azo initiators, e.g. 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis (N, N-dimethylene) isobutyramidine dihydrochloride, 2- (carbamoylazo) isobutyronitrile and 4,4'-azobis - (4-cyanovaleric acid).
  • azo initiators e.g. 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis (N, N-dimethylene) isobutyramidine dihydrochloride, 2- (carbamoylazo) isobutyronitrile and 4,4'-azobis - (4-cyanovaleric acid).
  • the polymerization initiators mentioned are used in conventional amounts, for. B. in amounts of 0.01 to 5, preferably 0.1 to 2 mol%, based on the monomers to be polymerized.
  • the redox initiators contain as oxidizing component at least one of the abovementioned per compounds and a reducing component, for example ascorbic acid, glucose, sorbose, ammonium or alkali metal hydrogen sulfite, sulfite, thiosulfate, hyposulfite, pyrosulfite or sulfide, metal salts such as iron-II ions or silver ions or sodium hydroxymethylsulfoxylate.
  • reducing component of the redox initiator ascorbic acid or sodium pyrosulfite is preferably used.
  • these components are used in the concentrations 1 ⁇ 10 "2 mol% hydrogen peroxide, 0.084 mol% Natriumperoxo- disulfate and 2,5 ⁇ 10" used 3 mol% based on the monomers ascorbic acid.
  • the aqueous monomer solution may contain the initiator dissolved or dispersed. However, the initiators can also be fed to the polymerization reactor separately from the monomer solution.
  • the preferred polymerization inhibitors require dissolved oxygen for optimum performance. Therefore, the polymerization inhibitors before the polymerization by inerting, ie, flowing through with an inert gas, preferably nitrogen, are freed of dissolved oxygen. This is done by means of inert gas, which can be introduced in cocurrent, countercurrent or intermediate inlet angles. Good mixing can be achieved, for example, with nozzles, static or dynamic mixers or bubble columns.
  • the oxygen content of the monomer solution before polymerization is reduced to less than 1 ppm by weight, more preferably less than 0.5 ppm by weight.
  • the monomer solution is optionally passed through the reactor with an inert gas stream.
  • the at least one superabsorber is preferably obtained by polymerization of an aqueous monomer solution and optionally subsequent comminution of the superabsorber.
  • Suitable preparation methods are e.g.
  • Emulsion polymerization in which bead polymers of relatively narrow gel size distribution are already produced.
  • In-situ polymerization of a fabric layer which was sprayed previously in continuous operation previously with aqueous monomer solution and then subjected to photopolymerization.
  • the reaction is preferably carried out in a kneader or on a belt reactor.
  • a particularly preferred process within the scope of this invention is continuous gel polymerization.
  • a monomer mixture is first prepared by the neutralization agent, optional comonomers and / or other auxiliaries are added to the acrylic acid solution in temporally and / or spatially separate addition sequence, and the mixture is then transferred to the reactor, or is already presented in the reactor. The last addition is the metering of the initiator system to start the polymerization.
  • the reaction takes place to the polymer gel (ie, in the solvent of the polymerization - usually water - swollen to the gel polymer), which is already comminuted in the case of a stirred polymerization in advance.
  • the polymer gel is then dried, if necessary, also crushed and sieved and transferred for further surface treatment.
  • the acid groups of the superabsorbents obtained are usually partially neutralized, generally at least> 25 mol%, preferably at least> 27 mol% and in a particularly preferred form at least> 40 mol% and in general at most ⁇ 85 mol% , preferably at most ⁇ 80 mol% and in a particularly preferred form at most ⁇ 75 mol%, to which the customary neutralizing agents can be used, preferably alkali metal hydroxides, alkali metal oxides, alkali metal carbonates or alkali metal bicarbonates and mixtures thereof. Instead of alkali metal salts and ammonium salts can be used.
  • Sodium and potassium are particularly preferred as alkali metals, most preferably, however, sodium hydroxide, sodium carbonate or sodium bicarbonate and mixtures thereof.
  • the neutralization is achieved by mixing the neutralizing agent as an aqueous solution or preferably as a solid.
  • sodium hydroxide with a water content significantly below ⁇ 50 wt .-% may be present as a waxy mass with a melting point above> 23 ° C. In this case, a dosage as general cargo or melt at elevated temperature is possible.
  • the neutralization can be carried out after the polymerization at the hydrogel stage. However, it is also possible to carry out the neutralization to the desired degree of neutralization completely or partially before the polymerization.
  • partial neutralization before the polymerization generally at least> 10 mol%, preferably at least> 15 mol% and generally at most ⁇ 40 mol%, preferably at most ⁇ 30 mol% and in a particularly preferred form at most ⁇ 25 mol% % of the acid groups in the monomers used before polymerization neutralized by a part of the neutralizing agent is already added to the monomer solution.
  • the desired final degree of neutralization is in this case set only towards the end or after the polymerization, preferably at the stage of the hydrogel before it is dried.
  • the monomer solution is neutralized by mixing in the neutralizing agent.
  • the superabsorber can be comminuted mechanically during neutralization, for example by means of a meat grinder or similar apparatus for comminuting gelatinous masses, wherein the neutralizing agent is sprayed, sprinkled or poured over and then carefully mixed in.
  • the gel mass obtained can be further gewolfft for homogenization.
  • the monomer solution is adjusted to the desired final degree of neutralization prior to polymerization by addition of the neutralizing agent.
  • the gels obtained from the polymerization are optionally for some time, for example at least> 30 minutes, preferably at least> 60 minutes and more preferably at least> 90 minutes and generally at most ⁇ 12 hours, preferably at most ⁇ 8 hours, and most preferably Mold at most ⁇ 6 hours at a temperature of generally at least > 50 0 C and preferably at least> 70 0 C and generally at most ⁇ 130 0 C and preferably kept at most ⁇ 100 0 C, whereby their properties can often be improved.
  • the neutralized superabsorber is then dried with a belt or drum dryer until the residual moisture content is preferably below 15% by weight, in particular below 10% by weight, the water content being that recommended by EDANA (European Disposables and Nonwovens Association) Test Method No. 430.2-02 "Moisture Content" is determined.
  • the dry superabsorbent consequently contains up to ⁇ 15% by weight of moisture, preferably at most ⁇ 10% by weight.
  • Decisive for the classification as "dry” is in particular for handling as a powder (for example for pneumatic conveying, filling, screening or other process steps from the solid process technology) sufficient flowability Alternatively, for drying but also a fluidized bed dryer or a heated ploughshare shear can be used.
  • ⁇ 80 wt .-% is.
  • Particularly advantageous is the ventilation of the dryer with nitrogen or other non-oxidizing inert gas.
  • sufficient ventilation and removal of the water vapor also lead to an acceptable product.
  • Advantageous in terms of color and product quality is usually the shortest possible drying time.
  • the dried hydrogel (which is no more gel - even if so often called) - but a dry polymer with superabsorbent properties, which falls under the term "superabsorbent”) is preferably ground and sieved, wherein for milling usually roller mills, pin mills, hammer mills,
  • the particle size of the sieved, dry superabsorber is preferably below ⁇ 1000 ⁇ m, particularly preferably below ⁇ 900 ⁇ m, very particularly preferably below ⁇ 850 ⁇ m, and preferably above ⁇ 800 ⁇ m, particularly preferably above> 90 ⁇ m, most preferably over> 100 microns. Very particular preference is given to a particle size (sieve cut) of> 106 to ⁇ 850 ⁇ m.
  • the particle size is determined according to the test method No. 420.2-02 "Particle size distribution" recommended by the EDANA (European Disposables and Nonwovens Association).
  • the superabsorbent polymers prepared in this way are usually referred to as "base polymers” and are preferably subsequently surface-postcrosslinked Surface postcrosslinking can be carried out in a manner known per se with dried, ground and screened polymer particles react under crosslinking, usually in the form of a solution applied to the surface of the base polymer particles.
  • Di- or polyepoxides for example di- or polyglycidyl compounds, such as phosphonic acid diglycidyl esters, ethylene glycol diglycidyl ethers or bischlorohydrin ethers of polyalkylene glycols,
  • Polyaziridines compounds containing aziridine units based on polyethers or substituted hydrocarbons, for example bis-N-aziridino methane,
  • Polyols such as ethylene glycol, 1, 2-propanediol, 1, 4-butanediol, glycerol, methyltriglycol, polyethylene glycols having an average molecular weight Mw of 200 to 10,000, di- and polyglycerol, pentaerythritol, sorbitol, the ethoxylates of these polyols and their
  • Esters with carboxylic acids or carbonic acid such as ethylene carbonate or propylene carbonate,
  • Carbonic acid derivatives such as urea, thiourea, guanidine, dicyandiamide, 2-oxazolidinone and its derivatives, bisoxazoline, polyoxazolines, di- and polyisocyanates,
  • Di- and poly-N-methylol compounds such as, for example, methylenebis (N-methylolmethacrylamide) or melamine-formaldehyde resins,
  • acid catalysts such as p-toluenesulfonic acid, phosphoric acid, boric acid or ammonium dihydrogen phosphate may be added.
  • Particularly suitable postcrosslinkers are di- or polyglycidyl compounds such as ethylene glycol diglycidyl ether, the reaction products of polyamidoamines with epichlorohydrin, 2-oxazolidinone and N-hydroxyethyl-2-oxazolidinone.
  • the surface postcrosslinking (often only "postcrosslinking") is usually carried out in such a way that a solution of the surface postcrosslinker (often only "postcrosslinker”) is sprayed onto the superabsorber or the dry base polymer powder.
  • the solvent used for the surface postcrosslinker is a conventional suitable solvent, for example water, alcohols, DMF, DMSO and mixtures thereof. Particularly preferred are water and water / alcohol mixtures such as water / methanol, water / isopropanol, water / 1, 2-propanediol and water / 1, 3-propanediol.
  • the spraying of a solution of the postcrosslinker is preferably carried out in mixers with agitated mixing tools, such as screw mixers, paddle mixers, disk mixers, ploughshare mixers and paddle mixers.
  • agitated mixing tools such as screw mixers, paddle mixers, disk mixers, ploughshare mixers and paddle mixers.
  • Vertical mixers are particularly preferred, plowshare mixers and paddle mixers are very particularly preferred.
  • Suitable and known mixers include for example Lödige ® - sawn pex ® - Nauta ® - Processall® ® - and Schugi ® mixer. Very particular preference high speed mixer lizer for example of the Schugi Flexomix ® or Turbo ®, are used.
  • the crosslinker solution may optionally follow a temperature treatment step, essentially to perform the surface postcrosslinking reaction (yet usually referred to only as “drying"), preferably in a downstream heated mixer (“dryer”), at a temperature of generally at least> 50 0 C, preferably at least> 80 0 C and in a particularly preferred form at least> 90 0 C and generally at most ⁇ 250 0 C, preferably at most ⁇ 200 0 C and in a particularly preferred form at most ⁇ 150 0 C.
  • drying surface postcrosslinking reaction
  • dryer downstream heated mixer
  • the average residence time (ie the average residence time of the individual superabsorbent particles) of the superabsorbent to be treated in the drier is generally at least 1 1 minute, preferably at least 3 3 minutes and more preferably at least 5 5 minutes, and generally at most ⁇ 6 hours, preferably at most ⁇ 2 hours most preferably at most ⁇ 1 hour.
  • the thermal drying is carried out in conventional dryers, such as tray dryers, rotary kilns or heatable screws, preferably in contact dryers.
  • dryers in which the product is moved ie heated mixers, particularly preferably paddle dryers, most preferably disc dryers.
  • Suitable dryers include for example Bepex ® -T dryers and Nara ® -T Rockner.
  • fluidized-bed dryers can also be used.
  • the drying can also be done in the mixer itself, by heating the jacket or blowing a preheated gas such as air. But it can also be, for example, an azeotropic distillation be used as a drying process.
  • the crosslinking reaction can take place both before and during drying.
  • the hydrophilicity of the particle surface of the base polymers is additionally modified by the formation of complexes.
  • the formation of the complexes on the outer shell of the particles is carried out by spraying solutions of divalent or polyvalent cations, wherein the cations can react with the acid groups of the polymer to form complexes.
  • divalent or polyvalent cations are polymers which are formally wholly or partially composed of vinylamine monomers, such as partially or completely hydrolyzed polyvinylamide (so-called "polyvinylamine”), whose amine groups are always partially protonated to ammonium groups, even at very high pH values, or metal cations such as Mg 2+ , Ca 2+ , Al 3+ , Sc 3+ , Ti 4+ , Mn 2+ , Fe 2+ / 3+ , Co 2+ , Ni 2+ , Cu 2+ , Zn 2+ , Y 3 + , Zr 4+ , La 3+ , Ce 4+ , Hf 4+ , and Au 3+ Preferred metal cations are Mg 2+ , Ca 2+ , Al 3+ , Ti 4+ , Zr 4+ and La 3 + , and particularly preferred metal cations are Al 3+ , Ti 4+ and Zr 4 + .
  • the metal cations can be used both alone and in
  • aluminum sulfate is used.
  • solvents for the metal salts water, alcohols, DMF, DMSO and mixtures of these components can be used. Particularly preferred are water and water / alcohol mixtures such as water / methanol, water / isopropanol, water / 1, 2-propanediol and water / 1, 3-propanediol.
  • the treatment of the base polymer with solution of a di- or polyvalent cation is carried out in the same way as with surface postcrosslinkers, including the optional drying step.
  • Surface postcrosslinker and polyvalent cation can be sprayed in a common solution or as separate solutions.
  • the spraying of the metal salt solution onto the superabsorbent particles can be carried out both before and after the surface postcrosslinking.
  • the spraying of the metal salt solution is carried out in the same step by spraying the crosslinker solution, wherein both solutions are sprayed separately successively or simultaneously via two nozzles, or crosslinker and metal salt solution can be sprayed together via a nozzle.
  • a drying step is carried out after the surface postcrosslinking and / or treatment with complexing agent, it is advantageous, but not absolutely necessary, to cool the product after drying.
  • the cooling can be continuous or discontinuous, conveniently the product is continuously conveyed to a dryer downstream cooler.
  • This can any apparatus known for the removal of heat from powdered solids, in particular any apparatus mentioned above as a drying apparatus, unless it is supplied with a heating medium, but with a cooling medium such as cooling water, so that over the walls and depending on the construction also on the stirring elements or other heat exchange surfaces do not introduce heat into the superabsorbent but are removed therefrom.
  • Bepex ® coolers the use of coolers in which the product is moved, that is, cooled mixers, for example, blade coolers, disk coolers or paddle coolers, for example Nara ® is preferred.
  • the superabsorber can also be cooled in the fluidized bed by blowing in a cooled gas such as cold air. The conditions of the cooling are adjusted so that a superabsorbent is obtained with the temperature desired for further processing.
  • an average residence time in the cooler of generally at least> 1 minute, preferably at least> 3 minutes and more preferably at least> 5 minutes, and generally at most ⁇ 6 hours, preferably at most ⁇ 2 hours and most preferably at most ⁇ 1 Set hour and the cooling capacity so that the product obtained has a temperature of generally at least> 0 0 C, preferably at least> 10 0 C and in a particularly preferred form at least> 20 0 C and generally at most ⁇ 100 0 C, preferably Höchs - At least ⁇ 80 0 C and in a particularly preferred form at most ⁇ 60 0 C has.
  • a further modification of the superabsorbents by admixing finely divided inorganic solids such as, for example, silicon dioxide, aluminum oxide, titanium dioxide and iron (II) oxide, can be carried out, whereby the effects of the surface post-treatment are further enhanced.
  • finely divided inorganic solids such as, for example, silicon dioxide, aluminum oxide, titanium dioxide and iron (II) oxide
  • admixture of hydrophilic silica or alumina with an average size of the primary particles of> 4 to ⁇ 50 nm and a specific surface area of> 50 - ⁇ 450 m 2 / g.
  • the admixture of finely divided inorganic solids is preferably carried out after the surface modification by crosslinking / complex formation, but can also be carried out before or during these surface modifications.
  • the superabsorbent is provided with other common additives and adjuvants that affect storage or handling properties. Examples include stains, opaque additives to improve the visibility of swollen gel, which is desirable in some applications, additives to improve the flow behavior of the powder, surfactants or the like. Often the dedusting or dust binder is added to the superabsorbent.
  • Dust-removing or dust-binding agents are known, for example polyether glycols such as polyethylene glycol having a molecular weight of> 400 to ⁇ 20,000 g / mol, polyols such as glycerol, sorbitol, neopentyl glycol or trimethylolpropane, which are optionally ethoxylated> 7 to ⁇ 20-fold , used. Even a finite water content of the superabsorbent can be adjusted by adding water, if desired.
  • the solids, additives and auxiliaries can each be added in separate process steps, but usually the most convenient method is to add them to the superabsorber in the cooler, for example by spraying a solution or adding it in finely divided solid or in liquid form.
  • the surface postcrosslinked superabsorbent is optionally ground and / or sieved in the usual way. Milling is typically not required here, but most often, the setting of the desired particle size distribution of the product, the screening of formed agglomerates or fine grain is appropriate. Agglomerates and fines are either discarded or preferably recycled to the process in a known manner and at a suitable location; Agglomerates after comminution.
  • the particle size of the superabsorbent particles is preferably at most ⁇ 1000 .mu.m, more preferably at most ⁇ 900 .mu.m, very preferably at most ⁇ 850 .mu.m, and preferably at least> 80 .mu.m, more preferably at least> 90 .mu.m, most preferably at least> 100 .mu.m.
  • Typical sieve cuts are, for example,> 106 to 850 ⁇ m or> 150 to ⁇ 850 ⁇ m.
  • the present invention also relates to a use of the method according to the invention and / or use of the inventive use strug for or in connection with
  • the 5 soil types were then mixed with various amounts of superabsorbent (Luquasorb, Fa. Basf) and once 0.2% (dry weight Luquasorb / dry weight soil), 0.4% and 0% (control).
  • Fifteen seedlings (four months old) of each of the nine plant species studied were spiked in a suitable pot with 3 kg soil each of the 5 soil types.
  • the individual pots were randomly distributed and watered at 1 liter per day for a period of 4-8 weeks, until the seedlings had established themselves in the new environment. This was confirmed by the growth of new branches and leaves.
  • the irrigation was then stopped and simulated in the greenhouse water stress and drying conditions were set in the 25 ° C temperature and 50% humidity. Subsequently, the seedlings were monitored to determine the time of death.
  • Table 2 shows the survival rate (in days) as well as the available amount of water and transpiration for the individual seedlings on sandy soil.
  • Table 3 shows the available water quantity, survival rate and evapotranspiration rate for the seedlings on loamy sandy soil.
  • Table 4 shows the available water quantity, survival rate and water use efficiency (WUE) for the seedlings on clay soil.
  • Table 5 shows the available water quantity, survival rate and water use efficiency (WUE) for the seedlings on flooded clay soil.
  • Table 6 shows the available amount of water, survival rate and water use efficiency (WUE) for the seedlings on clay.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Soil Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Botany (AREA)
  • Ecology (AREA)
  • Forests & Forestry (AREA)
  • Environmental Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention se rapporte à l'utilisation d'agents superabsorbants pour stimuler l'efficacité d'utilisation de l'eau chez des plantes se trouvant dans un milieu de culture contenant des agents superabsorbants.
PCT/EP2009/061910 2008-09-30 2009-09-15 Réduction de l'évapotranspiration de plantes soumises à un stress hydrique au moyen d'agents superabsorbants WO2010037631A1 (fr)

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DE102008049745A DE102008049745A1 (de) 2008-09-30 2008-09-30 Verringerung der Evapotranspiration von Pflanzen unter Wasserstress durch Superabsorber
DE102008049745.2 2008-09-30

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* Cited by examiner, † Cited by third party
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WO2024148163A1 (fr) * 2023-01-04 2024-07-11 Corbet Scientific, Llc Compositions servant à améliorer l'efficacité d'irrigation et procédés d'utilisation associés

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WO1999003321A1 (fr) * 1997-07-21 1999-01-28 Salestrom Ronald D Melange agricole ameliorant la retention et l'ecoulement de l'eau
US20040065012A1 (en) * 2002-09-18 2004-04-08 Byles Joe Don Water and air retaining flower and landscape planter pot method and apparatus
WO2007053862A1 (fr) * 2005-11-08 2007-05-18 Bios4-Systemic Sustainability Solutions, Rammel Und Partner Oeg Systeme d'irrigation
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US6484441B1 (en) 1998-03-26 2002-11-26 Stockhausen Gmbh Method for increasing the pH value in acidic soil
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US20040065012A1 (en) * 2002-09-18 2004-04-08 Byles Joe Don Water and air retaining flower and landscape planter pot method and apparatus
WO2007053862A1 (fr) * 2005-11-08 2007-05-18 Bios4-Systemic Sustainability Solutions, Rammel Und Partner Oeg Systeme d'irrigation
WO2007104720A1 (fr) * 2006-03-10 2007-09-20 Basf Se Compositions pesticides destinees a la lutte contre les organismes nuisibles arthropodes, les escargots et les nematodes

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024148163A1 (fr) * 2023-01-04 2024-07-11 Corbet Scientific, Llc Compositions servant à améliorer l'efficacité d'irrigation et procédés d'utilisation associés

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