EP0726707A1 - Rooting inhibitors - Google Patents
Rooting inhibitorsInfo
- Publication number
- EP0726707A1 EP0726707A1 EP94931545A EP94931545A EP0726707A1 EP 0726707 A1 EP0726707 A1 EP 0726707A1 EP 94931545 A EP94931545 A EP 94931545A EP 94931545 A EP94931545 A EP 94931545A EP 0726707 A1 EP0726707 A1 EP 0726707A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- phenoxycarboxylic acid
- phenoxycarboxylic
- carrier material
- inorganic carrier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
- A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
- A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
- A01N39/04—Aryloxy-acetic acids; Derivatives thereof
Definitions
- the present invention relates to substances and preparations which protect buildings, seals and insulation against ingrowth and through-growth of roots.
- the substances are used for the production of root-resistant building materials such as bitumen mixtures, sealants and insulating materials.
- Root growth in building materials leads to unwanted material damage. Particularly plastic materials, such as sealing compounds, roofing membranes, but also asphalt can be destroyed by plant roots.
- plastic materials such as sealing compounds, roofing membranes, but also asphalt can be destroyed by plant roots.
- the penetration of roots in the seals of sewers and sewage pipes, in flat roof covers, in bitumen insulation of pipes, bridges and water structures as well as the ingrowth and ingrowth of roots on light bitumen roads are generally known problems. This can result in leaks, corrosion, damage to buildings, roads and pipelines.
- herbicides such as, for example, 2,4-dichlorophenoxyacetic acid, 2,4,5-trichlorophenoxyacetic acid and ⁇ -naphthylacetic acid or their salts, amides or esters, for example isooctyl ester or esters of l-hydroxy-2-butoxyethane, furthermore phenyl- N-isopropyl carbaminate and p-chlorophenyldimethylurea can be used as root inhibitors (DE 1 108 833).
- phenoxycarbon acids as herbicides has long been known (see, eg, The Agrochemicals Handbook, 3 r d Ed, Royal Soc Chem., Cambridge 1993).
- Building materials include to understand bituminous building materials as well as concrete or building materials containing concrete, as well as those that e.g. be described in WO 92/10 537.
- the application therefore relates to the use of phenoxycarboxylic acid bonded to an inorganic support material for protecting buildings, insulation and seals against root penetration.
- R 1 to R 5 independently of one another represent F_-Br, CI, F, CF3, CF2H, methyl, ethyl, propyl, methoxy, OCF3 and R 6 stands for H, Me, Et
- Preferred compounds of the formula (I) are those in which R 1 represents Me, CI, CF 3 , R 2 to R 5 represent H, CI, F, methyl, CF 3 and R 6 represents H, Me.
- R 2 , R 4 , R 5 stand for H, R 3 is CI and R 6 is Me.
- Suitable support materials include: e.g. nat. and synthetic zeolites, layered silicates, clays, precipitated silicas, diatomaceous earth, silica gels, aerosils, bentonites, kaolins, activated carbons, natural and synthetic clay minerals, TiO 2, ZnO, calcium carbonate, dolomites, pumice stones, attapulgites, sepiolites, ball clays, clays, as well as aluminophosphates , Metal aluminophosphates and crystalline silicas with pore structure.
- zeolites or molecular sieves which come under the following formula, have proven to be particularly suitable support materials:
- M is an exchangeable cation
- E ⁇ means a trivalent element
- E 2 is a tetravalent element, E ⁇ and E 2 being the anionic skeleton,
- n / m is the ratio of the elements E ⁇ and E 2 and can have values of 1 to 3,000, preferably 1 to 2,000,
- the zeolites having pore sizes of at least 4 ⁇ , for example pore sizes in the range from 4 to 8 ⁇ , preferably in the range 5 to 8 ⁇ .
- the basic structure is made of zeolites from a network of SiO-4 and AIO4
- Tetrahedron constructed, whereby the individual tetrahedra are linked with each other by oxygen bridges via their corners and form a spatial network that is moderately crisscrossed by channels and cavities.
- the aluminum as a representative of the element E * can be partially replaced by other trivalent or divalent elements such as B, Ga, In, Fe, Cr, V, As, Sb or Be, Cu and Co.
- the silicon as a representative of the element E 2 can be replaced by other tetravalent elements, such as Ge. Interchangeable cations are stored to compensate for the negative charge of the lattice caused by the trivalent elements.
- the individual zeolite structures (types) also differ in the arrangement and size of the channels and cavities.
- Zeolites always contain q H 2 O as a sorbed water phase, which can be removed reversibly without the structure losing its structure.
- a detailed description of zeolites can be found, for example, in the monograph "Introduction to Zeolite Science and Practice” Ed. H. van Bekkum, EM Flanigen, JC Jansen in the series Studies in Surface Science and Catalysis, Vol. 58, Elsevier, Amsterdam, Oxford, New York, Tokyo, 1991.
- aluminophosphates such as e.g. A1PO-5, A1PO-11, AJPO-8, A1PO-17 and silicoaluminophosphates such as e.g. S.APO-5, SAPO-11, SAPO-34, SAPO 17 and others.
- layered silicates such as e.g. Magadiit or SKS-6 suitable as a carrier material.
- zeolites Preferred among the zeolites are the easily accessible zeolite structures such as zeolite A and faujasite with the types zeolite X and zeolite Y and the following formulas: Type A Na 12 [(AlO 2 ) ⁇ 2 • (SiO 2 ) ⁇ ] • 2 ? H 2 0
- Type X Na 86 [AlO 2 ) 86 • (SiO 2 ) 106 ] • 2 64 H 2 O
- the various ion-exchanged forms are also suitable as a carrier material.
- the carriers are loaded with the phenoxycarboxylic acids in different ways adapted to the respective carrier material. Such techniques would e.g. described in DE 1 219 008.
- the loading of molecular sieves or zeolites e.g. in that the molecular sieve is first freed of water by heating, which e.g. can be done by heating to 400 to 450 ° C for several hours, and then brought into contact with the active substance.
- Loading takes place in any way, e.g. by passing the active substance brought into the vapor form through the zeolite or by immersing the zeolite in the liquid or molten active substance or a solution of the active substance in a non-polar, volatile solvent with subsequent evaporation of the solvent.
- the amount of active substance with which the carrier material is loaded can vary within wide limits. It depends on the active ingredient used and the conditions under which the carrier / active ingredient combination is to be used.
- amounts of from 0.1 to about 90% by weight of active compound, preferably 5 to 70%, particularly preferably 10 to 50%, based on the carrier material, are applied.
- the maximum loading is preferably selected in order to achieve a high active ingredient concentration per mass of starting material.
- the phenoxycarboxylic acid is preferably mixed in its crystalline form with the carrier material and together to a temperature above its melting point warmed up.
- the carrier material water, oxygen, air etc. may have to be excluded.
- auxiliaries can also be added to the mixture of carrier material and phenoxycarboxylic acid, e.g. reduce dusting of the mixture or sensitivity to water.
- phenoxycarboxylic acid / carrier combinations are used directly or in the form of other preparations such as e.g. mixed with bitumen, tar pitch, building materials or insulating materials. It is also possible to separate the carrier material and the phenoxycarboxylic acid separately but at the same time to add it to the building materials.
- the content of phenoxycarboxylic acid in the bitumen is 0.01 to 20% by weight, preferably 0.1 to 5%, particularly preferably 0.3 to 2%.
- the content of phenoxycarboxylic acid in bituminous building * _ ⁇ n results from the application concentration of the acid in the bitumen and the bitumen content in the building materials. It is generally 0.05 to 0.5%.
- the fixed phenoxycarboxylic acid can also be added to these and worked in together with them.
- Example 2 Analogously to Example 1, only with H zeolite Y, a dealuminated zeolite Y with an SiO 2 / Al 2 ⁇ 3 ratio of 90.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The application describes building materials, sealants and insulating compounds containing a combination of special phenoxycarboxylic acids that are bonded to an inorganic substrate.
Description
DurchwurzelungsinhibitorenRoot penetration inhibitors
Die vorliegende Erfindung betrifft Substanzen und Zubereitungen, die Bauwerke, Dichtungen und Isolierungen gegen Ein- und Durchwachsen von Wurzeln schützen. Die Substanzen werden verwendet zur Herstellung von wurzelfesten Baustoffe wie Bitumen-Mischungen, Dichtstoffen und Isoliermassen.The present invention relates to substances and preparations which protect buildings, seals and insulation against ingrowth and through-growth of roots. The substances are used for the production of root-resistant building materials such as bitumen mixtures, sealants and insulating materials.
Bei Baustoffen führt Wurzeldurchwuchs zu unerwürschten Materialschäden. Beson¬ ders plastische Materiahen, wie Dichtungsmassen, Dachbahnen, aber auch Asphalt können von Pflanzenwurzeln zerstört werden. Das Eindringen von Wurzeln in Dichtungen von Kanälen und Abwasserleitungen, in Flachdachabdeckungen, in Bitu¬ menisolierungen von Rohrleitungen, Brücken- und Wasserbauten sowie das Ein- und Durchwachsen von Wurzeln bei leichten Bitumen-Straßen sind allgemein bekannte Probleme. Undichtigkeiten, Korrosion, Schäden an Gebäuden, Straßen und Rohrlei¬ tungen können die Folge sein.Root growth in building materials leads to unwanted material damage. Particularly plastic materials, such as sealing compounds, roofing membranes, but also asphalt can be destroyed by plant roots. The penetration of roots in the seals of sewers and sewage pipes, in flat roof covers, in bitumen insulation of pipes, bridges and water structures as well as the ingrowth and ingrowth of roots on light bitumen roads are generally known problems. This can result in leaks, corrosion, damage to buildings, roads and pipelines.
Der Zusatz von wurzelwidrigen Wirkstoffen zu Baustoffen ist bekannt und z.B. in F. Hegemann, Abiogene Bitumenadditive, Bitumen-Teere- Asphalte-Peche 24, 105 (1973) beschrieben.The addition of anti-root active ingredients to building materials is known and e.g. in F. Hegemann, Abiogene Bitumenadditive, Bitumen-Teere-Asphalte-Peche 24, 105 (1973).
Desweiteren ist bekannt, daß Herbizide wie z.B. 2,4-Dichlorphenoxyessigsäure, 2,4,5-Trichlorphenoxyessigsäure und α-Naphthylessigsäure bzw. deren Salze, Amide oder Ester, z.B. Isooctylester oder Ester des l-Hydroxy-2-butoxyethans, femer Phenyl-N-isopropylcarbaminat und p-Chlorphenyldimethylharnstoff als Durchwurze¬ lungsinhibitoren genutzt werden können (DE 1 108 833).
Auf der anderen Seite sind Phenoxycarbonsäuren als Herbizide seit langem bekannt (s. z.B. The Agrochemicals Handbook, 3rd Ed, Royal Soc Chem., Cambridge 1993).Furthermore, it is known that herbicides such as, for example, 2,4-dichlorophenoxyacetic acid, 2,4,5-trichlorophenoxyacetic acid and α-naphthylacetic acid or their salts, amides or esters, for example isooctyl ester or esters of l-hydroxy-2-butoxyethane, furthermore phenyl- N-isopropyl carbaminate and p-chlorophenyldimethylurea can be used as root inhibitors (DE 1 108 833). On the other side are phenoxycarbon acids as herbicides has long been known (see, eg, The Agrochemicals Handbook, 3 r d Ed, Royal Soc Chem., Cambridge 1993).
Diese Säuren sind jedoch nicht ausreichend als Durchwurzelungsinhibitoren brauchbar, da sie einerseits als Herbizide starke pflanzenschädigende Wirkung haben und andererseits keinen Langzeitschutz für die Baustoffe bieten.However, these acids are not sufficiently usable as rooting inhibitors, since on the one hand they have strong plant-damaging effects as herbicides and on the other hand they offer no long-term protection for the building materials.
Überraschenderweise wurde jetzt jedoch gefunden, daß wenn man Phenoxycarbonsäuren, chemisch und/oder physikalisch (adsorptiv) an anorganische Trägermaterialien bindet und in dieser Form in die Baustoffe, Dichtstoffe und Isoliermassen einarbeitet, eine sehr gute und lang anhaltende Schutzwirkung erzielt wird.Surprisingly, however, it has now been found that if phenoxycarboxylic acids are chemically and / or physically (adsorptively) bound to inorganic carrier materials and incorporated in this form into the building materials, sealants and insulating materials, a very good and long-lasting protective effect is achieved.
Unter Baustoffen sind hier u.a. bitumenhaltige Baustoffe als auch Beton, bzw. beton¬ haltige Baumaterialien zu verstehen, sowie solche, die z.B. in WO 92/10 537 beschrieben werden.Building materials include to understand bituminous building materials as well as concrete or building materials containing concrete, as well as those that e.g. be described in WO 92/10 537.
Gegenstand der Anmeldung ist daher die Verwendung von an anorganischem Trägermaterial gebundener Phenoxycarbonsäure zum Schutz von Bauwerken, Isolierungen und Dichtungen gegen Durchwurzelung.The application therefore relates to the use of phenoxycarboxylic acid bonded to an inorganic support material for protecting buildings, insulation and seals against root penetration.
Als Phenoxycarbonsäuren kommen vorzugsweise die folgenden Verbindungen der Formel (I)The following compounds of the formula (I) are preferably used as phenoxycarboxylic acids
in welcherin which
R1 bis R5 unabhängig voneinander für F_- Br, CI, F, CF3, CF2H, Methyl, Ethyl, Propyl, Methoxy, OCF3 stehen und
R6 für H, Me, Et stehtR 1 to R 5 independently of one another represent F_-Br, CI, F, CF3, CF2H, methyl, ethyl, propyl, methoxy, OCF3 and R 6 stands for H, Me, Et
in Frage.in question.
Bevorzugt sind Verbindungen der Formel (I), in welcher R1 für Me, CI, CF3 steht, R2 bis R5 für H, CI, F, Methyl, CF3 stehen und R6 für H, Me steht.Preferred compounds of the formula (I) are those in which R 1 represents Me, CI, CF 3 , R 2 to R 5 represent H, CI, F, methyl, CF 3 and R 6 represents H, Me.
Besonders bevorzugt sind Verbindungen der Formel (I) in welcher R1 für Me, CI steht, R2, R4, R5 für H steht, R3 für Me, CI steht und R6 Me bedeutet.Particularly preferred are compounds of formula (I) in which R 1 is Me, CI, R 2 , R 4 , R 5 is H, R 3 is Me, CI and R 6 is Me.
Ganz besonders bevorzugt ist eine Verbindung der Formel (I) in welcher R1 Me ist,A compound of the formula (I) in which R 1 is Me is very particularly preferred,
R2, R4, R5 für H stehen, R3 CI ist und R6 Me ist.R 2 , R 4 , R 5 stand for H, R 3 is CI and R 6 is Me.
Insbesondere komen auch die folgenden Phenoxycarbonsäuren in Frage:The following phenoxycarboxylic acids are also particularly suitable:
Phenoxypropionsäure, 2-Methyl-4-chlor-phenoxypropionsäure, 2,4-Dichlorphenoxy- propionsäure, 2-Methyl-4-chlorphenoxyessigsäure, 2-[4-(2,4-Dichlorphenoxy)-phen- oxy]-propionsäure (Dichlofop), 2-[4-(6-Chloro-l,3-benzoxyzol-2-yl-oxy)-phenoxy]- propionsäure (Fenoxaprop), 2-[4-(6-Chloro-2-chinoxalinyloxy)-phenoxy]-propion- säure (Quizalfop), 2-[4-(3-Chlqro-5-trifluormethyl-2-pyridoxyloxy)-phenoxy]-pro- pionsäure (Haloxyfop), 0-[5-(2-Chloro-α,α,α-trifluoro-p-tolyloxy)-2-nitrobenzoyl]- glykolsäure (Fluoroglykofen), - 0-[5-(2-Chloro-α,α,α-trifluoro-p-tolyloxy)-2-nitroben- zoyl]-milchsäure (Lactofen), 9-Hydroxyfluoren-9-carbonsäure (Flurenol), N-Benzoyl- N-(3-Chloro-4-fluoropheny_)-D,L-Alanin (Flamprop), 3-[l-(4-Chlorphenyl)-3-oxobu- tyl]-4-hydroxycumarin (Cumachlor), 4,4'-Dichlorbenzilsäure (Chlorobenzilat), 2- Chloro-9-hydroxyfluoren-9-carbonsäure (Chlorflurenol), 5-Chloro-l-H-3-indazol-3-
essigsaure (Ethylchlozate), 5-(2,4-Dichlorphenoxy)-2-nitrobenzoesäure (Difenox), 2- (2,4-Dichlorphenoxy)-propionsäure, 2-(3-Chlorophenoxy)-propionsäure.Phenoxypropionic acid, 2-methyl-4-chlorophenoxypropionic acid, 2,4-dichlorophenoxy propionic acid, 2-methyl-4-chlorophenoxyacetic acid, 2- [4- (2,4-dichlorophenoxy) phenoxy] propionic acid (dichlofop) , 2- [4- (6-chloro-l, 3-benzoxyzol-2-yl-oxy) phenoxy] - propionic acid (fenoxaprop), 2- [4- (6-chloro-2-quinoxalinyloxy) phenoxy] - propionic acid (quizalfop), 2- [4- (3-chloro-5-trifluoromethyl-2-pyridoxyloxy) phenoxy] propionic acid (haloxyfop), 0- [5- (2-chloro-α, α, α-trifluoro-p-tolyloxy) -2-nitrobenzoyl] - glycolic acid (fluoroglycofen), - 0- [5- (2-chloro-α, α, α-trifluoro-p-tolyloxy) -2-nitrobenzoyl] - lactic acid (lactofen), 9-hydroxyfluorene-9-carboxylic acid (flurenol), N-benzoyl-N- (3-chloro-4-fluoropheny _) - D, L-alanine (Flamprop), 3- [l- (4-chlorophenyl ) -3-oxobutyl] -4-hydroxycoumarin (cumachlor), 4,4'-dichlorobenzilic acid (chlorobenzilate), 2-chloro-9-hydroxyfluorene-9-carboxylic acid (chlorofluorene), 5-chloro-1H-3-indazole -3- acetic acid (ethyl chlorozate), 5- (2,4-dichlorophenoxy) -2-nitrobenzoic acid (difenox), 2- (2,4-dichlorophenoxy) propionic acid, 2- (3-chlorophenoxy) propionic acid.
Als geeignete Trägermaterialien seien genannt: z.B. nat. und synth. Zeolithe, Schichtsilikate, Tonerden, Fällungskieselsäuren, Kieselgure, Kieselgele, Aerosile, Bentonite, Kaoline, Aktivkohlen, natürliche und synthetische Tonmineralien, Tiθ2, ZnO, Calciumcarbonat, Dolomite, Bimssteine, Attapulgite, Sepiolite, Ballclays, Tone, sowie Alumophosphate, Silicoalumophosphate, Metallalumophosphate und kristalline Kieselsäuren mit Porenstruktur.Suitable support materials include: e.g. nat. and synthetic zeolites, layered silicates, clays, precipitated silicas, diatomaceous earth, silica gels, aerosils, bentonites, kaolins, activated carbons, natural and synthetic clay minerals, TiO 2, ZnO, calcium carbonate, dolomites, pumice stones, attapulgites, sepiolites, ball clays, clays, as well as aluminophosphates , Metal aluminophosphates and crystalline silicas with pore structure.
Als . besonders geeignete Trägermaterialien haben sich die Zeolithe bzw. Molekularsiebe erwiesen, die unter die nachstehende Formel fallen:As . The zeolites or molecular sieves, which come under the following formula, have proven to be particularly suitable support materials:
Mmlz [mElθ2 • nE2O2] • qH2OM mlz [mElθ 2 • nE 2 O 2 ] • qH 2 O
in derin the
M ein austauschbares Kation bedeutet,M is an exchangeable cation,
E^ ein dreiwertiges Element bedeutet,E ^ means a trivalent element
E2 ein vierwertiges Element bedeutet, wobei E^ und E2 das anionische Gerüst darstellen,E 2 is a tetravalent element, E ^ and E 2 being the anionic skeleton,
n/m das Verhältnis der Elemente E^ und E2 bedeuten und Werte von 1 bis 3 000, bevorzugt 1 bis 2 000, annehmen kann,n / m is the ratio of the elements E ^ and E 2 and can have values of 1 to 3,000, preferably 1 to 2,000,
z für die Wertigkeit des austauschbaren Kations steht undz stands for the value of the exchangeable cation and
q die Menge des sorbierten Wassers bedeutet,q means the amount of water sorbed,
wobei die Zeolithe Porenweiten von mindestens 4Ä haben, beispielsweise Porenwei¬ ten im Bereich von 4 bis 8Ä, bevorzugt im Bereich 5 bis 8Ä.the zeolites having pore sizes of at least 4 Å, for example pore sizes in the range from 4 to 8 Å, preferably in the range 5 to 8 Å.
Von der Grundstruktur her sind Zeolithe aus einem Netzwerk von SiO-4- und AIO4-The basic structure is made of zeolites from a network of SiO-4 and AIO4
Tetraedem aufgebaut, wobei die einzelnen Tetraeder mit Sauerstoffbrücken über ihre Ecken untereinander verknüpft sind und ein räumliches Netzwerk bilden, das gleich-
mäßig von Kanälen und Hohlräumen durchzogen ist. Das Aluminium als Repräsentant des Elementes E* kann durch andere dreiwertige oder auch zweiwertige Elemente, wie B, Ga, In, Fe, Cr, V, As, Sb oder Be, Cu und Co teilweise ersetzt sein. Weiterhin kann das Silicium als Repräsentant für das Element E2 durch andere vierwertige Elemente ersetzt werden, wie z.B. Ge. Als Ausgleich für die durch die dreiwertigen Elemente hervorgerufene negative Ladung des Gitters sind austauschbare Kationen eingelagert. Die einzelnen Zeolith-Strukturen (Typen) unterscheiden sich femer durch die Anordnung und Größe der Kanäle und Hohlräume. Zeolithe enthalten stets q H2O als sorbierte Wasserphase, die reversibel entfernbar ist, ohne daß das Gerüst seine Struktur verliert. Eine ausführliche Darstellung von Zeolithen ist beispielsweise in der Monographie "Introduction to Zeolite Science and Practice" Ed. H. van Bekkum, E. M. Flanigen, J.C. Jansen in der Reihe Studies in Surface Science and Catalysis, Vol. 58, Elsevier, Amsterdam, Oxford, New York, Tokio, 1991, gegeben.Tetrahedron constructed, whereby the individual tetrahedra are linked with each other by oxygen bridges via their corners and form a spatial network that is moderately crisscrossed by channels and cavities. The aluminum as a representative of the element E * can be partially replaced by other trivalent or divalent elements such as B, Ga, In, Fe, Cr, V, As, Sb or Be, Cu and Co. Furthermore, the silicon as a representative of the element E 2 can be replaced by other tetravalent elements, such as Ge. Interchangeable cations are stored to compensate for the negative charge of the lattice caused by the trivalent elements. The individual zeolite structures (types) also differ in the arrangement and size of the channels and cavities. Zeolites always contain q H 2 O as a sorbed water phase, which can be removed reversibly without the structure losing its structure. A detailed description of zeolites can be found, for example, in the monograph "Introduction to Zeolite Science and Practice" Ed. H. van Bekkum, EM Flanigen, JC Jansen in the series Studies in Surface Science and Catalysis, Vol. 58, Elsevier, Amsterdam, Oxford, New York, Tokyo, 1991.
In bevorzugter Weise kommen Zeolithe der folgenden Strukturtypen und entspre- chende Analoga für die erfindungsgemäße Phenoxycarbonsäure/Trägerkombination in Frage:Zeolites of the following structure types and corresponding analogs are preferred for the phenoxycarboxylic acid / carrier combination according to the invention:
Zeolith A, Chabasit, Cancrinit, Gmelinit, Zeolith L, Heulandit, Mazzet, Mordenit, Offretit, EU-1, Fanjasit, Ferrierit, Gismondin, ZK-5, ZSM 5, ZSM 11, ZSM 23, ZSM 22, ZSM 12, Zeolith ß, PSH-3, Zeolith Rho.Zeolite A, chabazite, cancrinite, gmelinite, zeolite L, heulandite, mazzet, mordenite, offretite, EU-1, fanjasite, ferrierite, gismondin, ZK-5, ZSM 5, ZSM 11, ZSM 23, ZSM 22, ZSM 12, zeolite ß, PSH-3, zeolite Rho.
Ebenfalls bevorzugt sind Alumophosphate wie z.B. A1PO-5, A1PO-11, AJPO-8, A1PO-17 und Silicoalumophosphate wie z.B. S.APO-5, SAPO-11, SAPO-34, SAPO 17 und andere.Also preferred are aluminophosphates such as e.g. A1PO-5, A1PO-11, AJPO-8, A1PO-17 and silicoaluminophosphates such as e.g. S.APO-5, SAPO-11, SAPO-34, SAPO 17 and others.
Neben Zeolithen sind vorzugsweise auch Schichtsilikate wie z.B. Magadiit oder SKS- 6 als Trägermaterial geeignet.In addition to zeolites, layered silicates such as e.g. Magadiit or SKS-6 suitable as a carrier material.
Bevorzugt unter den Zeolithen sind die leicht zugänglichen Zeolith-Strukturen wie Zeolith- A und Faujasit mit den Typen Zeolith X und Zeolith Y und den folgenden Formeln:
Typ A Na12 [(AlO2)ι2 • (SiO2)ι ] • 2? H20Preferred among the zeolites are the easily accessible zeolite structures such as zeolite A and faujasite with the types zeolite X and zeolite Y and the following formulas: Type A Na 12 [(AlO 2 ) ι 2 • (SiO 2 ) ι] • 2 ? H 2 0
Typ X Na86 [AlO2)86 • (SiO2)106] • 264 H2OType X Na 86 [AlO 2 ) 86 • (SiO 2 ) 106 ] • 2 64 H 2 O
Typ Y Na56 [AlO2)56 • (SiO2)136] ■ 250 H2OType Y Na 56 [AlO 2 ) 56 • (SiO 2 ) 136 ] ■ 250 H 2 O
Neben den Syntheseformen der Zeolithe sind auch die verschiedenen ionenausge- tauschten Formen als Trägermaterial geeignet.In addition to the synthetic forms of the zeolites, the various ion-exchanged forms are also suitable as a carrier material.
Die Beladung der Träger mit den Phenoxycarbonsäuren erfolgt auf unterschiedlichen, dem jeweiligen Trägermaterial angepaßten, Wegen. Derartige Techniken würden z.B. in der DE 1 219 008 beschrieben.The carriers are loaded with the phenoxycarboxylic acids in different ways adapted to the respective carrier material. Such techniques would e.g. described in DE 1 219 008.
Demnach kann die Beladung von Molekularsieben bzw. Zeolithen z.B. dadurch erfolgen, daß das Molekularsieb durch Erhitzen zunächst vom Wasser befreit wird, was z.B. durch mehrstündiges Erhitzen auf 400 bis 450°C erfolgen kann, und anschließend mit der Wirksubstanz in Kontakt gebracht wird. Die Beladung erfolgt in beliebiger Weise, z.B. durch Durchleiten des in die Dampfform gebrachten Wirkstoffes durch den Zeolith oder durch Eintauchen des Zeolith in den flüssigen bzw. geschmolzenen Wirkstoff oder einer Lösung des Wirkstoffs in einem nicht polaren, flüchtigen Lösungsmittel mit einschließendem Abdampfen des Lösungs¬ mittels.Accordingly, the loading of molecular sieves or zeolites e.g. in that the molecular sieve is first freed of water by heating, which e.g. can be done by heating to 400 to 450 ° C for several hours, and then brought into contact with the active substance. Loading takes place in any way, e.g. by passing the active substance brought into the vapor form through the zeolite or by immersing the zeolite in the liquid or molten active substance or a solution of the active substance in a non-polar, volatile solvent with subsequent evaporation of the solvent.
Die Menge des Wirkstoffes mit dem das Trägermaterial beladen wird, kann innerhalb weiter Grenzen variieren. Sie hängt von dem verwendeten Wirkstoff und den Einsatzbedingungen ab, bei dem die Träger/Wirkstoff-Kombination verwendet werden soll.The amount of active substance with which the carrier material is loaded can vary within wide limits. It depends on the active ingredient used and the conditions under which the carrier / active ingredient combination is to be used.
Im allgemeinen werden Mengen von 0,1 bis etwa 90 Gew.-% Wirkstoff, bevorzugt 5 bis 70 %, besonders bevorzugt 10 bis 50 %, bezogen auf das Trägermaterial, aufge¬ bracht. Vorzugsweise wird die maximale Beladung gewählt, um eine hohe Wirkstoff- Konzentration pro Masse Einsatzstoff zu erzielen.In general, amounts of from 0.1 to about 90% by weight of active compound, preferably 5 to 70%, particularly preferably 10 to 50%, based on the carrier material, are applied. The maximum loading is preferably selected in order to achieve a high active ingredient concentration per mass of starting material.
Bevorzugt wird die Phenoxycarbonsäure in ihrer kristallinen Form mit dem Träger¬ material gemischt und gemeinsam auf eine Temperatur oberhalb ihres Schmelzpunktes
erwärmt. Dabei sind gegebenenfalls je nach Trägermaterial Wasser, Sauerstoff, Luft etc., auszuschließen.The phenoxycarboxylic acid is preferably mixed in its crystalline form with the carrier material and together to a temperature above its melting point warmed up. Depending on the carrier material, water, oxygen, air etc. may have to be excluded.
Dem Gemisch von Trägermaterial und Phenoxycarbonsäure können auch noch weitere Hilfsstoffe beigefügt werden, um z.B. das Stauben der Mischung oder die Empfindlichkeit gegenüber Wasser einzudämmen.Additional auxiliaries can also be added to the mixture of carrier material and phenoxycarboxylic acid, e.g. reduce dusting of the mixture or sensitivity to water.
Zur wurzelfesten Ausrüstung werden die Phenoxycarbonsäure/Trägerkominationen direkt oder in Form von sonstigen Zubereitungen wie z.B. mit Bitumen, Teerpechen den Baustoffen oder Isoliermassen zugemischt. Dabei ist es auch möglich das Trägermaterial und die Phenoxycarbonsäure getrennt aber gleichzeitig den Baustoffen beizumischen.The phenoxycarboxylic acid / carrier combinations are used directly or in the form of other preparations such as e.g. mixed with bitumen, tar pitch, building materials or insulating materials. It is also possible to separate the carrier material and the phenoxycarboxylic acid separately but at the same time to add it to the building materials.
Der Gehalt von Phenoxycarbonsäure im Bitumen beträgt erfindungsgemäß 0,01 bis 20 Gew.-%, bevorzugt 0,1 bis 5 %, besonders bevorzugt 0,3 bis 2 %.According to the invention, the content of phenoxycarboxylic acid in the bitumen is 0.01 to 20% by weight, preferably 0.1 to 5%, particularly preferably 0.3 to 2%.
Der Gehalt von Phenoxycarbonsäure in bituminösen Baust* _≤n ergibt sich aus der Anwendungskonzentration der Säure im Bitumen und dem Bitumenanteil in den Baustoffen. Er liegt im allgemein bei 0,05 bis 0,5 %.The content of phenoxycarboxylic acid in bituminous building * _≤n results from the application concentration of the acid in the bitumen and the bitumen content in the building materials. It is generally 0.05 to 0.5%.
Werden andere Zuschlagstoffe dem Bitumen hinzugefügt (s. Dachpappe), kann die fixierte Phenoxycarbonsäure auch diesen beigegeben und gemeinsam mit diesen ein¬ gearbeitet werden.
If other additives are added to the bitumen (see roofing felt), the fixed phenoxycarboxylic acid can also be added to these and worked in together with them.
BeispieleExamples
Beispiel 1example 1
3 g kommerziell erhältliche 4-Chlor-2-methyl-phenoxypropionsäure werden fein gepulvert zu 27 g Na-Zeolith X (wasserfrei) gegeben, erneut gepulvert und bei 120°C 10 Stunden lang unter Ausschluß von Wasser getempert. Man erhält 30 g feines Material.3 g of commercially available 4-chloro-2-methylphenoxypropionic acid are added to 27 g of Na zeolite X (anhydrous), finely powdered, powdered again and heat-treated at 120 ° C. for 10 hours with the exclusion of water. 30 g of fine material are obtained.
Beispiel 2Example 2
Analog Beispiel 1 nur mit Na-Zeolith Y (wasserfrei)Analogous to example 1, only with Na zeolite Y (anhydrous)
Beispiel 3Example 3
Analog Beispiel 1 nur mit H-Zeolith Y, ein dealuminierter Zeolith Y mit einem SiO2/Al2θ3 -Verhältnis von 90.
Analogously to Example 1, only with H zeolite Y, a dealuminated zeolite Y with an SiO 2 / Al 2 θ3 ratio of 90.
Prüfung auf Wurzelfestigkeit nach DIN 4062Root strength test according to DIN 4062
eingesetzter Lupinensamen: 40Lupine seeds used: 40
Probe Probenmaterial Substanz aus (Gehalt in Gew.-%)Sample Sample material Substance from (content in% by weight)
Topf l Bitumen 80 (Referenzprobe)Pot l bitumen 80 (reference sample)
Topf2 - 3 + 8,0 % Beispiel 1Pot2 - 3 + 8.0% Example 1
Topf 4 - 5 + 8,0 % Beispiel 2Pot 4 - 5 + 8.0% example 2
Topf 6 - 7 + 8,0 % Beispiel 3Pot 6 - 7 + 8.0% example 3
Topf 1Pot 1
A 38-40 38-40 38-40 38-40 38-40 38-40 38-40A 38-40 38-40 38-40 38-40 38-40 38-40 38-40
B 39 40 38 38 38 37 38B 39 40 38 38 38 37 38
C alle alle alle alle alle alle alleC all all all all all all
DD
E 0 0 0 0 0 0E 0 0 0 0 0 0
F ca.10F ca.10
A Wuchshöhe in cmA Height in cm
B angewachsene PflanzenB grown plants
C Aufwuchs-AnzahlC Number of growths
D Einwuchs-AnzahlD number of ingrowths
E Durchwuchs-AnzahlE number of growths
F Wurzellänge unter Testmaterial in cm
F Root length under test material in cm
Claims
1. Baustoffe, Dichtstoffe und Isoliermassen, enthaltend mindestens eine an einem anorganischen Trägermaterial gebundene Phenoxycarbonsäure.1. Building materials, sealants and insulating compositions containing at least one phenoxycarboxylic acid bonded to an inorganic carrier material.
2. Stoffe gemäß Anspruch 1, enthaltend als Phenoxycarbonsäure mindestens eine Verbindung der Formel (I)2. Substances according to claim 1, containing as phenoxycarboxylic acid at least one compound of formula (I)
in welcherin which
R1 bis R5 unabhängig voneinander für H, Br, CI, F, CF3, CF2H Methyl, Ethyl, Propyl, Methoxy, OCF3 stehen undR 1 to R 5 independently of one another represent H, Br, CI, F, CF 3 , CF 2 H methyl, ethyl, propyl, methoxy, OCF 3 and
R6 für H, Me, Et stehtR 6 stands for H, Me, Et
3. Stoffe gemäß Anspruch 1, enthaltend als Phenoxycarbonsäure die 4-Chlor-2- methyl-phenoxypropionsäure.3. Substances according to claim 1, containing the 4-chloro-2-methyl-phenoxypropionic acid as phenoxycarboxylic acid.
4. Stoffe gemäß Anspruch 1, enthaltend als anorganisches Trägermaterial nat. und synth. Zeolithe, Schichtsilikate, Tonerden, Fällungskieselsäuren, Kieselgure, Kieselgele, Aerosile, Bentonite, Kaoline, Aktivkohlen, natürliche und synthetische Tonmineralien, TiO , ZnO, Calciumcarbonat, Dolomite, Bimssteine, Attapulgite, Sepiolite, Ballclays, Tone, u.a. Alumophosphate, Silicoalumophosphate, Metallalumophosphate, kristalline Kieselsäuren mit Porenstruktur.4. Substances according to claim 1, containing nat as inorganic carrier material. and synthetic zeolites, layered silicates, clays, precipitated silicas, diatomaceous earth, silica gels, aerosils, bentonites, kaolins, activated carbons, natural and synthetic clay minerals, TiO, ZnO, calcium carbonate, dolomites, pumice stones, attapulgites, sepiolites, ball clays, clays, etc. Aluminum phosphates, silicoaluminophosphates, metal aluminophosphates, crystalline silicas with pore structure.
5. Verfahren zum Schutz von Bauwerken, Dichtungen und Isolierungen gegen Ein- und Durchwachsen von Wurzeln, dadurch gekennzeichnet, daß man Baustoffe, Dichtstoffe oder Isoliermassen mit an anorganischem Trägermaterial gebundener Phenoxycarbonsäure versetzt. 5. A method for protecting buildings, seals and insulation against ingrowth and growth of roots, characterized in that building materials, sealants or insulating materials are mixed with phenoxycarboxylic acid bound to an inorganic carrier material.
6. Verwendung einer Phenoxycarbonsäure/Träger-Kombination zum Schutz von Bauwerken, Isolierungen und Dichtungen gegen Durchwurzelung.6. Use of a phenoxycarboxylic acid / carrier combination to protect buildings, insulation and seals against root penetration.
7. Phenoxycarbonsäure/Träger-Kombination, enthaltend mindestens eine Verbin¬ dung der Formel (I) nach Ansprach 2 und anorganische Trägermaterialien nach Anspruch 4.7. phenoxycarboxylic acid / carrier combination containing at least one compound of the formula (I) according to spoke 2 and inorganic carrier materials according to claim 4.
8. Verfahren zur Herstellung einer Phenoxycarbonsäure/Träger-Kombination nach Ansprach 7, dadurch gekennzeichnet, daß man anorganisches Trägermaterial mit Verbindungen der Formel (I) nach Anspruch 2 beläd. 8. A process for the preparation of a phenoxycarboxylic acid / carrier combination according to spoke 7, characterized in that loading inorganic carrier material with compounds of formula (I) according to claim 2.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19934337844 DE4337844A1 (en) | 1993-11-05 | 1993-11-05 | Root penetration inhibitors |
DE4337844 | 1993-11-05 | ||
PCT/EP1994/003492 WO1995012312A1 (en) | 1993-11-05 | 1994-10-24 | Rooting inhibitors |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0726707A1 true EP0726707A1 (en) | 1996-08-21 |
Family
ID=6501924
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94931545A Withdrawn EP0726707A1 (en) | 1993-11-05 | 1994-10-24 | Rooting inhibitors |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0726707A1 (en) |
JP (1) | JPH10508001A (en) |
AU (1) | AU8059894A (en) |
CZ (1) | CZ130796A3 (en) |
DE (1) | DE4337844A1 (en) |
PL (1) | PL314176A1 (en) |
WO (1) | WO1995012312A1 (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SE512783C2 (en) * | 1998-03-30 | 2000-05-15 | Hoeganaes Ab | Stator assembly for an electric machine |
AU2002328296A1 (en) | 2002-06-19 | 2004-01-06 | Thor Gmbh | Coating material with biocide microcapsules |
GB0822004D0 (en) * | 2008-12-02 | 2009-01-07 | Syngenta Participations Ag | Building materials resistant to root penetration and methods for making the same |
DE202015105377U1 (en) * | 2015-10-12 | 2017-01-13 | Rehau Ag + Co | pipe arrangement |
AT517786A1 (en) * | 2015-10-13 | 2017-04-15 | Zsifkovits Wilhelm | Use of aryloxyphenoxypropionic acid herbicides for protection of structural waterproofing and bituminous sheeting containing them |
JP7430878B2 (en) * | 2020-01-23 | 2024-02-14 | ユニチカ株式会社 | Vine prevention sheet |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1108833B (en) * | 1958-08-05 | 1961-06-15 | Bayer Ag | Root-resistant or root-repellent sealing and casting compounds for underground water pipes |
NL249420A (en) * | 1959-03-17 | |||
DD98102A1 (en) * | 1972-09-04 | 1973-06-12 | ||
DD130269A1 (en) * | 1977-03-28 | 1978-03-15 | Gerhard Schmaland | PROCESS FOR PROTECTION OF SEALING ELEMENTS IN WATER CONSTRUCTION AGAINST PLANT GROWTH |
EP0001328A1 (en) * | 1977-09-23 | 1979-04-04 | FISONS plc | Method and composition for combating weeds |
DE3329100A1 (en) * | 1983-08-11 | 1985-02-28 | Oskar Dipl.-Ing. Innsbruck Hohenbruck | Method of protecting buried objects against damage due to plant roots |
JP2668064B2 (en) * | 1988-07-15 | 1997-10-27 | 世紀東急工業株式会社 | Filling joints for seams, forming joints for seams, and seam treatment methods for the purpose of suppressing weed growth at the seam between the asphalt pavement side end and the concrete structure |
DE4014924A1 (en) * | 1990-05-10 | 1991-11-14 | Basf Ag | HERBICIDAL AGENT FROM A DERIVATIVE OF N-PHENYL-3,4,5,6-TETRAHYDROPHTHALIMID AND A PHENOXYALCANIC CARBONIC ACID DERIVATIVE |
-
1993
- 1993-11-05 DE DE19934337844 patent/DE4337844A1/en not_active Withdrawn
-
1994
- 1994-10-24 EP EP94931545A patent/EP0726707A1/en not_active Withdrawn
- 1994-10-24 PL PL94314176A patent/PL314176A1/en unknown
- 1994-10-24 AU AU80598/94A patent/AU8059894A/en not_active Abandoned
- 1994-10-24 WO PCT/EP1994/003492 patent/WO1995012312A1/en not_active Application Discontinuation
- 1994-10-24 CZ CZ961307A patent/CZ130796A3/en unknown
- 1994-10-24 JP JP7512986A patent/JPH10508001A/en active Pending
Non-Patent Citations (1)
Title |
---|
See references of WO9512312A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO1995012312A1 (en) | 1995-05-11 |
PL314176A1 (en) | 1996-08-19 |
AU8059894A (en) | 1995-05-23 |
JPH10508001A (en) | 1998-08-04 |
DE4337844A1 (en) | 1995-05-11 |
CZ130796A3 (en) | 1996-07-17 |
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