WO1995012312A1

WO1995012312A1 - Rooting inhibitors

Info

Publication number: WO1995012312A1
Application number: PCT/EP1994/003492
Authority: WO
Inventors: Lutz Heuer; Heinz-Joachim Rother; Lothar Puppe
Original assignee: Bayer Aktiengesellschaft
Priority date: 1993-11-05
Filing date: 1994-10-24
Publication date: 1995-05-11
Also published as: CZ130796A3; AU8059894A; EP0726707A1; PL314176A1; DE4337844A1; JPH10508001A

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

Root penetration inhibitors

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. 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.

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).

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).

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.

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.

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.

The following compounds of the formula (I) are preferably used as phenoxycarboxylic acids

in which

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

in question.

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.

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.

A compound of the formula (I) in which R ^{1 is} Me is very particularly preferred,

R ² , R ⁴ , R ⁵ stand for H, R ^{3 is} CI and R ^{6 is} Me.

The following phenoxycarboxylic acids are also particularly suitable:

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.

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.

As . The zeolites or molecular sieves, which come under the following formula, have proven to be particularly suitable support materials:

M _mlz [mElθ ₂ ^• nE ² O ₂ ] ^• qH ₂ O

in the

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,

z stands for the value of the exchangeable cation and

q means the amount of water sorbed,

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.

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. 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.

Zeolites of the following structure types and corresponding analogs are preferred for the phenoxycarboxylic acid / carrier combination according to the invention:

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.

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.

In addition to zeolites, layered silicates such as e.g. Magadiit or SKS-6 suitable as a carrier material.

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 ) ι ₂ ^• (SiO ₂ ) ι] ^{• 2} ? H ₂ 0

Type X Na ₈₆ [AlO ₂ ) ₈₆ ^• (SiO ₂ ) ₁₀₆ ] ^{• 2} 64 H ₂ O

Type Y Na ₅₆ [AlO ₂ ) ₅₆ ^• (SiO ₂ ) ₁₃₆ ] ^■ 250 H ₂ O

In addition to the synthetic forms of the zeolites, 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.

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.

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.

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.

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.

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.

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.

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%.

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%.

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.

Examples

example 1

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.

Example 2

Analogous to example 1, only with Na zeolite Y (anhydrous)

Example 3

Analogously to Example 1, only with H zeolite Y, a dealuminated zeolite Y with an SiO ₂ / Al ₂ θ3 ratio of 90.

Root strength test according to DIN 4062

Lupine seeds used: 40

Sample Sample material Substance from (content in% by weight)

Pot l bitumen 80 (reference sample)

Pot2 - 3 + 8.0% Example 1

Pot 4 - 5 + 8.0% example 2

Pot 6 - 7 + 8.0% example 3

Pot 1

A 38-40 38-40 38-40 38-40 38-40 38-40 38-40

B 39 40 38 38 38 37 38

C all all all all all all

D

E 0 0 0 0 0 0

F ca.10

A Height in cm

B grown plants

C Number of growths

D number of ingrowths

E number of growths

F Root length under test material in cm

Claims

claims

1. Building materials, sealants and insulating compositions containing at least one phenoxycarboxylic acid bonded to an inorganic carrier material.

2. Substances according to claim 1, containing as phenoxycarboxylic acid at least one compound of formula (I)

in which

R 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

R ^{6 stands} for H, Me, Et

3. Substances according to claim 1, containing the 4-chloro-2-methyl-phenoxypropionic acid as phenoxycarboxylic acid.

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. 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. Use of a phenoxycarboxylic acid / carrier combination to protect buildings, insulation and seals against root penetration.

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. 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.