EP1206512B1 - Use of polyoxypropylene/polyoxyethylene terpene compounds as degreasing agents for hard surfaces - Google Patents

Use of polyoxypropylene/polyoxyethylene terpene compounds as degreasing agents for hard surfaces Download PDF

Info

Publication number
EP1206512B1
EP1206512B1 EP00958691A EP00958691A EP1206512B1 EP 1206512 B1 EP1206512 B1 EP 1206512B1 EP 00958691 A EP00958691 A EP 00958691A EP 00958691 A EP00958691 A EP 00958691A EP 1206512 B1 EP1206512 B1 EP 1206512B1
Authority
EP
European Patent Office
Prior art keywords
compound
radical
formula
use according
degreasing
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.)
Expired - Lifetime
Application number
EP00958691A
Other languages
German (de)
French (fr)
Other versions
EP1206512A1 (en
Inventor
Jean-Luc Joye
Jean-Guy Le Helloco
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Chimie SAS
Original Assignee
Rhodia Chimie SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rhodia Chimie SAS filed Critical Rhodia Chimie SAS
Publication of EP1206512A1 publication Critical patent/EP1206512A1/en
Application granted granted Critical
Publication of EP1206512B1 publication Critical patent/EP1206512B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2006—Monohydric alcohols
    • C11D3/2037—Terpenes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/263—Ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3227—Ethers thereof
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/16—Metals

Definitions

  • the present invention relates to the use of terpene compounds comprising oxypropylene and oxyethylenated units, as agents of degreasing / cleaning of hard surfaces, especially surfaces metal.
  • the compounds currently used in this field are essentially ethoxylated alkylphenols. These compounds intrinsically exhibit properties degreasing very satisfactory. However, they have a significant disadvantage, that of promoting the appearance of foam. This crippling phenomenon in this application, is reduced by the addition of a defoaming agent, such as for example alkoxylated linear alcohols. However, the presence of this type of compound decreases non-negligible way, and this in a definitive way, the degreasing activity of ethoxylated alkylphenol. Indeed, it is not possible to compensate the loss of activity by a further addition of alkylphenol, so as to recover the initial level of activity.
  • the present invention aims to propose the use of a terpenic compound particular, satisfying the two criteria mentioned previously, in the application of the cleaning / degreasing of hard surfaces, especially metal surfaces, and at low concentrations.
  • a first type of compound is defined by the formula (I) wherein X is -CH 2 -C (R 1 ) (R 2 ) -O-.
  • this compound hereinafter compound (Ia), corresponds to the following formula: Z-CH 2 -C (R 1 ) (R 2 ) -O- [CH (R 3 ) -CH (R 4 ) -O] n - [CH 2 CH 2 -O] p -R 5 wherein Z, R 1 , R 2 , R 3 , R 4 , R 5 , n and p have the general meaning indicated above.
  • the radical Z is chosen from the radicals of formulas c) to g).
  • radical Z is more particularly related to the rest of the chain through any one of carbon atoms 1 to 6; the atoms carbon numbers 1, 5 and 6 being preferred.
  • radical Z may be substituted on at least one of its carbon atoms by two C 1 -C 6 alkyl radicals, preferably two methyl radicals.
  • carbon 7 is substituted by these two alkyl radicals, more precisely two methyls.
  • One of the preferred compounds of the invention therefore consists of a compound whose radical Z corresponds to one of those appearing in Figure c) to g), and more preferably, the radicals d) and e); the radical Z being substituted by two methyl radicals, localized on carbon 7.
  • the radical Z corresponds to formulas d) or e), attached to the rest of the chain by carbon 5 or 1, and carrying two methyl substituents on carbon 7.
  • R 1 , R 2 which may be identical or different, represent a hydrogen or a methyl radical.
  • R 1 , R 2 represent a hydrogen atom.
  • radicals R 3 and R 4 which may be identical or different, represent hydrogen or a hydrocarbon radical, saturated or non-saturated, linear, branched or cyclic, with C 1 -C 22 , provided that at least one of R 3 or R 4 is different from hydrogen.
  • said radicals represent hydrogen or a C 1 -C 6 alkyl radical, preferably the methyl radical or the ethyl radical, with the proviso that at least one of these two radicals is different from hydrogen.
  • one of the radicals represents hydrogen and the other a methyl radical.
  • R 5 is a hydrocarbon radical
  • the latter is more particularly a C 1 -C 6 alkyl radical, or an alkylphenyl radical, optionally substituted by a halogen (such as chlorine for example).
  • R 5 is a hydrogen atom.
  • n is an integer or not, between 3 and 5 inclusive and p is a integer or not, between 6 and 10, the terminals being excluded.
  • n 3.
  • p is more particularly between 6.2 and 7, terminals included.
  • p is between 6.3 and 7, inclusive.
  • n is included between 4 and 5, terminals included.
  • the value of p is preferably comprised of 7 inclusive and 10 excluded, of preferably between 8 inclusive and 10 excluded.
  • a second type of compound is defined by the formula (I) wherein X is -O-CH (R ' 1 ) -CH (R' 2 ) -O-.
  • this compound hereinafter compound (Ib), corresponds to the following formula: ZO-CH (R ' 1 ) -CH (R' 2 ) -O- [CH (R 3 ) -CH (R 4 ) -O] n - [CH 2 CH 2 -O] p -R 5 wherein Z, R ' 1 , R' 2 , R 3 , R 4 , R 5 , n and p have the general meaning indicated above.
  • radical Z corresponds to radical c), the bicyclic compound having no double bond.
  • radical Z is more particularly related to the rest of the chain through any of the carbon 1 to 6.
  • the atoms of carbon 1, 3, 4 or 6 are more particularly retained.
  • radical Z may be substituted on at least one of its carbon atoms by two C 1 -C 6 alkyl radicals, preferably two methyl radicals.
  • carbon 7 is substituted by these two alkyl radicals, more precisely two methyls.
  • radical Z bears on one of the carbon atoms 2 or 5, a C 1 -C 6 alkyl substituent, preferably a methyl radical.
  • radicals R ' 1 and R' 2 which are identical or different, represent hydrogen or a saturated or unsaturated, linear, branched or cyclic, C 1 -C 22 hydrocarbon-based radical.
  • said radicals represent hydrogen or a C 1 -C 6 alkyl radical, preferably the methyl radical.
  • a particularly advantageous embodiment of the present invention is constituted by the use of the compound of type (la) previously described.
  • the reaction may further be carried out in the presence of a catalyst.
  • Suitable catalysts include strong bases such as alkali metal, alkaline-earth or quaternary ammonium hydroxides of N (R) 4 + type , in which R, which may be identical or different, represent hydrogen or a radical.
  • R which may be identical or different, represent hydrogen or a radical.
  • the hydroxides of sodium, potassium and tetramethylammonium are suitable for carrying out this reaction.
  • catalysts chosen from metal alkoxides alkali or alkaline earth metals, such as methylate, ethylate, tert-butylate sodium or potassium. It should be noted that it is also possible to register as a catalyst, primary, secondary or tertiary amines, preferably amines aliphatic, these amines may include other functions such as ether functions. By way of example of a catalyst of this type, mention may be made of N, N-dimethyllaurylamine.
  • the amount is more particularly included between 0.5 and 40 mg based on the weight of the final product.
  • the amount of acid catalyst varies more particularly between 0.1 and 10 mmol per mole of reagent (Ila) or (Ilb).
  • the contacting is carried out at a temperature sufficient to allow the completion of the reaction.
  • the temperature is greater than 100 ° C, more particularly between 120 and 250 ° C, and preferably between 150 and 200 ° C.
  • the reaction is carried out under an inert atmosphere in the reaction conditions, such as nitrogen, or a rare gas such as argon or carbon monoxide. Nitrogen is preferred.
  • the reaction can take place under atmospheric pressure, under reduced pressure or slight overpressure. Usually, we prefer to work under pressure between 1 and 4 bar.
  • the amounts of the compounds (IIIop) and (IIIoe) are calculated according to the characteristics of formula (I), more particularly desired values of n and p.
  • the reaction mixture is preferably neutralized in order to to obtain a pH of between 5 and 8, preferably 6 and 7.
  • the neutralization is made with acetic acid, or with hydroxide, with carbonate or sodium bicarbonate, depending on the nature of the catalyst involved in the reaction.
  • the compound (I) is such that the radical R 5 is hydrogen.
  • the compounds according to the invention are therefore used as a degreasing agent hard surfaces and more particularly metal surfaces.
  • the compounds according to the invention can be used in the metal processing, but also in any application in which one puts in degreasing such surfaces as the degreasing of wells or platforms oil exploitation.
  • the compound used according to the invention is with a quantity of between 0.01 and 10 g / l at the time of use.
  • the concentration in compound is more particularly between 0.01 and 5 g / l during use.
  • the compound concentration is between 0.01 and 10 g / l at the time of use, the compound used according to the invention.
  • the compound according to the invention is implemented with a concentration of preferably between 0.01 and 5 g / l.
  • Aqueous degreasing or detergent media containing the compounds according to the invention are preferably used at a temperature at least of the order of their cloud temperature.
  • the concentration of alkaline lye in use is between 1 and 100 g / l, more particularly between 5 and 20 g / l.
  • concentrations of these compounds vary in the usual ranges of field. However, by way of illustration, the content of each of the compounds varies from 0 at 1.5 g / l at the time of use.
  • the concentrations of these compounds vary in the ranges usual domain.
  • the content of each of the compounds varies from 0 at 1.5 g / l at the time of use.
  • surfactants anionic, cationic, zwitterionic, amphoteric
  • low foaming preferably low foaming
  • This example relates to the synthesis of 6,6-dimethylbicyclo [3.1.1] hept-2-ene-2 ethanol comprising oxypropylene units (OP) and oxyethylenated units (EO) variables.
  • OP oxypropylene units
  • EO oxyethylenated units
  • the reaction medium is dehydrated at 120 ° C. under a stream of nitrogen.
  • reaction medium is then cooled, neutralized by addition of acetic acid until the pH is 7.
  • acetic acid until the pH is 7.
  • the resulting liquid is filtered on absorbent soil (Clarcel DIC).
  • This example aims to compare the degreasing properties of compounds according to the invention 1 and 3, comparative compounds 8, 9 and 10, as well as those obtained with Igepal NP10 defoamed.
  • Pre-greased steel plates of "Q-Panel” brand Stock No. R-36 type "Dull matt finish" of 0.8 x 76 x 152 mm are immersed for 2 minutes in a lubricating whole oil formulated for rolling steel sheets for automobiles, QUAKER brand 6130 N from Quaker Chemicals, then suspended for draining for 24 hours.
  • the greased plates are introduced into a degreasing machine by CIEMME LARO 350 sprinkler.
  • the degreasing temperature is 45 ° C and the pressure of 2 bar.
  • the plates are rinsed under a net running water 2 ml / min for 5 seconds on each side.
  • a basic degreasing medium (pH 12-13) is prepared by dilution in water 20 g / l of an aqueous solution containing 45% by weight of active ingredient constituted equal amounts by weight of potassium hydroxide, sodium metasilicate (SIMET GA5, granules of anhydrous metasilicate and metasilicate pentahydrate, marketed by Rhodia Chimie) and tetrapotassium pyrophosphate, and addition of 1 g / l of the compound to test.
  • SIMET GA5 sodium metasilicate
  • granules of anhydrous metasilicate and metasilicate pentahydrate marketed by Rhodia Chimie
  • tetrapotassium pyrophosphate tetrapotassium pyrophosphate
  • This example aims to compare the degreasing properties of compounds according to the invention 4 to 7, as well as those obtained with Igepal NP9 not defoamed.
  • Pennzoil 80W-90 brand oil marketed by Pennzoil Products Company was brushed onto 0.8 x 24 x 101 mm pre-degreased steel plates to obtain a coating of oil. about 0.015 g / cm 2 . They are then stored in the air for 24 hours.
  • the amount of oil is measured by weighing the plate before and after application oil.
  • the plate is immersed in one liter of degreasing medium, with stirring magnetic (100 rpm), at 50 ° C for 10 minutes.
  • the plates are rinsed under a net running water 2 ml / min for 5 seconds on each side, then dried at 80 ° C.
  • the measurement of the efficiency of the operation is calculated by weighing the front plate and after treatment with the degreasing medium.
  • a basic degreasing medium (pH 12-13) is prepared by dilution in water 20 g / l of an aqueous solution containing 1.5 g / l of tetrapotassium pyrophosphate, and addition of 1 g / l of the test compound.
  • This example aims to compare the foaming properties of compounds obtained in Examples 1 to 7, as well as those obtained with the compounds comparative Igepal blunted, Igepal alone.
  • a basic degreasing medium (pH 12-13) is prepared by dilution in water 20 g / l of an aqueous solution containing 45% by weight of active ingredient constituted equal amounts by weight of potassium hydroxide, sodium metasilicate (SIMET GA5, granules of anhydrous metasilicate and metasilicate pentahydrate, marketed by Rhodia Chimie) and tetrapotassium pyrophosphate and addition of 1 g / l of the compound to test.
  • SIMET GA5 sodium metasilicate
  • granules of anhydrous metasilicate and metasilicate pentahydrate marketed by Rhodia Chimie
  • tetrapotassium pyrophosphate tetrapotassium pyrophosphate
  • the test is carried out at 50 ° C.
  • the foam is obtained by stirring 900 g of solution with a stirrer. turbine (40mm turbine, 2000rpm speed) for 5 minutes.
  • the level of foam is read in a test tube after 5 minutes of rest.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Lubricants (AREA)
  • External Artificial Organs (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Materials For Medical Uses (AREA)
  • Polyethers (AREA)

Abstract

The invention concerns the use in degreasing/cleansing applications of hard surfaces, such as metal surfaces, of at least a compound derived from a terpene and comprising a number of oxypropylene units ranging between 3 and 5, and a number of oxyethylene units ranging between 6 and 10, exclusively. The compound is provided with a concentration lower than 10 g/l, more particularly between 0.01 and 5 g/l, when used.

Description

La présente invention a pour objet l'utilisation de composés terpéniques comprenant des motifs oxypropylénés et oxyéthylénés, en tant qu'agents de dégraissage/nettoyage de surfaces dures, et plus particulièrement de surfaces métalliques.The present invention relates to the use of terpene compounds comprising oxypropylene and oxyethylenated units, as agents of degreasing / cleaning of hard surfaces, especially surfaces metal.

Le domaine du nettoyage/dégraissage de surfaces métalliques demande des performances très élevées, notamment pour ce qui concerne le pouvoir dégraissant de la composition mise en oeuvre, ainsi que sa capacité à ne pas créer de mousse. Notons de plus que ces résultats sont bien souvent requis alors que les conditions de mises en oeuvre sont très difficiles. Ainsi, les méthodes d'aspersion sont très favorables à l'apparition de mousse, du fait que le bain de traitement est appliqué sous pression.The field of cleaning / degreasing of metal surfaces requires very high performance, particularly with regard to the degreasing power of the composition used, as well as its ability not to create foam. note Moreover, these results are often required while the conditions for work are very difficult. Thus, the sprinkling methods are very favorable to the appearance of foam, because the treatment bath is applied under pressure.

Les composés actuellement mis en oeuvre dans ce domaine sont pour l'essentiel des alkylphénols éthoxylés. Ces composés présentent intrinsèquement des propriétés de dégraissage très satisfaisantes. Cependant, ils présentent un important inconvénient, celui de favoriser l'apparition de mousse. Ce phénomène rédhibitoire dans cette application, est diminué par l'ajout d'un agent démoussant, comme par exemple des alcools linéaires alcoxylés. Cependant, la présence de ce type de composé diminue de manière non négligeable, et ceci de façon définitive, l'activité dégraissante de l'alkylphénol éthoxylé. En effet, il n'est pas possible de compenser la perte d'activité par un ajout supplémentaire d'alkylphénol, de manière à récupérer le niveau d'activité initial.The compounds currently used in this field are essentially ethoxylated alkylphenols. These compounds intrinsically exhibit properties degreasing very satisfactory. However, they have a significant disadvantage, that of promoting the appearance of foam. This crippling phenomenon in this application, is reduced by the addition of a defoaming agent, such as for example alkoxylated linear alcohols. However, the presence of this type of compound decreases non-negligible way, and this in a definitive way, the degreasing activity of ethoxylated alkylphenol. Indeed, it is not possible to compensate the loss of activity by a further addition of alkylphenol, so as to recover the initial level of activity.

Dans le brevet WO 96/01245 sont décrits des composés terpéniques alcoxylés présentés comme de bons dégraissants favorisant peu l'apparition de mousse. Les composés exemplifiés sont dérivés de composés terpéniques du type du nopol ou de l'arbanol, et comprennent 0 à 2 motifs oxypropylénés et 3,3 à 10,3 motifs oxyéthylénés.In patent WO 96/01245 are described alkoxylated terpene compounds presented as good degreasers that do not favor the appearance of foam. The exemplified compounds are derived from terpene compounds of the nopol type or arbanol, and comprise 0 to 2 oxypropylene units and 3.3 to 10.3 oxyethylenated units.

Ces composés dont l'intérêt n'est pas remis en doute ici, ne donnent cependant pas de bons résultats dans l'application très particulière du traitement des surfaces dures et notamment métalliques. En effet, ils ne répondent pas simultanément aux deux critères requis dans ce domaine, que sont une activité de dégraissage élevée et une action défavorable à l'apparition de mousse. Ceci a pour conséquence de rendre nécessaire l'augmentation de la teneur en composé dans la formulation et/ou de l'ajout d'un agent démoussant, avec les inconvénients que l'on sait. Il est en outre précisé que malgré l'ajout de quantités importantes de ces composés, les niveaux de dégraissage atteints sont au plus équivalents à ceux des alkylphénols éthoxylés. These compounds, the interest of which is not called into question here, no good results in the very particular application of surface treatment hard and especially metallic. Indeed, they do not respond simultaneously to both criteria in this area, which are a high level of degreasing activity and a unfavorable action to the appearance of foam. This has the consequence of rendering necessary to increase the compound content in the formulation and / or the addition a defoaming agent, with the disadvantages that we know. It is further specified that despite the addition of significant amounts of these compounds, the levels of degreasing affected are at most equivalent to those of ethoxylated alkylphenols.

Comme on peut le constater, il est nécessaire de pouvoir disposer de composés dont le pouvoir dégraissant est très élevé, et qui ne soient pas à l'origine de l'apparition d'un niveau de mousse important. L'utlisation de tels composés présenterait le double avantage de ne pas rendre nécessaire l'emploi de quantités importantes de ce composé, ni l'ajout de composés supplémentaires, comme des agents démoussants.As can be seen, it is necessary to have available compounds whose degreasing power is very high, and which are not the cause of the appearance a high level of foam. The use of such compounds would be double advantage of not making necessary the use of large quantities of this compound, nor the addition of additional compounds, such as defoaming agents.

La présente invention a pour objectif de proposer d'utiliser un composé terpénique particulier, satisfaisant au double critère mentionné auparavant, dans l'application du nettoyage/dégraissage de surfaces dures et notamment de surfaces métalliques, et ce, à des concentrations faibles.The present invention aims to propose the use of a terpenic compound particular, satisfying the two criteria mentioned previously, in the application of the cleaning / degreasing of hard surfaces, especially metal surfaces, and at low concentrations.

Ainsi, la présente invention a pour objet l'utilisation pour le nettoyage/dégraissage de surfaces dures, d'au moins un composé, mis en oeuvre avec une concentration comprise entre 0,01 et 10 g/l, lors de l'utilisation de ce dernier, de formule suivante : Z- X -[CH(R3)-CH(R4)-O]n-[CH2CH2-O]p-R5 formule dans laquelle

  • Z représente un radical bicyclo[a,b,c]heptényle ou bicyclo[a,b,c]heptyle, avec a+b+c = 5
  • a = 2, 3 ou 4,
  • b = 2 ou 1
  • c = 0 ou 1,
    • ledit radical étant éventuellement substitué par au moins un radical alkyle de C1-C6, et comprenant un squelette Z choisi parmi ceux indiqués ci-dessous, ou aux squelettes correspondants, dépourvus de double liaison :
    Figure 00020001
    Figure 00020002
    Figure 00020003
  • X représente -CH2-C(R1)(R2)-O- ou -O-CH(R'1)-CH(R'2)-O- dans lesquelles:
    • R1, R2, R'1 et R'2, identiques ou différents, représentent l'hydrogène ou un radical hydrocarboné, saturé ou non, linéaire, ramifié ou cyclique, en C1-C22, de préférence en C1-C6,
    • R3 et R4, identiques ou différents, représentent l'hydrogène ou un radical hydrocarboné, saturé ou non, linéaire, ramifié ou cyclique, en C1-C22, à la condition qu'au moins l'un des radicaux R3 ou R4 soit différent de l'hydrogène ;
    • R5 représente l'hydrogène, un radical hydrocarboné, saturé ou non, linéaire, ramifié ou cyclique, aromatique ou non, en C1-C22, éventuellement substitué, ou un groupement choisi parmi les suivants :
    • -SO3M
    • -OPO3(M)2
    • -(CH2)r - COOM
    • -(CH2)z-SO3M,
      • formules dans lesquelles
      • M représente l'hydrogène, un métal alcalin ou une fonction ammonium N(R)4 +, dans laquelle R, identiques ou non, représentent l'hydrogène ou un radical hydrocarboné, saturé ou non, linéaire, ramifié ou cyclique, en C1-C22, éventuellement hydroxylé ;
      • r est compris entre 1 et 6 ;
      • z est compris entre 1 et 6 ;
    • n est un nombre entier ou non, compris entre 3 et 5 inclus ;
    • p est un nombre entier ou non compris entre 6 et 10, les bornes étant exclues.
Thus, the present invention relates to the use for the cleaning / degreasing of hard surfaces, of at least one compound, used with a concentration of between 0.01 and 10 g / l, when using the latter, of the following formula: Z- X - [CH (R 3 ) -CH (R 4 ) -O] n - [CH 2 CH 2 -O] p -R 5 formula in which
  • Z represents a bicyclo [a, b, c] heptenyl or bicyclo [a, b, c] heptyl radical, with a + b + c = 5
  • a = 2, 3 or 4,
  • b = 2 or 1
  • c = 0 or 1,
    • said radical being optionally substituted with at least one alkyl radical of C 1 -C 6 , and comprising a backbone Z chosen from those indicated below, or corresponding skeletons, devoid of double bond:
    Figure 00020001
    Figure 00020002
    Figure 00020003
  • X represents -CH 2 -C (R 1 ) (R 2 ) -O- or -O-CH (R ' 1 ) -CH (R' 2 ) -O- in which:
    • R 1 , R 2 , R ' 1 and R' 2 , which are identical or different, represent hydrogen or a hydrocarbon radical, saturated or non-saturated, linear, branched or cyclic, in C 1 -C 22 , preferably in C 1 - C 6 ,
    • R 3 and R 4 , which may be identical or different, represent hydrogen or a saturated or unsaturated, linear, branched or cyclic C 1 -C 22 hydrocarbon radical, with the proviso that at least one of the radicals R 3 or R 4 is different from hydrogen;
    • R 5 represents hydrogen, a hydrocarbon radical, saturated or unsaturated, linear, branched or cyclic, aromatic or non-aromatic, optionally substituted C 1 -C 22 , or a group chosen from the following:
    • -SO 3 M
    • -OPO 3 (M) 2
    • - (CH 2 ) r - COOM
    • - (CH 2 ) z -SO 3 M,
      • formulas in which
      • M represents hydrogen, an alkali metal or an ammonium N (R) 4 + functional group , in which R, which may be identical or different, represents hydrogen or a hydrocarbon radical, saturated or unsaturated, linear, branched or cyclic, in C 1 -C 22 , optionally hydroxylated;
      • r is from 1 to 6;
      • z is from 1 to 6;
    • n is an integer or not, from 3 to 5 inclusive;
    • p is an integer or not between 6 and 10, the terminals being excluded.

Mais d'autres caractéristiques et avantages de la présente invention apparaítront plus clairement à la lecture de la description et des exemples qui vont suivre.But other features and advantages of the present invention will become apparent more clearly on reading the description and examples that follow.

Les composés mis en oeuvre dans le cadre de la présente invention vont tout d'abord être décrits.The compounds used in the context of the present invention are all first be described.

Un premier type de composés est défini par la formule (I) dans laquelle X est égal à -CH2-C(R1)(R2)-O-.A first type of compound is defined by the formula (I) wherein X is -CH 2 -C (R 1 ) (R 2 ) -O-.

Ainsi, ce composé, ci-après composé (la), correspond à la formule suivante : Z-CH2-C(R1)(R2)-O-[CH(R3)-CH(R4)-O]n-[CH2CH2-O]p-R5 formule dans laquelle Z, R1, R2, R3, R4, R5, n et p ont la signification générale indiquée auparavant.Thus, this compound, hereinafter compound (Ia), corresponds to the following formula: Z-CH 2 -C (R 1 ) (R 2 ) -O- [CH (R 3 ) -CH (R 4 ) -O] n - [CH 2 CH 2 -O] p -R 5 wherein Z, R 1 , R 2 , R 3 , R 4 , R 5 , n and p have the general meaning indicated above.

Selon un mode de réalisation préféré de l'invention, le radical Z est choisi parmi les radicaux des formules c) à g).According to a preferred embodiment of the invention, the radical Z is chosen from the radicals of formulas c) to g).

Il est à noter que le radical Z est plus particulièrement rattaché au reste de la chaíne par l'intermédiaire de l'un quelconque des atomes de carbone 1 à 6 ; les atomes de carbone 1, 5 et 6 étant préférés. It should be noted that the radical Z is more particularly related to the rest of the chain through any one of carbon atoms 1 to 6; the atoms carbon numbers 1, 5 and 6 being preferred.

Par ailleurs, le radical Z peut être substitué sur au moins l'un de ses atomes de carbone, par deux radicaux alkyles en C1-C6, de préférence deux radicaux méthyles.Moreover, the radical Z may be substituted on at least one of its carbon atoms by two C 1 -C 6 alkyl radicals, preferably two methyl radicals.

Plus particulièrement, le carbone 7 est substitué par ces deux radicaux alkyles, plus précisément deux méthyles.More particularly, carbon 7 is substituted by these two alkyl radicals, more precisely two methyls.

L'un des composés préférés de l'invention est donc constitué par un composé dont le radical Z correspond à l'un de ceux apparaissant sur la figure c) à g), et de manière plus préférée, les radicaux d) et e) ; le radical Z étant substitué par deux radicaux méthyles, localisés sur le carbone 7.One of the preferred compounds of the invention therefore consists of a compound whose radical Z corresponds to one of those appearing in Figure c) to g), and more preferably, the radicals d) and e); the radical Z being substituted by two methyl radicals, localized on carbon 7.

Selon un mode encore plus avantageux de l'invention, le radical Z correspond aux formules d) ou e), rattaché au reste de la chaíne par le carbone 5 ou 1, et portant deux substituants méthyles sur le carbone 7.According to an even more advantageous embodiment of the invention, the radical Z corresponds to formulas d) or e), attached to the rest of the chain by carbon 5 or 1, and carrying two methyl substituents on carbon 7.

De préférence, R1, R2, identiques ou non, représentent un hydrogène, ou un radical méthyle. De préférence, R1, R2, représentent un atome d'hydrogène.Preferably, R 1 , R 2 , which may be identical or different, represent a hydrogen or a methyl radical. Preferably, R 1 , R 2 , represent a hydrogen atom.

Ainsi que cela a été indiqué auparavant, les radicaux R3 et R4, identiques ou différents, représentent l'hydrogène ou un radical hydrocarboné, saturé ou non, linéaire, ramifié ou cyclique, en C1-C22, à la condition qu'au moins l'un des radicaux R3 ou R4 soit différent de l'hydrogène.As indicated above, the radicals R 3 and R 4 , which may be identical or different, represent hydrogen or a hydrocarbon radical, saturated or non-saturated, linear, branched or cyclic, with C 1 -C 22 , provided that at least one of R 3 or R 4 is different from hydrogen.

Plus particulièrement, lesdits radicaux représentent l'hydrogène ou un radical alkyle en C1-C6, de préférence le radical méthyle ou le radical éthyle, à la condition qu'au moins l'un de ces deux radicaux soit différent de l'hydrogène. De préférence, l'un des radicaux représente l'hydrogène, l'autre un radical méthyle.More particularly, said radicals represent hydrogen or a C 1 -C 6 alkyl radical, preferably the methyl radical or the ethyl radical, with the proviso that at least one of these two radicals is different from hydrogen. . Preferably, one of the radicals represents hydrogen and the other a methyl radical.

R5 représente l'hydrogène, un radical hydrocarboné, saturé ou non, linéaire, ramifié ou cyclique, aromatique ou non, éventuellement substitué, en C1-C22, ou un groupement choisi parmi -SO3M, -OPO3(M)2, -(CH2)rCOOM, -(CH2)z-SO3M ; formules
dans lesquelles :

  • M représente l'hydrogène, un métal alcalin ou une fonction ammonium N(R)4 +, dans laquelle R, identiques ou non, représentent l'hydrogène ou un radical hydrocarboné, saturé ou non, linéaire, ramifié ou cyclique, en C1-C22, de préférence en C1-C6-éventuellement hydroxylé ;
  • r est compris entre 1 et 6 ;
  • z est compris entre 1 et 6.
R 5 represents hydrogen, a hydrocarbon radical, saturated or unsaturated, linear, branched or cyclic, aromatic or non-aromatic, optionally substituted, C 1 -C 22 , or a group chosen from -SO 3 M, -OPO 3 (M ) 2, - (CH 2) r -COOM, - (CH 2) z -SO 3 M; formulas
in which :
  • M represents hydrogen, an alkali metal or an ammonium N (R) 4 + functional group , in which R, which may be identical or different, represents hydrogen or a hydrocarbon radical, saturated or unsaturated, linear, branched or cyclic, in C 1 -C 22 , preferably C 1 -C 6 - optionally hydroxylated;
  • r is from 1 to 6;
  • z is between 1 and 6.

Dans le cas ou R5 est un radical hydrocarboné, ce dernier est plus particulièrement un radical alkyle en C1-C6, ou un radical alkylphényle, éventuellement substitué par un halogène (tel que le chlore par exemple).In the case where R 5 is a hydrocarbon radical, the latter is more particularly a C 1 -C 6 alkyl radical, or an alkylphenyl radical, optionally substituted by a halogen (such as chlorine for example).

De préférence, R5 est un atome d'hydrogène.Preferably, R 5 is a hydrogen atom.

Enfin, n est un nombre entier ou non, compris entre 3 et 5 inclus et p est un nombre entier ou non, compris entre 6 et 10, les bornes étant exclues. Finally, n is an integer or not, between 3 and 5 inclusive and p is a integer or not, between 6 and 10, the terminals being excluded.

Selon un premier mode de réalisation particulier de la présente invention, la valeur de n est de 3.According to a first particular embodiment of the present invention, the value of n is 3.

En outre, la valeur de p est plus particulièrement comprise entre 6,2 et 7, bornes comprises. De préférence, p est compris entre 6,3 et 7, bornes comprises.In addition, the value of p is more particularly between 6.2 and 7, terminals included. Preferably, p is between 6.3 and 7, inclusive.

Selon un second mode de réalisation particulier de l'invention, n est compris entre 4 et 5, bornes comprises.According to a second particular embodiment of the invention, n is included between 4 and 5, terminals included.

De plus, la valeur de p est de préférence comprise 7 inclus et 10 exclu, de préférence entre 8 inclus et 10 exclu.Moreover, the value of p is preferably comprised of 7 inclusive and 10 excluded, of preferably between 8 inclusive and 10 excluded.

Un second type de composés est défini par la formule (I) dans laquelle X représente -O-CH(R'1)-CH(R'2)-O-.A second type of compound is defined by the formula (I) wherein X is -O-CH (R ' 1 ) -CH (R' 2 ) -O-.

Ainsi, ce composé, ci-après composé (Ib), correspond à la formule suivante : Z-O-CH(R'1)-CH(R'2)-O-[CH(R3)-CH(R4)-O]n-[CH2CH2-O]p-R5 formule dans laquelle Z, R'1, R'2, R3, R4, R5, n et p ont la signification générale indiquée auparavant.Thus, this compound, hereinafter compound (Ib), corresponds to the following formula: ZO-CH (R ' 1 ) -CH (R' 2 ) -O- [CH (R 3 ) -CH (R 4 ) -O] n - [CH 2 CH 2 -O] p -R 5 wherein Z, R ' 1 , R' 2 , R 3 , R 4 , R 5 , n and p have the general meaning indicated above.

Selon un mode de réalisation préféré de l'invention, le radical Z correspond au radical c), le composé bicyclique ne comportant pas de double liaison.According to a preferred embodiment of the invention, the radical Z corresponds to radical c), the bicyclic compound having no double bond.

Là encore, il est à noter que le radical Z est plus particulièrement rattaché au reste de la chaíne par l'intermédiaire de l'un quelconque des carbone 1 à 6. Les atomes de carbone 1, 3, 4 ou 6 sont plus particulièrement retenus.Again, it should be noted that the radical Z is more particularly related to the rest of the chain through any of the carbon 1 to 6. The atoms of carbon 1, 3, 4 or 6 are more particularly retained.

Par ailleurs, le radical Z peut être substitué sur au moins l'un de ses atomes de carbone, par deux radicaux alkyles en C1-C6, de préférence deux radicaux méthyles.Moreover, the radical Z may be substituted on at least one of its carbon atoms by two C 1 -C 6 alkyl radicals, preferably two methyl radicals.

Plus particulièrement, le carbone 7 est substitué par ces deux radicaux alkyles, plus précisément deux méthyles.More particularly, carbon 7 is substituted by these two alkyl radicals, more precisely two methyls.

De plus, le radical Z porte sur l'un des atomes de carbone 2 ou 5, un substituant alkyle en C1-C6, de préférence un radical méthyle.In addition, the radical Z bears on one of the carbon atoms 2 or 5, a C 1 -C 6 alkyl substituent, preferably a methyl radical.

Plus particulièrement, et comme mentionné auparavant, les radicaux R'1 et R'2, identiques ou différents, représentent l'hydrogène ou un radical hydrocarboné, saturé ou non, linéaire, ramifié ou cyclique, en C1-C22.More particularly, and as previously mentioned, the radicals R ' 1 and R' 2 , which are identical or different, represent hydrogen or a saturated or unsaturated, linear, branched or cyclic, C 1 -C 22 hydrocarbon-based radical.

Selon un mode de réalisation particulier de l'invention, lesdits radicaux représentent l'hydrogène ou un radical alkyle en C1-C6, de préférence le radical méthyle.According to a particular embodiment of the invention, said radicals represent hydrogen or a C 1 -C 6 alkyl radical, preferably the methyl radical.

Ce qui a été indiqué à propos des radicaux R3, R4 et R5, ainsi que des valeurs de n et p et des variantes préférées liées à ces valeurs, reste valable et ne sera pas repris à nouveau.What has been said about the radicals R 3 , R 4 and R 5 , as well as values of n and p and preferred variants related to these values, remains valid and will not be repeated again.

Un mode de réalisation particulièrement avantageux de la présente invention est constitué par l'utilisation des composé de type (la) décrit auparavant.A particularly advantageous embodiment of the present invention is constituted by the use of the compound of type (la) previously described.

Les composés selon l'invention peuvent être préparés en faisant réagir :

  • pour l'obtention de composés (la), un réactif de formule (IIa)
    Figure 00060001
  • ou pour l'obtention de composé (Ib), un réactif de formule (IIb)
    Figure 00060002
  • avec, dans un premier temps, un réactif de formule (IIIop)
    Figure 00060003
  • puis, dans un second temps, avec un réactif de formule (IIIoe)
    Figure 00060004
    • The compounds according to the invention can be prepared by reacting:
  • for obtaining compounds (Ia), a reagent of formula (IIa)
    Figure 00060001
  • or to obtain compound (Ib), a reagent of formula (IIb)
    Figure 00060002
  • with, initially, a reagent of formula (IIIop)
    Figure 00060003
  • then, in a second step, with a reagent of formula (IIIoe)
    Figure 00060004
    •

    Les radicaux Z, R1, R2, R'1, R'2, R3 et R4 ont été définis auparavantThe radicals Z, R 1 , R 2 , R '1 , R ' 2 , R 3 and R 4 have been defined before

    La réaction peut de plus être mise en oeuvre en présence d'un catalyseur.The reaction may further be carried out in the presence of a catalyst.

    Parmi les catalyseurs convenables, on peut citer les bases fortes comme les hydroxydes de métaux alcalins, alcalino-terreux ou d'ammonium quaternaires de type N(R)4 +, dans laquelle R, identiques ou non, représentent l'hydrogène ou un radical alkyle en C1-C6, de préférence le méthyle, l'éthyle. Les hydroxydes de sodium, potassium, de tétraméthylammonium conviennent à la réalisation de cette réaction.Suitable catalysts include strong bases such as alkali metal, alkaline-earth or quaternary ammonium hydroxides of N (R) 4 + type , in which R, which may be identical or different, represent hydrogen or a radical. C 1 -C 6 alkyl, preferably methyl, ethyl. The hydroxides of sodium, potassium and tetramethylammonium are suitable for carrying out this reaction.

    On peut de même utiliser des catalyseurs choisis parmi les alcoxydes de métaux alcalins ou alcalino-terreux, comme par exemple le méthylate, l'éthylate, le tertiobutylate de sodium ou de potassium. Il est à noter que l'on aussi peut mettre en oeuve, à titre de catalyseur, des amines primaires, secondaires ou tertiaires, de préférence les amines aliphatiques, ces amines pouvant comporter d'autre fonctions comme notamment des fonctions éther. A titre d'exemple de catalyseur de ce type, on peut citer la N,N-diméthyllaurylamine.It is likewise possible to use catalysts chosen from metal alkoxides alkali or alkaline earth metals, such as methylate, ethylate, tert-butylate sodium or potassium. It should be noted that it is also possible to register as a catalyst, primary, secondary or tertiary amines, preferably amines aliphatic, these amines may include other functions such as ether functions. By way of example of a catalyst of this type, mention may be made of N, N-dimethyllaurylamine.

    Dans le cas d'un catalyseur basique, la quantité est plus particulièrement comprise entre 0,5 et 40 mg rapportée au poids de produit final.In the case of a basic catalyst, the amount is more particularly included between 0.5 and 40 mg based on the weight of the final product.

    il est envisageable de mettre en oeuvre cette réaction en présence d'un acide de Lewis, comme BF3 (gazeux ou en solution dans un éther), SnCl4, SbCl5.it is conceivable to carry out this reaction in the presence of a Lewis acid, such as BF 3 (gaseous or in solution in an ether), SnCl 4 , SbCl 5 .

    La quantité de catalyseur acide varie plus particulièrement entre 0,1 et 10 mmoles par mole de réactif (Ila) ou (Ilb).The amount of acid catalyst varies more particularly between 0.1 and 10 mmol per mole of reagent (Ila) or (Ilb).

    La mise en contact est effectuée à une température suffisante pour permettre l'accomplissement de la réaction. A titre indicatif, la température est supérieure à 100°C, plus particulièrement comprise entre 120 et 250°C, et de préférence comprise entre 150 et 200°C. The contacting is carried out at a temperature sufficient to allow the completion of the reaction. As an indication, the temperature is greater than 100 ° C, more particularly between 120 and 250 ° C, and preferably between 150 and 200 ° C.

    Avantageusement, la réaction est réalisée sous une atmosphère inerte dans les conditions de la réaction, comme l'azote, ou un gaz rare comme l'argon ou encore le monoxyde de carbone. L'azote est préféré.Advantageously, the reaction is carried out under an inert atmosphere in the reaction conditions, such as nitrogen, or a rare gas such as argon or carbon monoxide. Nitrogen is preferred.

    La réaction peut se dérouler sous pression atmosphérique, sous pression réduite ou en légère surpression. Habituellement, on préfère travailler sous une pression comprise entre 1 et 4 bar.The reaction can take place under atmospheric pressure, under reduced pressure or slight overpressure. Usually, we prefer to work under pressure between 1 and 4 bar.

    La préparation des réactifs (IIa) et (IIb) a été décrite dans la demande WO 96/01245, à laquelle on pourra se référer.The preparation of the reagents (IIa) and (IIb) has been described in the application WO 96/01245, to which reference may be made.

    Les quantités des composés (IIIop) et (IIIoe) sont calculées en fonction des caractéristiques de la formule (I), plus particulièrement des valeurs souhaitées de n et p.The amounts of the compounds (IIIop) and (IIIoe) are calculated according to the characteristics of formula (I), more particularly desired values of n and p.

    Ces deux composés sont introduits successivement, de manière à obtenir un composé de formule (I) séquence.These two compounds are introduced successively, so as to obtain a compound of formula (I) sequence.

    A l'issue de la réaction, on neutralise de préférence le mélange réactionnel, afin d'obtenir un pH compris entre 5 et 8, de préférence 6 et 7.At the end of the reaction, the reaction mixture is preferably neutralized in order to to obtain a pH of between 5 and 8, preferably 6 and 7.

    La neutralisation est faite au moyen d'acide acétique, ou d'hydroxyde, de carbonate ou de bicarbonate de sodium, selon la nature du catalyseur mis en jeu dans la réaction.The neutralization is made with acetic acid, or with hydroxide, with carbonate or sodium bicarbonate, depending on the nature of the catalyst involved in the reaction.

    A l'issue de cette réaction, le composé (I) est tel que le radical R5 est l'hydrogène.At the end of this reaction, the compound (I) is such that the radical R 5 is hydrogen.

    Il est tout à fait possible de mettre en oeuvre une étape de fonctionnalisation dudit radical, c'est-à-dire une étape visant à transformer l'hydrogène terminal en l'un des autres radicaux R5, tels que définis auparavant. Ainsi, on peut mettre en oeuvre une opération d'éthérification ou d'estérification de l'atome d'hydrogène terminal ; cette étape est bien connue en ette-mème : elle est de préférence réalisée après la neutralisation.It is quite possible to implement a step of functionalizing said radical, that is to say a step for converting the terminal hydrogen into one of the other R 5 radicals, as defined previously. Thus, it is possible to carry out an etherification or esterification operation of the terminal hydrogen atom; this step is well known in itself: it is preferably carried out after the neutralization.

    Ainsi, peut être réalisée la préparation :

    • d'éthersulfates (R5 = -SO3M ), selon le mode opératoire décrit dans GB 1 111 208 ou US 3,392,185
    • d'étherphosphates (R5 = -OPO3(M)2), selon le mode opératoire décrit dans US 3,331,896
    • d'éthercarboxylates (R5 = -(CH2)r-COOM), selon le mode opératoire décrit dans US 2,623,900 ou US 2,983,738
    • d'éthersulfonates (R5 = -(CH2)z-SO3M), selon le mode opératoire décrit dans US 2,115,192, US 4,978,780 ou K. SUGA, Austr. J. Chem., 21, 2333 (1968)
    • d'alkyléthers (R5 = radical hydrocarboné), selon le mode opératoire décrit dans US 2,913,416.
    Thus, the preparation can be carried out:
    • of ethersulfates (R 5 = -SO 3 M), according to the procedure described in GB 1 111 208 or US 3,392,185
    • of ether phosphates (R 5 = -OPO 3 (M) 2 ), according to the procedure described in US 3,331,896
    • ether carboxylates (R5 = - (CH 2) r -COOM), according to the procedure described in US 2,623,900 or US 2,983,738
    • ethersulfonates (R 5 = - (CH 2 ) z -SO 3 M), according to the procedure described in US 2,115,192, US 4,978,780 or K. SUGA, Austr. J. Chem., 21 , 2333 (1968)
    • of alkyl ethers (R 5 = hydrocarbon radical), according to the procedure described in US 2,913,416.

    De plus amples détails concernant ces modes de fonctionnalisation sont décrits dans WO 96/01245. Further details concerning these modes of functionalization are described in WO 96/01245.

    Les composés selon l'invention sont donc utilisés en tant qu'agent de dégraissage de surfaces dures et plus particulièrement de surfaces métalliques.The compounds according to the invention are therefore used as a degreasing agent hard surfaces and more particularly metal surfaces.

    Ainsi les composés selon l'invention peuvent être utilisés dans l'industrie du traitement des métaux, mais aussi dans toute application dans laquelle on met en oeuvre un dégraissage de telles surfaces comme le dégraissage des puits ou plates-formes d'exploitation pétrolière.Thus the compounds according to the invention can be used in the metal processing, but also in any application in which one puts in degreasing such surfaces as the degreasing of wells or platforms oil exploitation.

    Ainsi que cela a été indiqué auparavant, le composé mis en oeuvre selon l'invention, l'est avec une quantité comprise entre 0,01 et 10 g/l, au moment de l'utilisation.As has been indicated previously, the compound used according to the invention is with a quantity of between 0.01 and 10 g / l at the time of use.

    Dans le cas du dégraissage de plaques ou tôles métalliques, la concentration en composé est plus particulièrement comprise entre 0,01 et 5 g/l lors de l'utilisation.In the case of the degreasing of metal plates or sheets, the concentration in compound is more particularly between 0.01 and 5 g / l during use.

    Dans le domaine de l'exploitation pétrolière, et plus particulièrement du dégraissage des plates-formes, la concentration en composé est comprise entre 0,01 et 10 g/l au moment de l'utilisation, en composé mis en oeuvre selon l'invention.In the field of oil exploitation, and more particularly platform degreasing, the compound concentration is between 0.01 and 10 g / l at the time of use, the compound used according to the invention.

    Pour ce qui a plus particulièrement trait au nettoyage du puits, le composé selon l'invention est mis en oeuvre avec une concentration de préférence comprise entre 0,01 et 5 g/l.As regards more particularly the cleaning of the well, the compound according to the invention is implemented with a concentration of preferably between 0.01 and 5 g / l.

    Les milieux aqueux dégraissants ou détergents contenant les composés selon l'invention, sont de préférence utilisés à une température au moins de l'ordre de leur température de trouble.Aqueous degreasing or detergent media containing the compounds according to the invention are preferably used at a temperature at least of the order of their cloud temperature.

    Les formulations de dégraissage des tôles ou plaques métalliques en milieu alcalin, comprennent, en plus du composé mis en oeuvre selon l'invention, une lessive alcaline comprenant au moins l'un des composés suivants :

    • au moins un agent contrôlant le pH, comme les hydroxydes, les carbonates, les sesquicarbonates, bicarbonate de métaux alcalins ou alcalino-terreux,
    • au moins un polyphosphate, comme le tripolyphosphate, le pyrophosphate, l'orthophosphate, l'hexamétaphosphate de métal alcalin, alcalino-tereux, d'ammonium du type N(R4)+ avec R représentant l'hydrogène, un radical alkyle en C1-C4 comprenant éventuellement un atome d'oxygène,
    • au moins un silicate de métal alcalin, comme par exemples les métasilicates de métal alcalin, anhydre ou non, ou leurs mélanges.
    The degreasing formulations of metal sheets or plates in an alkaline medium comprise, in addition to the compound used according to the invention, an alkaline lye comprising at least one of the following compounds:
    • at least one pH-controlling agent, such as hydroxides, carbonates, sesquicarbonates, alkali metal or alkaline earth metal bicarbonates,
    • at least one polyphosphate, such as tripolyphosphate, pyrophosphate, orthophosphate, alkali metal hexametaphosphate, alkaline tereux of ammonium type N (R 4) + with R representing hydrogen, an alkyl radical C 1 -C 4 optionally comprising an oxygen atom,
    • at least one alkali metal silicate, such as, for example, alkali metal metasilicates, anhydrous or not, or mixtures thereof.

    La concentration en lessive alcaline lors de l'utilisation est comprise entre 1 et 100 g/l, plus particulièrement entre 5 et 20 g/l.The concentration of alkaline lye in use is between 1 and 100 g / l, more particularly between 5 and 20 g / l.

    Les formulations peuvent en outre comprendre :

    • au moins un électrolyte hydrotrope tel que les benzènesulfonates, les mono- ou di-alkyl (C1-C4) benzènesulfonates, les toluène-, xylène- ou cumène-sulfonates, les alcools et les glycols,
    • au moins un agent séquestrant tel que l'acide nitriloacétique, l'acide éthylènediamine tétraacétique, l'acide éthylènediamine tétraméthylphosphonique, l'acide nitrilo-triméthylène phosphonique ou leurs sels,
    • des agents tampons tels que les alcanolamines, l'éthylènediamine,
    • des agents inhibiteurs de corrosion des métaux.
    The formulations may further include:
    • at least one hydrotrope electrolyte such as benzenesulphonates, mono- or di-(C 1 -C 4 ) alkylbenzenesulfonates, toluene-, xylene- or cumene-sulphonates, alcohols and glycols,
    • at least one sequestering agent such as nitriloacetic acid, ethylenediamine tetraacetic acid, ethylenediamine tetramethylphosphonic acid, nitrilo-trimethylenephosphonic acid or their salts,
    • buffering agents such as alkanolamines, ethylenediamine,
    • inhibitors of corrosion of metals.

    Les concentrations en ces composés varient dans les gammes habituelles du domaine. Cependant, à titre d'illustration, la teneur en chacun des composés varie de 0 à 1,5 g/l au moment de l'utilisation.The concentrations of these compounds vary in the usual ranges of field. However, by way of illustration, the content of each of the compounds varies from 0 at 1.5 g / l at the time of use.

    Les compositions aqueuses mises en oeuvre pour le dégraissage des plates-formes pétrolières peuvent comprendre, outre le composé selon l'invention:

    • au moins un électrolyte hydrotrope tel que les benzènesulfonates, les mono- ou di-alkyl (C1-C4) benzènesulfonates, les toluène-, xylène- ou cumène-sulfonates, les alccols et les glycols,
    • au moins un agent contrôlant le pH, tel que, par exemple, les carbonates, les sesquicarbonates, les bicarbonates de métaux alcalins,
    • des additifs comme les enzymes, des agents inhibiteurs de corrosion des métaux.
    The aqueous compositions used for the degreasing of the oil platforms can comprise, besides the compound according to the invention:
    • at least one hydrotrope electrolyte such as benzenesulphonates, mono- or di-(C 1 -C 4 ) alkylbenzenesulfonates, toluene-, xylene- or cumenesulphonates, alccols and glycols,
    • at least one pH-controlling agent, such as, for example, carbonates, sesquicarbonates, alkali metal bicarbonates,
    • additives such as enzymes, corrosion inhibitors of metals.

    Là encore, les concentrations en ces composés varient dans les gammes habituelles du domaine. A titre d'exemple, la teneur en chacun des composés varie de 0 à 1,5 g/l au moment de l'utilisation.Again, the concentrations of these compounds vary in the ranges usual domain. By way of example, the content of each of the compounds varies from 0 at 1.5 g / l at the time of use.

    Les milieux aqueux mis en oeuvre pour le nettoyage des puits de pétrole peuvent comprendre, outre le composé selon l'invention :

    • au moins un agent permettant d'ajuster le pH, tel que, par exemple, les carbonates, les sesquicarbonates, les bicarbonates de métaux alcalins, les hydroxydes de métaux alcalins ou alcalino-terreux,
    • des additifs comme les enzymes en quantité pouvant aller jusqu'à 5 % du poids total de la composition aqueuse, des agents inhibiteurs de corrosion des métaux,
    • si nécessaire, des agents alourdissants de manière à maintenir une pression hydrostatique satisfaisante dans le puits.
    A titre d'exemple de tels composés, on peut citer les sels solubles ou au moins partiellement solubles comme les halogénures de métaux alcalin ou alcalino-terreux. On peut de même utiliser les sulfates, les carbonates, les bicarbonates, les silicates, les phosphates de métaux alcalins ou alcalino-terreux, seuls ou en mélange. On peut de même utiliser des sels d'acides organiques, comme les formiates, les acétates de métaux alcalins ou alcalino-terreux.
    Il est possible de mettre en oeuvre, bien que non préférés, des sels insolubles tels que les sulfates, silicates ou carbonates de métaux alcalino-terreux ; les bromures de métaux alcalino-terreux ou de zinc. - des hydrocolloïdes comme les polysaccharides d'origine végétale, tels que les polygalactomannanes, la cellulose, les amidons et leurs dérivés ; les polysaccharides d'origine bactérienne comme la gomme xanthane ou des dérivés désacétylés.The aqueous media used for the cleaning of the oil wells may comprise, in addition to the compound according to the invention:
    • at least one agent for adjusting the pH, such as, for example, carbonates, sesquicarbonates, alkali metal bicarbonates, alkali or alkaline earth metal hydroxides,
    • additives such as enzymes in an amount of up to 5% of the total weight of the aqueous composition, metal corrosion inhibitors,
    • if necessary, weighting agents so as to maintain a satisfactory hydrostatic pressure in the well.
    Examples of such compounds include soluble or at least partially soluble salts such as alkali or alkaline earth metal halides. It is likewise possible to use sulphates, carbonates, bicarbonates, silicates or phosphates of alkali or alkaline earth metals, alone or as a mixture. It is likewise possible to use salts of organic acids, such as formates, acetates of alkali or alkaline earth metals.
    It is possible to implement, although not preferred, insoluble salts such as alkaline earth metal sulfates, silicates or carbonates; alkaline earth metal bromides or zinc. hydrocolloids such as polysaccharides of plant origin, such as polygalactomannans, cellulose, starches and their derivatives; polysaccharides of bacterial origin such as xanthan gum or deacetylated derivatives.

    On ne sortirait pas du cadre de la présente invention, bien que non préféré, en ajoutant aux formulations précédemment décrites, des agents tensioactifs (anioniques, cationiques, zwiterrioniques, amphotères), de préférence peu moussants, ainsi que d'autres additifs.It would not be outside the scope of the present invention, although not preferred, in adding to the previously described formulations, surfactants (anionic, cationic, zwitterionic, amphoteric), preferably low foaming, as well as other additives.

    Des exemples concrets mais non limitatifs de l'invention vont maintenant être présentés.Concrete but non-limiting examples of the invention will now be presented.

    EXEMPLE 1EXAMPLE 1

    Cet exemple a pour objet la synthèse de 6,6-diméthylbicyclo[3.1.1]hept-2-ène-2 éthanol comprenant des motifs oxypropylénés (OP) et motifs oxyéthylénés (OE) variables.This example relates to the synthesis of 6,6-dimethylbicyclo [3.1.1] hept-2-ene-2 ethanol comprising oxypropylene units (OP) and oxyethylenated units (EO) variables.

    La synthèse du 6,6-diméthylbicyclo[3.1.1]hept-2-ène-2 éthanol comprenant x motifs oxypropylénés (OP) et y motifs oxyéthylénés (OE) est réalisée comme suit :Synthesis of 6,6-dimethylbicyclo [3.1.1] hept-2-ene-2 ethanol including x oxypropylene units (OP) and oxyethylenated units (OE) are produced as follows:

    Le 6,6-diméthylbicyclo[3.1.1]hept-2-ène-2 éthanol (nopol) utilisé est commercialisé par la société Fluka.The 6,6-dimethylbicyclo [3.1.1] hept-2-ene-2 ethanol (nopol) used is marketed by the company Fluka.

    Dans un réacteur d'éthoxylation de 5 litres, on introduit le nopol (6 moles) et une solution aqueuse d'hydroxyde de potassium (50%, 3,1 g).In a 5-liter ethoxylation reactor, the nopol (6 moles) and a aqueous solution of potassium hydroxide (50%, 3.1 g).

    Le milieu réactionnel est déshydraté à 120°C sous un flux d'azote.The reaction medium is dehydrated at 120 ° C. under a stream of nitrogen.

    On chauffe ensuite à 170°C et l'on introduit de l'oxyde de propylène (x équivalents molaires). Une fois l'oxyde de propylène introduit, on ajoute l'oxyde d'éthylène (y équivalents molaires).Then heated to 170 ° C and introduced propylene oxide (x equivalents molar). Once the propylene oxide is introduced, the ethylene oxide is added (y molar equivalents).

    Le milieu réactionnel est ensuite refroidi, neutralisé par addition d'acide acétique jusqu'à obtenir un pH de 7. Le liquide obtenu est filtré sur une terre absorbante (Clarcel DIC). The reaction medium is then cooled, neutralized by addition of acetic acid until the pH is 7. The resulting liquid is filtered on absorbent soil (Clarcel DIC).

    Tableau des composés synthétisés selon la méthode indiquée ci-dessus : Composés Nombre d'OP (x) Nombre d'OE (y) Selon l'invention 1 3 6,3 2 3 7 3 3 7,5 4 4 7 5 4 8 6 5 7 7 5 8 Comparatifs 8 3 6 9 3 10 10 2 5 Table of compounds synthesized according to the method indicated above: compounds Number of PO (x) Number of OE (y) According to the invention 1 3 6.3 2 3 7 3 3 7.5 4 4 7 5 4 8 6 5 7 7 5 8 comparative 8 3 6 9 3 10 10 2 5

    EXEMPLE 2EXAMPLE 2

    Cet exemple a pour objectif de comparer les propriétés de dégraissage des composés selon l'invention 1 et 3, des composés comparatifs 8, 9 et 10, ainsi que celles obtenus avec l'Igepal NP10 démoussé.This example aims to compare the degreasing properties of compounds according to the invention 1 and 3, comparative compounds 8, 9 and 10, as well as those obtained with Igepal NP10 defoamed.

    - Graissage- Lubrication

    Des plaques en acier prédégraissées de marque "Q-Panel" Stock n° R-36 type "Dull matt finish" de 0,8 x 76 x 152 mm sont immergées pendant 2 minutes dans une huile entière lubrifiante formulée pour laminage de tôles en acier pour automobiles, de marque QUAKER 6130 N de Quaker Chemicals, puis suspendues pour égouttage pendant 24 heures.Pre-greased steel plates of "Q-Panel" brand Stock No. R-36 type "Dull matt finish" of 0.8 x 76 x 152 mm are immersed for 2 minutes in a lubricating whole oil formulated for rolling steel sheets for automobiles, QUAKER brand 6130 N from Quaker Chemicals, then suspended for draining for 24 hours.

    - Nettoyage et rinçage- Cleaning and rinsing

    Les plaques graissées sont introduites dans une machine de dégraissage par aspersion CIEMME LARO 350. La température de dégraissage est de 45°C et la pression de 2 bar.The greased plates are introduced into a degreasing machine by CIEMME LARO 350 sprinkler. The degreasing temperature is 45 ° C and the pressure of 2 bar.

    Avant lecture de la qualité du dégraissage, les plaques sont rincées sous filet d'eau courante 2 ml/min pendant 5 secondes sur chaque face. Before reading the quality of degreasing, the plates are rinsed under a net running water 2 ml / min for 5 seconds on each side.

    - Milieu de dégraissage- Degreasing medium

    On prépare un milieu de dégraissage basique (pH 12-13) par dilution dans l'eau de 20 g/l d'une lessive aqueuse contenant 45% en poids de matière active constituée de quantités pondérales égales de potasse, métasilicate de sodium (SIMET GA5, granulés de métasilicate anhydre et de métasilicate pentahydraté, commercialisé par Rhodia Chimie) et de pyrophosphate tétrapotassique, et ajout de 1 g/l du composé à tester.A basic degreasing medium (pH 12-13) is prepared by dilution in water 20 g / l of an aqueous solution containing 45% by weight of active ingredient constituted equal amounts by weight of potassium hydroxide, sodium metasilicate (SIMET GA5, granules of anhydrous metasilicate and metasilicate pentahydrate, marketed by Rhodia Chimie) and tetrapotassium pyrophosphate, and addition of 1 g / l of the compound to test.

    Les résultats sont rassemblés dans le tableau ci-dessous : Composé Temps de dégraissage 1 30 secondes 3 30 secondes 8 comparatif 45 secondes 9 comparatif 55 secondes 10 comparatif > 2 minutes Igepal démoussé 45 secondes The results are summarized in the table below: Compound Degreasing time 1 30 seconds 3 30 seconds 8 comparative 45 seconds 9 comparative 55 seconds 10 comparative > 2 minutes Igepal deflated 45 seconds

    On constate bien que le produit conforme à l'invention est toujours plus actif que les agents mis en oeuvre à titre de comparaison.It is clear that the product according to the invention is always more active than the agents used for comparison.

    EXEMPLE 3EXAMPLE 3

    Cet exemple a pour objectif de comparer les propriétés de dégraissage des composés selon l'invention 4 à 7, ainsi que celles obtenus avec l'Igepal NP9 non démoussé.This example aims to compare the degreasing properties of compounds according to the invention 4 to 7, as well as those obtained with Igepal NP9 not defoamed.

    - Graissage- Lubrication

    On applique au pinceau, sur des plaques en acier prédégraissées de 0,8 x 24 x 101 mm, une huile de marque Pennzoil 80W-90 commercialisée par Pennzoil Products Company (Houston, Texas), de manière à obtenir un dépôt d'huile d'environ 0.015 g/cm2. Elles sont ensuite stockées à l'air pendant 24 heures.A Pennzoil 80W-90 brand oil marketed by Pennzoil Products Company (Houston, Texas) was brushed onto 0.8 x 24 x 101 mm pre-degreased steel plates to obtain a coating of oil. about 0.015 g / cm 2 . They are then stored in the air for 24 hours.

    La quantité d'huile est mesurée par pesée de la plaque avant et après application de l'huile. The amount of oil is measured by weighing the plate before and after application oil.

    - Nettoyage et rinçage- Cleaning and rinsing

    On immerge la plaque dans un litre de milieu de dégraissage, sous agitation magnétique (100 tr/min), à 50°C pendant 10 minutes.The plate is immersed in one liter of degreasing medium, with stirring magnetic (100 rpm), at 50 ° C for 10 minutes.

    Avant lecture de la qualité du dégraissage, les plaques sont rincées sous filet d'eau courante 2 ml/min pendant 5 secondes sur chaque face, puis séchées à 80°C.Before reading the quality of degreasing, the plates are rinsed under a net running water 2 ml / min for 5 seconds on each side, then dried at 80 ° C.

    La mesure de l'efficacité de l'opération est calculée par pesée de la plaque avant et après traitement avec le milieu de dégraissage.The measurement of the efficiency of the operation is calculated by weighing the front plate and after treatment with the degreasing medium.

    - Milieu de dégraissage- Degreasing medium

    On prépare un milieu de dégraissage basique (pH 12-13) par dilution dans l'eau de 20 g/l d'une lessive aqueuse contenant 1,5 g/l de pyrophosphate tétrapotassique, et ajout de 1 g/l du composé à tester.A basic degreasing medium (pH 12-13) is prepared by dilution in water 20 g / l of an aqueous solution containing 1.5 g / l of tetrapotassium pyrophosphate, and addition of 1 g / l of the test compound.

    Les résultats sont rassemblés dans le tableau ci-dessous : Composé % d'huile enlevée 4 58 5 62 6 54 7 72 Igepal 51 The results are summarized in the table below: Compound % of oil removed 4 58 5 62 6 54 7 72 Igepal 51

    On constate que les produits selon l'invention sont toujours plus efficaces que le produit de référence Igepal.It is found that the products according to the invention are always more effective than the Igepal reference product.

    EXEMPLE 4EXAMPLE 4

    Cet exemple a pour objectif de comparer les propriétés de moussage des composés obtenus aux exemples 1 à 7, ainsi que celles obtenues avec les composés comparatifs Igepal démoussé, Igepal seul.This example aims to compare the foaming properties of compounds obtained in Examples 1 to 7, as well as those obtained with the compounds comparative Igepal blunted, Igepal alone.

    Test de mousse :Foam test:

    On prépare un milieu de dégraissage basique (pH 12-13) par dilution dans l'eau de 20 g/l d'une lessive aqueuse contenant 45% en poids de matière active constituée de quantités pondérales égales de potasse, métasilicate de sodium (SIMET GA5, granulés de métasilicate anhydre et de métasilicate pentahydraté, commercialisé par Rhodia Chimie) et de pyrophosphate tétrapotassique et ajout de 1 g/l du composé à tester.A basic degreasing medium (pH 12-13) is prepared by dilution in water 20 g / l of an aqueous solution containing 45% by weight of active ingredient constituted equal amounts by weight of potassium hydroxide, sodium metasilicate (SIMET GA5, granules of anhydrous metasilicate and metasilicate pentahydrate, marketed by Rhodia Chimie) and tetrapotassium pyrophosphate and addition of 1 g / l of the compound to test.

    Le test est réalisé à 50°C.The test is carried out at 50 ° C.

    La mousse est obtenue par agitation de 900 g de solution à l'aide d'un agitateur à turbine (turbine 40mm, vitesse 2000tr/min) pendant 5 minutes.The foam is obtained by stirring 900 g of solution with a stirrer. turbine (40mm turbine, 2000rpm speed) for 5 minutes.

    La lecture du niveau de mousse est faite dans une éprouvette après 5 minutes de repos.The level of foam is read in a test tube after 5 minutes of rest.

    Les résultats sont rassemblés dans le tableau ci-dessous : Composé Niveau de mousse 1 20 ml 3 70 ml 4 20 ml 5 50 ml 6 20 ml 7 30 ml Igepal démoussé 70 ml Igepal seul 950 ml The results are summarized in the table below: Compound Foam level 1 20 ml 3 70 ml 4 20 ml 5 50 ml 6 20 ml 7 30 ml Igepal deflated 70 ml Igepal alone 950 ml

    Le tableau ci-dessus, en combinaison avec les résultats de dégraissage des exemples précédents, montre que seul les composés selon l'invention satisfont au double critère pouvoir dégraissant élevé et niveau de mousse compatible avec une utilisation pour le dégraissage de plaques métalliques.The table above, in combination with the degreasing results of the examples, shows that only the compounds according to the invention satisfy the double criterion high degreasing power and level of foam compatible with a use for the degreasing of metal plates.

    Claims (13)

    1. Use in applications for degreasing/cleaning hard surfaces, such as metal surfaces, of at least one compound, employed with a concentration between 0.01 and 10 g/l, when this compound is used, of following formula (I): Z-X-[CH(R3)-CH(R4)-O]n-[CH2CH2-O]p-R5 in which formula:
      Z represents a bicyclo[a.b.c]heptenyl or bicyclo-[a.b.c]heptyl radical with a+b+c = 5
      a = 2, 3 or 4,
      b = 2 or 1,
      c = 0 or 1,
      the said radical being optionally substituted by at least one C1-C6 alkyl radical and comprising a skeleton Z chosen from those indicated below or with the corresponding skeletons devoid of a double bond:
      Figure 00220001
      Figure 00230001
      Figure 00230002
      X represents -CH2-C(R1)(R2)-O- or -O-CH(R'1)-CH(R'2)-O-, in which:
      R1, R2, R'1 and R'2, which are identical or different, represent hydrogen or a saturated or unsaturated, linear, branched or cyclic, C1-C22, preferably C1-C6, hydrocarbonaceous radical,
      R3 and R4, which are identical or different, represent hydrogen or a saturated or unsaturated, linear, branched or cyclic, C1-C22 hydrocarbonaceous radical, provided that at least one of the R3 or R4 radicals is other than hydrogen;
      R5 represents hydrogen, an optionally substituted, saturated or unsaturated, linear, branched or cyclic, aromatic or nonaromatic, C1-C22 hydrocarbonaceous radical, or a group chosen from the following:
      -SO3M,
      -OPO3(M)2,
      - (CH2)r-COOM,
      - (CH2)z-SO3M,
      in which formulae:
      M represents hydrogen, an alkali metal or an ammonium functional group N(R)4 +, in which R, which are identical or different, represent hydrogen or an optionally hydroxylated, saturated or unsaturated, linear, branched or cyclic, C1-C22 hydrocarbonaceous radical;
      r is between 1 and 6;
      z is between 1 and 6;
      n is an integer or noninteger between 3 and 5 inclusive;
      p is an integer or noninteger between 6 and 10, excluding the limits.
    2. Use according to the preceding claim, characterized in that the compound is such that, in the formula (I), n is equal to 3.
    3. Use according to either one of the preceding claims, characterized in that the compound is such that, in the formula (I), p is between 6.2 and 7, including the limits, preferably between 6.3 and 7, including the limits.
    4. Use according to claim 1, characterized in that the compound is such that, in the formula (I), n is between 4 and 5.
    5. Use according to the preceding claim, characterized in that the compound is such that, in the formula (I), p is between 7 inclusive and 10 exclusive, preferably between 8 inclusive and 10 exclusive.
    6. Use according to any one of the preceding claims, characterized in that the compound is such that, in the formula (I), the radical Z is substituted on at least one of its carbons by two C1-C6 alkyl groups.
    7. Use according to any one of the preceding claims, characterized in that the compound is such that, in the formula (I), X represents -CH2-C(R1)(R2)-O-and in that the skeleton Z is selected from the formulae c) to g).
    8. Use according to the preceding claim, characterized in that the compound is such that, in the formula (I), the skeleton Z is chosen from the formulae d) and e).
    9. Use according to any one of claims 1 to 5, characterized in that the compound is such that, in the formula (I), X represents -O-CH(R'1)-CH(R'2)-O- and in that the radical Z corresponds to the skeleton c), the bicyclic skeleton being devoid of a double bond.
    10. Use according to the preceding claim, characterized in that the compound is such that, in the formula (I), the radical Z is substituted by a C1-C6 alkyl radical, preferably a methyl radical, on the 2- or 5-carbon of the bicycle.
    11. Use according to any one of the preceding claims, characterized in that the compound is employed for the degreasing/cleaning of metal sheets; the concentration of compound being between 0.01 and 5 g/l during use.
    12. Use according to any one of claims 1 to 10, characterized in that the compound is employed for the degreasing/cleaning of platforms; the concentration of compound being between 0.01 and 10 g/l during use.
    13. Use according to any one of claims 1 to 10, characterized in that the compound is employed for the degreasing/cleaning of oil production wells, the concentration of compound according to the invention being between 0.01 and 5 g/l.
    EP00958691A 1999-08-17 2000-08-16 Use of polyoxypropylene/polyoxyethylene terpene compounds as degreasing agents for hard surfaces Expired - Lifetime EP1206512B1 (en)

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    FR9910559 1999-08-17
    FR9910559A FR2797643B1 (en) 1999-08-17 1999-08-17 USE OF POLYOXYPROPYLENE / POLYOXYETHYLENE TERPENIC COMPOUNDS AS A DEGREASING AGENT FOR HARD SURFACES
    PCT/FR2000/002325 WO2001012765A1 (en) 1999-08-17 2000-08-16 Use of polyoxypropylene/polyoxyethylene terpene compounds as degreasing agents for hard surfaces

    Publications (2)

    Publication Number Publication Date
    EP1206512A1 EP1206512A1 (en) 2002-05-22
    EP1206512B1 true EP1206512B1 (en) 2004-04-07

    Family

    ID=9549189

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP00958691A Expired - Lifetime EP1206512B1 (en) 1999-08-17 2000-08-16 Use of polyoxypropylene/polyoxyethylene terpene compounds as degreasing agents for hard surfaces

    Country Status (14)

    Country Link
    EP (1) EP1206512B1 (en)
    JP (1) JP3983543B2 (en)
    KR (1) KR100588273B1 (en)
    CN (1) CN1185328C (en)
    AT (1) ATE263826T1 (en)
    AU (1) AU759508B2 (en)
    BR (1) BR0013362B1 (en)
    CA (1) CA2382093C (en)
    DE (1) DE60009721T2 (en)
    DK (1) DK1206512T3 (en)
    ES (1) ES2214310T3 (en)
    FR (1) FR2797643B1 (en)
    MX (1) MXPA02001589A (en)
    WO (1) WO2001012765A1 (en)

    Families Citing this family (8)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    FR2918994B1 (en) * 2007-07-20 2012-10-19 Rhodia Operations FORMULATIONS OF CARBOXYLIC ACID DIESTERS AND THEIR USE FOR TREATING MATERIALS.
    FR2929954B1 (en) * 2008-04-09 2010-04-30 Rhodia Operations AQUEOUS TREATMENT COMPOSITION INHIBITING CORROSION AND ACID ATTACK ON METAL SURFACES
    FR2949116B1 (en) 2009-08-13 2012-08-31 Rhodia Operations GRAFFITI CLEANING COMPOSITION
    CN101993790B (en) * 2009-08-17 2012-06-06 中国石油化工股份有限公司 Cleaning agent of oil refining device and preparation method thereof
    FR2950627B1 (en) 2009-09-28 2011-12-09 Rhodia Operations DISPERSION OF A WATER-SOLUBLE POLYMER IN A LIQUID ENVIRONMENT
    KR101673589B1 (en) * 2009-10-30 2016-11-07 동우 화인켐 주식회사 A detergent composition for a glass substrate of flat panel display device
    CA2968977A1 (en) 2014-12-02 2016-06-09 Minerva Neurosciences, Inc. Compositions comprising 2-((1-(2(4-fluorophenyl)-2-oxoethyl)piperidin-4-yl)methyl)isoindolin-1-one for treating schizophrenia
    WO2019173172A1 (en) 2018-03-06 2019-09-12 Shrieve Chemical Products, Inc. Lubricant and refrigerant compositions comprising polyalkylene glycols and uses thereof

    Family Cites Families (2)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    FR2721921B1 (en) * 1994-07-01 1996-10-31 Rhone Poulenc Chimie DERIVATIVES OF TERPENIC ORIGIN, SURFACTANT AND / OR PERFUMING COMPOSITION CONTAINING AND DETERGENT FORMULATION BASED ON THIS COMPOSITION
    FR2757508B1 (en) * 1996-12-20 1999-02-26 Rhodia Chimie Sa POLYALCOXYLATED TERPENIC COMPOUNDS, PROCESS FOR THEIR PREPARATION, AND THEIR USE AS FOAMING AGENTS

    Also Published As

    Publication number Publication date
    KR100588273B1 (en) 2006-06-09
    MXPA02001589A (en) 2002-07-02
    JP3983543B2 (en) 2007-09-26
    KR20020019984A (en) 2002-03-13
    AU759508B2 (en) 2003-04-17
    ATE263826T1 (en) 2004-04-15
    BR0013362A (en) 2002-04-30
    JP2003507531A (en) 2003-02-25
    FR2797643A1 (en) 2001-02-23
    WO2001012765A1 (en) 2001-02-22
    DE60009721D1 (en) 2004-05-13
    ES2214310T3 (en) 2004-09-16
    DK1206512T3 (en) 2004-06-07
    DE60009721T2 (en) 2005-03-31
    AU7013500A (en) 2001-03-13
    FR2797643B1 (en) 2003-06-06
    CA2382093A1 (en) 2001-02-22
    BR0013362B1 (en) 2010-11-03
    CN1376193A (en) 2002-10-23
    CA2382093C (en) 2005-10-25
    CN1185328C (en) 2005-01-19
    EP1206512A1 (en) 2002-05-22

    Similar Documents

    Publication Publication Date Title
    JP6940652B2 (en) Cleaning composition with rapid foam crushing
    EP1206512B1 (en) Use of polyoxypropylene/polyoxyethylene terpene compounds as degreasing agents for hard surfaces
    EP2262927A1 (en) Aqueous treatment composition for inhibiting corrosion and acid attack on metallic surfaces
    EP0950043B1 (en) Polyalcoxylated terpenic compounds, method of preparation and use as antifoaming agents
    OA12940A (en) Heparin - derived polysaccharide mixtures, their preparation and pharmaceutical compositions containing them.
    WO2019043340A1 (en) Metal corrosion inhibitors
    FR2682679A1 (en) NOVEL ALKYLPOLYOSID DERIVATIVES, PROCESSES FOR PREPARING THEM AND APPLICATIONS AS SURFACE AGENTS.
    EP2588420B1 (en) Descaling of oxalates with acid compositions
    FR2495168A1 (en) NOVEL ALKYLPOLYOXYALKYLENE CARBOXYLATES, THEIR PREPARATION AND THEIR USE AS SURFACTANT AGENTS
    FR2526806A1 (en) LIQUID DETERGENT COMPOSITION
    CA2214388A1 (en) Cleaning and/or stripping ether or diacid ester based composition
    EP0021927A1 (en) Process for the preparation of aryl ethers
    JP2011225743A (en) Liquid bleaching agent composition for clothing material
    US20060079426A1 (en) Use of polyoxypropylene/polyoxyethylene terpene compounds as degreasing agents for hard surfaces
    EP1689807B1 (en) Novel dendritic polymers having monophosphonic terminations, method for preparing them, and their use
    WO2010032129A1 (en) Method for producing adamantyl compounds
    EP3271369B1 (en) Process for obtaining derivatives and compositions based on d-galacturonic acid directly from pectins
    JP3617830B2 (en) Production method of phosphate ester
    EP0278845A2 (en) Process for the preparation of hydroxybiphenyls
    JP4498910B2 (en) Production method of phosphate ester
    BE571485A (en)
    FR2616146A1 (en) PROCESS FOR THE PREPARATION OF NON-IONIC SURFACE AGENTS FROM GLYCEROL MONOCHLORHYDRIN IN AROMATIC SOLVENT, PRODUCTS OBTAINED AND COMPOSITIONS CONTAINING SAME
    FR3137921A1 (en) ALKOXYLATED AMMONIUM SALTS WITH HYDROTROPIC AND DETERGENT PROPERTIES
    JP2006241153A (en) Method for producing alkylene glycol
    WO2003053987A1 (en) Method for preparing surfactant compounds from polyols

    Legal Events

    Date Code Title Description
    PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

    Free format text: ORIGINAL CODE: 0009012

    17P Request for examination filed

    Effective date: 20020311

    AX Request for extension of the european patent

    Free format text: AL;LT;LV;MK;RO;SI

    GRAP Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOSNIGR1

    GRAS Grant fee paid

    Free format text: ORIGINAL CODE: EPIDOSNIGR3

    GRAA (expected) grant

    Free format text: ORIGINAL CODE: 0009210

    AK Designated contracting states

    Kind code of ref document: B1

    Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: FI

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20040407

    Ref country code: CY

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20040407

    REG Reference to a national code

    Ref country code: GB

    Ref legal event code: FG4D

    Free format text: NOT ENGLISH

    RTI1 Title (correction)

    Free format text: USE OF POLYOXYPROPYLENE/POLYOXYETHYLENE TERPENE COMPOUNDS AS DEGREASING AGENTS FOR HARD SURFACES

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: EP

    REF Corresponds to:

    Ref document number: 60009721

    Country of ref document: DE

    Date of ref document: 20040513

    Kind code of ref document: P

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: NV

    Representative=s name: KIRKER & CIE SA

    REG Reference to a national code

    Ref country code: IE

    Ref legal event code: FG4D

    Free format text: FRENCH

    REG Reference to a national code

    Ref country code: DK

    Ref legal event code: T3

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: SE

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20040707

    Ref country code: GR

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20040707

    GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

    Effective date: 20040712

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: MC

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20040831

    REG Reference to a national code

    Ref country code: ES

    Ref legal event code: FG2A

    Ref document number: 2214310

    Country of ref document: ES

    Kind code of ref document: T3

    LTIE Lt: invalidation of european patent or patent extension

    Effective date: 20040407

    PLBE No opposition filed within time limit

    Free format text: ORIGINAL CODE: 0009261

    STAA Information on the status of an ep patent application or granted ep patent

    Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

    26N No opposition filed

    Effective date: 20050110

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: PT

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20040907

    REG Reference to a national code

    Ref country code: DE

    Ref legal event code: R082

    Ref document number: 60009721

    Country of ref document: DE

    Representative=s name: VON ROHR PATENTANWAELTE PARTNERSCHAFT MBB, DE

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: LU

    Payment date: 20130902

    Year of fee payment: 14

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: IE

    Payment date: 20140812

    Year of fee payment: 15

    Ref country code: DK

    Payment date: 20140812

    Year of fee payment: 15

    Ref country code: CH

    Payment date: 20140812

    Year of fee payment: 15

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: AT

    Payment date: 20140728

    Year of fee payment: 15

    Ref country code: GB

    Payment date: 20140813

    Year of fee payment: 15

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: BE

    Payment date: 20140812

    Year of fee payment: 15

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: LU

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20140816

    REG Reference to a national code

    Ref country code: DK

    Ref legal event code: EBP

    Effective date: 20150831

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: PL

    REG Reference to a national code

    Ref country code: AT

    Ref legal event code: MM01

    Ref document number: 263826

    Country of ref document: AT

    Kind code of ref document: T

    Effective date: 20150816

    GBPC Gb: european patent ceased through non-payment of renewal fee

    Effective date: 20150816

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: LI

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20150831

    Ref country code: CH

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20150831

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: AT

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20150816

    REG Reference to a national code

    Ref country code: IE

    Ref legal event code: MM4A

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: PLFP

    Year of fee payment: 17

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: GB

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20150816

    Ref country code: IE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20150816

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: DK

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20150831

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: PLFP

    Year of fee payment: 18

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: BE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20150831

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: PLFP

    Year of fee payment: 19

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: NL

    Payment date: 20190712

    Year of fee payment: 20

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: IT

    Payment date: 20190821

    Year of fee payment: 20

    Ref country code: DE

    Payment date: 20190806

    Year of fee payment: 20

    Ref country code: ES

    Payment date: 20190904

    Year of fee payment: 20

    Ref country code: FR

    Payment date: 20190711

    Year of fee payment: 20

    REG Reference to a national code

    Ref country code: DE

    Ref legal event code: R071

    Ref document number: 60009721

    Country of ref document: DE

    REG Reference to a national code

    Ref country code: NL

    Ref legal event code: MK

    Effective date: 20200815

    REG Reference to a national code

    Ref country code: ES

    Ref legal event code: FD2A

    Effective date: 20201203

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: ES

    Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

    Effective date: 20200817