EP2212376A2 - Procédé de production d'une composition organique comprenant un n-nonylester - Google Patents

Procédé de production d'une composition organique comprenant un n-nonylester

Info

Publication number
EP2212376A2
EP2212376A2 EP08852584A EP08852584A EP2212376A2 EP 2212376 A2 EP2212376 A2 EP 2212376A2 EP 08852584 A EP08852584 A EP 08852584A EP 08852584 A EP08852584 A EP 08852584A EP 2212376 A2 EP2212376 A2 EP 2212376A2
Authority
EP
European Patent Office
Prior art keywords
composition
acid
nonyl
nonyl ester
oil
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP08852584A
Other languages
German (de)
English (en)
Inventor
Peter Daute
Anja Vonderhagen
Heinz Müller
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.)
Emery Oleochemicals GmbH
Original Assignee
Emery Oleochemicals GmbH
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
Priority claimed from DE102007055595A external-priority patent/DE102007055595A1/de
Priority claimed from DE200810009369 external-priority patent/DE102008009369A1/de
Application filed by Emery Oleochemicals GmbH filed Critical Emery Oleochemicals GmbH
Publication of EP2212376A2 publication Critical patent/EP2212376A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02—Well-drilling compositions
    • C09K8/03—Specific additives for general use in well-drilling compositions
    • C09K8/035—Organic additives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37—Esters of carboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
    • A61K8/585—Organosilicon compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02—Well-drilling compositions
    • C09K8/32—Non-aqueous well-drilling compositions, e.g. oil-based
    • C09K8/36—Water-in-oil emulsions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/68—Esters
    • C10M129/70—Esters of monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/68—Esters
    • C10M129/72—Esters of polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/284—Esters of aromatic monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/286—Esters of polymerised unsaturated acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/18—Anti-foaming property

Definitions

  • the present invention relates to a method for producing an organic see composition
  • a functional component selected from the group consisting of a thermoplastic polymer, an enzyme, a binder, a paraffin, an oil, a colorant and a hair or skin care substance, and an n-nonyl ester
  • a method for producing a shaped article a method for producing a packaged good, the use of at least one n-nonyl ester, the use of a shaped article, a method for cleaning the surfaces of boreholes, drilling equipment or cuttings, method for producing a Borehole and method for producing an oil or a gas.
  • pure alcohol and its derivatives such as, for example, ethers or esters
  • Pure Cs alcohol and its derivatives are characterized by deep solidification points, but have low boiling points and are therefore very volatile.
  • the branched i-nonanols are substance mixtures and are produced petrochemically. The branching of the alcohols leads to a poorer biodegradability.
  • a disadvantage in connection with the use of i-nonanols is still the too high melting point or too low boiling range of the derivatives such as esters, ethoxylates, sulfates, even if alcohol mixtures are used. Due to the non-ideal viscosity behavior, especially at lower temperatures, this product group is therefore limited.
  • the present invention was based on the object at least partially overcome the disadvantages resulting from the prior art.
  • the present invention has for its object to provide a method by means of which organic compositions containing esters of linear fatty alcohols short medium chain length can be provided as an additive, said organic compositions compared to the known from the prior art, comparable, organic compositions have less volatile components and have a satisfactory viscosity behavior even at low temperatures.
  • the present invention the object of the invention to provide a method by means of which organic compositions containing esters of linear fatty alcohols short to medium chain length can be provided as an additive, with as many components of these organic compositions on renewable resources or starting materials, which renewable raw materials can be obtained.
  • organic compositions obtainable by this process in comparison to those known from the prior art, organic compositions have improved performance properties.
  • the present invention was the object of specifying a compound Phyg, which can be used in particular as an additive in drilling fluids or cleaning agents for drilling equipment.
  • the present invention relates to a process for producing an organic composition which comprises a functional component selected from the group consisting of a thermoplastic polymer, an enzyme, a binder, a paraffin, an oil, a colorant and a hair or skin care substance , containing as process steps:
  • an n-nonyl ester as an additive which is obtainable by reacting an n-nonyl alcohol component with a further component which is capable of reacting with the n-nonyl alcohol component to form an n-nonyl ester,
  • component is preferably understood to mean a component which imparts its characteristic, functional property to the composition to which this functional component is added.
  • the functional component of a thermoplastic composition is the thermoplastic polymer, the functional component of an adhesive of the binder, the functional component of a lubricant formulation the oil, the functional component of a detergent the enzyme, the functional component of a defoamer the paraffin, the functional component of a paint or a colorant the colorant and the functional component of a cosmetic preparation Hair or skin care substance.
  • an "organic composition” is preferably understood as meaning a composition which consists of more than 50% by weight, based on the total weight of the organic composition, of organic components, wherein as an organic component it is preferable to use a carbon-containing compound Exception of CO 2 , CO, carbides, CSO and pure carbon compounds such as graphite, carbon black or diamond .
  • the organic component is a hydrocarbon compound having oxygen, nitrogen, phosphorus, sulfur or at least two of these atoms as heteroatoms can.
  • an n-nonyl ester is initially provided as an additive, which is obtainable by reaction of an n-nonyl alcohol component with a further component which is in contact with the n-nonyl ester.
  • Nonyl alcohol component is able to react to form an n-nonyl ester.
  • n-nonyl ester preferably comprises the following process steps:
  • ia2 providing a further component capable of reacting with the n-nonyl alcohol component to form an n-nonyl ester
  • an n-nonyl alcohol component is initially provided.
  • the n-nonyl alcohol component is at least 80% by weight, more preferably at least 90% by weight and most preferably at least 99% by weight.
  • % in each case based on the provided n-nonyl alcohol component, is obtained from pelargonic acid.
  • the catalytic hydrogenation of esters of pelargonic acid for example the catalytic hydrogenation of the methyl, ethyl, propyl or butyl ester of pelargonic acid.
  • the pelargonic acid itself can be obtained for example by ozonolysis of oleic acid and subsequent, oxidative work-up of the oleic ozone or by ozonolysis of erucic acid and subsequent oxidative workup of Erucaklaklads.
  • ozonolysis of oleic acid and subsequent, oxidative work-up of the oleic ozone or by ozonolysis of erucic acid and subsequent oxidative workup of Erucaklaklads.
  • Such a process is industrially carried out, for example, by Unilever Emery and Henkel and is described inter alia in "ozonation of alkenes in alcohols as solvent ''', thesis by Eberhard Rischbieter, University of Carolo-Wilhelmina to Brunswick, 2000 or in US 2,813,113.
  • the oxidation of the resulting in the oxidative workup of ozonides aldehydes and formation of the corresponding acid derivatives is described for example in DE-C-100 70 770.
  • the production of the oleic acid can in turn be carried out from tallow or tall oils, as described for example in US 6,498,261.
  • the pelargonic acid can also be obtained by isomerization of petrochemical raw materials. Also conceivable is the petrochemical production of pelargonic acid, as exemplified by Harold A., Witteoff, Bryan G., Reuben, Jeffrey S.
  • the n-nonyl alcohol component used for the preparation of the n-nonyl ester contains, in addition to the n-nonyl alcohol, further alcohols, for example Cs and / or Cio alcohols, but in this case it is particularly preferred that the n-nonyl alcohol component is less than 10% by weight, more preferably less than 7.5% by weight, and most preferably less than 5% by weight, based in each case on the n-nonyl alcohol component , Cs and Cio alcohols.
  • the proportion of n-nonyl alcohol in the n-nonyl alcohol component is in the case of use a mixture of n-nonyl alcohol and at least one further alcohol, preferably at least 90% by weight, more preferably at least 92.5% by weight and most preferably at least 95% by weight, based in each case on the total weight of the n-nonyl alcohol Component.
  • n-nonyl alcohol component is in particular that n-Nonylalkohol- component which is obtained by catalytic hydrogenation of the products marketed under the brand name EMERY ® 1202 EMERY ® 1203 and Emery ® 1210 pelargonic acid, wherein EMERY ® 1202 less than 1 Wt .-% of C ⁇ monocarboxylic acids, about 1 wt .-% of C 7 - monocarboxylic acids, about 4 wt .-% of Cs monocarboxylic acids, about 93 wt .-% of pelargonic acid and about 2 wt.
  • EMERY ® 1202 less than 1 Wt .-% of C ⁇ monocarboxylic acids, about 1 wt .-% of C 7 - monocarboxylic acids, about 4 wt .-% of Cs monocarboxylic acids, about 93 wt .-% of pelargonic acid and about 2 wt.
  • EMERY ® weight 1203 about 0.1 wt .-% of C ⁇ -Cs-monocarboxylic acids, to about 99 wt .-% of pelargonic acid and about 0.9.
  • step ia2) of the process for providing an n-nonyl ester at least one further component which is in contact with the n-nonyl alcohol
  • this further component is preferably an inorganic compound.
  • ganic acid in particular an inorganic acid selected from the group consisting of sulfuric acid, sulfurous acid, phosphoric acid or phosphorous acid, or an organic acid, in particular an organic acid selected from the group consisting of monocarboxylic acids, dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids or derivatives of The above-mentioned carboxylic acids.
  • carboxylic acid as used herein includes the carboxylic acid in its protonated form, the carboxylic acid in its deprotonated form (ie, especially salts of the carboxylic acid), and mixtures of the carboxylic acid in its protonated form and its deprotonated form
  • Term "carboxylic acid” basically all compounds which have at least one carboxylic acid group. It therefore also includes, in particular, compounds which, in addition to the at least one carboxylic acid group, also have other functional groups, such as, for example, hydroxyl groups, keto groups or ether groups.
  • derivative (s) of a carboxylic acid includes all derivatives of a carboxylic acid which, upon reaction with an alcohol, result in a corresponding ester of the carboxylic acid
  • acid derivative of a carboxylic acid includes the acid chlorides of the carboxylic acid and the acid anhydrides the carboxylic acid. These derivatives preferably have an increased reactivity of the carboxylic acid group compared to the carboxylic acid, so that ester formation is favored on reaction with an alcohol.
  • the use of mono-, di-, tri-, tetra- or polycarboxylic acids having more than four carboxyl groups, a derivative of such a carboxylic acid or a mixture of such a carboxylic acid and a derivative of such a carboxylic acid as further component is particularly preferred.
  • saturated or unsaturated carboxylic acids are used as carboxylic acid having a number of carbon atoms in a range of 6 to 26, more preferably in a range of 8 to 24, even more preferably in a range of 10 to 22, more preferably in a range of 12 to 20, and most preferably in one Range from 14 to 18 in consideration.
  • Carboxylic acids are therefore particularly preferred according to the invention.
  • carboxylic acids include, in particular, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, fish oil, palmitic acid, palmitic acid, pelagic acid, margaric acid, stearic acid, elaeostearic acid, isostearic acid, isotridecanoic acid, arachic acid, behenic acid, lignoceric acid, cerotic acid , Undecylenic acid, oleic acid, elaidic acid, vaccenic acid, icosenoic acid, rapeseed oil, cetoleic acid, erucic acid, nervonic acid, linoleic acid, linolenic acid, arachidonic acid, timnodonic acid, clupanodonic acid, petroselic acid, gadoleic acid or cervonic acid.
  • di-, tri- or tetracarboxylic acids or their anhydrides are also selected from the group consisting of phthalic anhydride, isophthalic acid, phthalic acid, terephthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, Diphenylmethane-4,4'-dicarboxylic acid, succinic acid, fumaric acid, adipic acid, sebacic acid, azelaic acid, trimellitic acid, pyromelic acid, mellitic acid and maleic anhydride into consideration, of these acids adipic acid, trimellitic acid, terephthalic acid and azelaic acid are particularly preferred.
  • hydroxycarboxylic acids are also included as suitable carboxylic acids, among these hydroxyfatty acids such as ricinoleic acid, 12-hydroxystearic acid, hydrogenated castor oil fatty acids (fatty acids containing small amounts of stearic acid and palmitic acid, as well as 12-hydroxystearic acid), sabinic acid, 2-hydroxytetradecanoic acid , Ipurolinic acid (3,11- Dihydroxytetradecanoic acid, 2-hydroxyhexadecanoic acid, jalapinolic acid, juniperic acid, ambrettolic acid, aleuritic acid, 2-hydroxyoctadecanoic acid, 18-hydroxyoctadecanoic acid, 9,10-dihydroxyoctadecanoic acid, camiolic acid, ferric acid, cerebronic acid, 9-hydroxystearic acid and 10-hydroxystearic acid are particularly preferred and 12-hydroxystearic acid and ricinoleic acid are most preferred. Also suitable are short-chain hydroxycarboxylic
  • the abovementioned fatty acids can be obtained from naturally occurring fats and oils, for example via lipid cleavage at elevated temperature and elevated pressure and subsequent separation of the fatty acid mixtures obtained, if appropriate after hydrogenation of the double bonds present.
  • technical fatty acids are used here, which generally represent mixtures of different fatty acids of a specific chain length range with a fatty acid as the main constituent.
  • fatty acids having 12 to 18 carbon atoms are provided alone or in admixture.
  • process step ia3) of the process for providing an n-nonyl ester the n-nonyl alcohol component is reacted with the at least one further component to form an n-nonyl ester.
  • n-nonyl esters can be carried out by any process known to those skilled in the art for preparing such an ester.
  • esterification catalysts acids such as sulfuric acid or p-toluenesulfonic acid, or metals and their compounds can be used. Suitable examples are tin, titanium, zirconium, which are used as finely divided metals or expediently in the form of their salts, oxides or soluble organic compounds.
  • the metal catalysts are high-temperature catalysts which usually reach their full activity only at temperatures above 180 ° C.
  • esterification catalysts are one or more divalent tin compounds or tin compounds or elemental tin, which can react with the educts to form divalent tin compounds.
  • divalent tin compounds or tin compounds or elemental tin can react with the educts to form divalent tin compounds.
  • the catalyst tin can be used as the catalyst tin, stannous chloride, stannous sulfate, stannous alcoholates or stannous salts of organic acids, especially of mono- and dicarboxylic acids.
  • Particularly preferred tin catalysts are tin (II) oxalate and tin (II) benzoate.
  • the esterification reaction between the n-nonyl alcohol component and the carboxylic acid or the derivative of the carboxylic acid can be carried out by methods known to the person skilled in the art. It may be particularly advantageous to remove the water formed during the reaction from the reaction mixture, wherein this removal of the water is preferably carried out by distillation, optionally by distillation with alcohol used in excess. Also, after carrying out the esterification reaction, unreacted alcohol can be removed from the reaction mixture, whereby this removal of the alcohol is preferably carried out by means of distillation. Furthermore, after completion of the esterification reaction, in particular after the separation of unreacted alcohol, the catalyst remaining in the reaction mixture, if appropriate after treatment with a base, can be separated off by filtration or by centrifuging.
  • the esterification reaction between the n-nonyl alcohol component and the carboxylic acid or the derivative of the carboxylic acid at a temperature in a range of 50 to 300 0 C, more preferably in a range of 100 to 275 0 C and most preferably in a range of 200 to 250 0 C fürzubowen.
  • the optimum temperatures depend on the alcohol (s) used, the reaction progress, the type of catalyst and the catalyst concentration. They can easily be determined by experiment for each individual case. Higher temperatures increase the reaction rates and promote side reactions, such as the removal of water from alcohols or the formation of colored by-products.
  • the desired temperature or the desired temperature range can be adjusted by the pressure in the reaction vessel (slight overpressure, atmospheric pressure or optionally negative pressure).
  • this can be used as a further method step, the step of
  • ether repeating units are preferably a - [0-CH 2 -CH 2 ] unit, a - [0-CH 2 -CH 2 -CH 2 ] unit or a mixture of these units ,
  • Such alkoxylated n-nonyl esters can be obtained, for example, by reacting the n-nonyl ester with ethylene oxide, propylene oxide or a mixture of ethylene oxide and propylene oxide in the presence of suitable catalysts in such relative amounts that 2 to 50 ether repeat units, in particular preferably 4 to 25 ether repeat units are incorporated in the ester bond.
  • suitable catalysts in such relative amounts that 2 to 50 ether repeat units, in particular preferably 4 to 25 ether repeat units are incorporated in the ester bond.
  • a functional component is provided.
  • the functional component is a thermoplastic polymer and the organic composition is therefore a thermoplastic, organic composition.
  • thermoplastic polymer refers to plastics that can be easily (thermo-plastic) deformed in a certain temperature range.This process is reversible and can be as often as desired by cooling and reheating to the molten state be repeated, as long as the thermal decomposition of the material does not start due to overheating.
  • thermoplastic polymers which can be used as the functional component according to the first variant of the inventive method, are generally polycondensates or chain polymers or a mixture of these two, in particular thermoplastic polyurethanes, thermoplastic polyesters, thermoplastic polyamides, thermoplastic polyolefins, thermoplastic polyvinyl esters, thermoplastic polyethers , thermoplastic polystyrenes, thermoplastic polyimides, thermoplastic sulfur polymers, thermoplastic polyacetals, thermoplastic fluoroplastics, thermoplastic styrene-olefin copolymers, thermoplastic Polyacrylates, thermoplastic ethylene-vinyl acetate copolymers or mixtures of two or more of the above-mentioned thermoplastic polymers in question.
  • thermoplastic polyurethanes thermoplastic polyesters, thermoplastic polyamides, thermoplastic polyolefins, thermoplastic polyvinyl esters, thermoplastic polyethers , thermoplastic polystyrenes, thermoplastic polyimides, thermoplastic sulfur polymers, thermoplastic polyace
  • thermoplastic polymer is more than 90 wt%, more preferably more than 95 wt%, still more preferably at least 99 wt%, and most preferably 100 wt%. -%, based in each case on the total weight of the thermoplastic polymer, based on thermoplastic polyesters.
  • polyester are in particular polymers obtained by polycondensation reaction between a polycarboxylic acid and a polyol (so-called “iA / BB-polyester”) or by polycondensation reaction of a hydroxycarboxylic acid or by ring-opening polymerization of a cyclic ester (
  • iA / BB-polyester polymers obtained by polycondensation reaction between a polycarboxylic acid and a polyol
  • polycarbonates which are obtainable by reaction of phosgene with diols can be excluded from the term "polyester” used according to the invention.
  • thermoplastic polyesters and copolyesters can be used.
  • polyesters include in
  • Substantially linear polyesters which have been prepared via a condensation reaction of at least one polycarboxylic acid, preferably a dicarboxylic acid (diacid) or an ester-forming derivative thereof and at least one polyol, preferably a dihydric alcohol (diol).
  • the preferred dibasic acid and preferably divalent diol may both be either aliphatic or aromatic, but aromatic and partially aromatic polyesters are particularly preferred as thermoplastic molding materials in view of their high softening points and hydrolytic stability.
  • aromatic polyesters essentially all ester linkages to the aromatic ones are Attached rings. They can be semi-crystalline and even exhibit liquid-crystalline behavior or be amorphous.
  • Partially aromatic polyesters obtained from at least one aromatic dicarboxylic acid or an ester-forming derivative thereof and at least one aliphatic diol are particularly preferred thermoplastic compounds according to the invention
  • polyester examples include terephthalic acid, 1,4-naphthalenedicarboxylic acid or 4,4'-biphenyldicarboxylic acid.
  • suitable aliphatic diols include alkylene diols, especially those containing 2 to 6 C atoms, preferably 2 to 4 C atoms, in which case in particular ethylene glycol, propylene diols and
  • butylene diols are mentioned.
  • ethylene glycol, 1,3-propylene diol or 1,4-butylene diol are used as the polyol or diol component for the production of the thermoplastic polyester contained in the composition according to the invention as component a).
  • Dicarboxylic acids with a diol are particularly suitable for use with polyalkylene terephthalates, for example polyethylene terephthalate (PET), polypropylene terephthalate (PPT) or polybutylene terephthalate (PBT), polyalkylene naphthalates, for example polyethylene naphthalate (PEN) or polybutylene naphthalate (PBN), polylactic acid (PBN). PLA), polyalkylene dibenzoates, for example polyethylene bibenzoate and mixtures of at least two of these thermoplastic polyesters.
  • PET polyethylene terephthalate
  • PPT polypropylene terephthalate
  • PBT polybutylene terephthalate
  • polyalkylene naphthalates for example polyethylene naphthalate (PEN) or polybutylene naphthalate (PBN), polylactic acid (PBN).
  • PLA polyalkylene dibenzoates, for example polyethylene bibenzoate and mixtures of at least two of these thermo
  • These partially aromatic polyesters described above may optionally contain a small amount of units selected from others
  • Dicarboxylic acids for example isophthalic acid, or other diols such as
  • Polyesters are so-called segmented or block copolyesters, which in addition to the abovementioned polyester segments (also “hard segment”) te “called), so-called” soft segments “included.
  • These soft segments are made of a flexible polymer; that is, a substantially amorphous polymer having a low glass transition temperature (T g ) and low rigidity, with reactive end groups, preferably two hydroxyl groups.
  • T g glass transition temperature
  • Soft segments below 0 ° C., more preferably below -20 ° C., and most preferably below -40 ° C.
  • Suitable examples of "soft segments” are aliphatic polyethers, aliphatic Polyester or aliphatic polycarbonates.
  • the molecular weight of the soft segments may vary within wide limits, but is preferably between 400 and 6,000 g / mol.
  • linear polyesters which via a polycondensation reaction of at least one polycarboxylic acid or a
  • thermoplastic polyesters which are obtainable by polycondensation of short-chain hydroxycarboxylic acids or by ring-opening reaction of cyclic esters.
  • thermoplastic polymers examples include in particular L-lactic acid, D-lactic acid, DL-lactic acid, glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 5-
  • thermoplastic polyesters examples include glycolide (a dimer of glycolic acid) and ⁇ -caprolactone (a cyclic ester of 6-hydroxycaproic acid).
  • glycolide a dimer of glycolic acid
  • ⁇ -caprolactone a cyclic ester of 6-hydroxycaproic acid
  • thermoplastic polymers preferred according to the invention are polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polylactic acid (PLA). Furthermore, according to the first variant of the process according to the invention, it is preferred that this thermoplastic polymer is used as the functional component in an amount of at least 60% by weight, preferably of at least
  • n-nonyl ester is used as an additive, in particular as a mold release agent, as an antifogging agent, as a plasticizer, as an antistatic agent.
  • tel or as a lubricant most preferably in a function as
  • Mold release agent preferably in an amount in a range of 0.001 to 40 wt .-%, more preferably in an amount in a range of 0.01 to 25 wt .-%, and most preferably in an amount in the range of 0.1 to 10 wt .-%, in each case based on the total weight of the thermoplastic composition is used.
  • additives which can be provided according to this first variant of the process according to the invention in method step ic), in particular sheath modifiers, filler materials, reinforcing agents, flame retardant compounds, heat and UV stabilizers are used.
  • Stabilizers antioxidants, other processing aids, nucleating agents, dyes and anti-drip agents in question.
  • suitable impact modifiers, filler materials, reinforcing agents and flame retardant compounds can be found, inter alia, in US 2005/0234171 A1.
  • These other additives will be preferably in an amount in a range of 0.001 to 20% by weight, more preferably in an amount in a range of 0.01 to 10% by weight, and most preferably in an amount in a range of 0.1 to 5 % By weight, based in each case on the total weight of the thermoplastic composition.
  • n-nonyl ester the functional component (thermoplastic polymer) and, where appropriate, the additive in the case of the first variant of the process according to the invention in process step ii) can be carried out using known techniques. That's how it works
  • blending may be a dry blending operation in which the various components are mixed below the melt processing temperature of the thermoplastic polymer, or a melt blending process wherein the components, optionally premixed and blended at the melt processing temperatures of the thermoplastic polymer.
  • Melt-mixing processes include, in particular, the melt-edge method preferred according to the invention, which is obtained, for example, by continuous melt-kneading using a single-screw Rnet machine, a twin-screw kneading machine of the same directional rotation type, different gear teeth.
  • the order and the manner of addition of the individual components ia), ib) and optionally ic) in the mixing device is basically not critical.
  • the thermal plastic polymer and optionally the additives are introduced into the mixing device and then added to the n-nonyl ester. It is also conceivable first to mix the n-nonyl ester or a part of the n-nonyl ester with one or more other components of the thermoplastic composition according to the invention, for example with one or more additives, and then mix this mixture either already in the mixing apparatus add present thermoplastic polymer or initially present this mixture in the mixing device and only then add the thermoplastic polymer.
  • the mixing takes place according to at least one of the following measures: Ml) at the glass transition temperature of the thermoplastic polymer or at a temperature above the glass transition temperature of the thermoplastic polymer; M2) wherein the n-nonyl ester is more fluid than the thermoplastic polymer; or M3) wherein at least a portion of the n-nonyl ester is added to the precursor of the thermoplastic polymer.
  • the mixing is carried out in the process steps ia), ib) and optionally ic) provided components in process step ii) of the process according to the invention by a melt mixing process.
  • the mixing in process step ii) takes place at the glass transition temperature of the thermoplastic polymer or at a temperature above the glass transition temperature of the thermoplastic polymer.
  • the mixing at a temperature in a range of 5 degrees below the glass transition temperature (T g ) to 200 0 C above the glass transition temperature of the thermoplastic polymer used, more preferably at a temperature in a range of 1 degree below the glass transition temperature (T g) to 180 0 C above the glass transition temperature of the thermoplastic polymer, and most preferably at a temperature in a range from 1 degree above the glass transition temperature (T g) to 150 0 C above the Glass transition temperature of the thermoplastic polymer used, but the upper limit of the temperature range is essentially limited by the decomposition temperature of the thermoplastic polymer used. Furthermore, it corresponds to embodiments of the invention, when the mixing takes place at temperatures in a range of 10 to 180 0 C and preferably 50 to 150 0 C above the glass transition temperature of the thermoplastic polymer used.
  • the n-nonyl ester is more liquid than the thermoplastic polymer
  • the n-nonyl ester is used at a temperature at which it is liquid and the thermoplastic polymer is not yet liquid.
  • the temperature of the thermoplastic polymer is below the glass transition temperature of this polymer.
  • the melting temperature of the n-nonyl ester, and the glass transition temperature of the thermo-plastic polymer by at least 5 ° C, preferably at least 10 0 C and more preferably at least 30 0 C distinguish.
  • the thermoplastic polymer is in this embodiment and also generally preferred to use the thermoplastic polymer as granules. In general, all known in the art granular forms with spherical or cylinder-like spatial form in the present case come into consideration. The determined by means of sieve analysis
  • Granule size is at least 70% by weight of the granules in a range of 0.01 to 5 cm and preferably in a range of 0.1 to 4 cm.
  • the surfaces of the granule particles can be at least partially coated with the n-nonyl ester, so that an at least partially coated thermoplastic polymer granules are obtained. This allows the most homogeneous possible distribution of the n-nonyl ester according to the invention in the thermoplastic composition, especially if this is formulated as a formulation for the subsequent extrusion.
  • n-nonyl esters in liquid and also in solid form come into consideration.
  • a precursor of the thermoplastic polymer basically all precursors known to those skilled in the art are considered prior to obtaining the thermoplastic polymer. These include in particular precursors which have a lower molecular weight than the final thermoplastic polymer. In this case, it is preferred that the molecular weight of the precursor be at least 1.1, preferably at least 1.5, and more preferably at least 2, of that of the finished thermoplastic polymer.
  • thermoplastic polymer which preferably consist of 2 to 100 monomers
  • a prepolymer which is polymerized, usually by heat treatment, to form the finished thermoplastic polymer is based Prepolymer to more than 100 monomers as repeat units, wherein the number of monomers as repeat units and thus the final molecular weight of the finished thermoplastic polymer is not achieved.
  • the functional component is an enzyme and the organic composition is a detergent.
  • Suitable enzymes are in particular amylases, proteases, lipases, cellulases, peroxidases or mixtures of at least two of these enzymes.
  • Amylases are added to remove starch and glycogen. Suitable for use according to the invention are alpha, beta and gamma amylases as well as glucoamylases and maltogenic amylases. Suitable amylases are commercially available for example under the names Duramyl ®, Termamyl ®, Fungamyl ® and BAN ® (Novo Nordisk), and Maxamyl ®, Purafect ® OxAm the o-. The amylases can be derived from any source, such as bacteria, fungi, pancreas glands of animal origin, germinated grains or yeasts. Genetically modified amylases may also be used, if desired, even as a functional component in the organic compositions according to the invention.
  • the amylase enzymes may be used in the compositions according to the invention in an amount of from 0.0001% by weight to 5% by weight, more preferably from 0.0001% by weight to 1% by weight and most preferably preferably from 0.0005 to 0.5 wt .-%, each based on the total weight of the organic composition, are present.
  • proteases for cleaving proteins and peptide residues can also be added to the organic compositions according to the invention in accordance with the second variant of the method according to the invention.
  • Proteases are particularly suitable for the hydrolytic cleavage and removal of protein residues, in particular dried-on protein residues.
  • Proteases suitable according to the invention are proteinases (endopeptidases) and peptidases (exopeptidases).
  • Useful proteases may be of plant, animal, bacterial and / or fungal origin. Suitable proteases are in particular serine, cysteine, aspartate and metal proteases. Also genetically modified proteases are, if appropriate even preferred, usable in the inventive compositions.
  • proteases are commercially available under the names Alcala- se ®, BLAP ®, Durazym ®, Esperase ®, Everlase® ®, Maxapem ®, Maxatase ®, options timase Purafect ® OxP or Savinase ®.
  • proteases are used in an amount of 0.00001 to 1.5 wt .-% and particularly preferably from 0.0001 to 0.75 wt .-%, each based on the total weight of the organic composition.
  • lipases can be used as a functional component according to the second variant of the method according to the invention. They serve to remove firmly adhering greasy soil. Lipases are thus a bio-alternative to surfactants and can support the cleaning action of the surfactants in the range from 0.0001 to 1% by weight, based on the total weight of the organic composition. Suitable lipases can be obtained from plants (for example, Rhizinusart), microorganisms and animal sources, such as pancreatic lipases. Commercially available lipases are, for example, Lipolase ®, Lipomax® ®, ® and Lipozym Lumafast® ®.
  • the above-mentioned enzymes may optionally be combined with any other enzymes to improve the purification performance of the
  • Detergent used to further improve organic composition is Detergent used to further improve organic composition.
  • Further enzymes which are suitable according to the invention are cellulases, hemicellulases, peroxidases, reductases, oxidases, ligninases, cutinases, pectinases, xylanases, phenoloxidases, lipoxygenases, tannases, pentosanases, malanases. Glucanases, arabinosidases and any mixtures of these enzymes.
  • the n-nonyl ester is preferably added to the detergent in the function of a surfactant, wherein it is preferred in this case that the n-nonyl ester in an amount of 0.001 to 40 wt .-%, particularly preferably from 0.01 to 30 wt .-%, more preferably from 0.1 to 20 wt .-% and most preferably from 1 to 10 wt .-%, each based on the total weight of the organic composition is used.
  • additives which can be provided in process step ic) according to this second variant of the process according to the invention, there are in particular further surfactants, builders, solvents, hydrophobic components, phase separation aides, thickeners, polymers, soil release, different from the n-nonyl ester Active ingredients, solubilizers, hydrotropes, such as, for example, sodium cumene sulphonate, octylsulfate, butylglucoside, butylglycol, emulsifiers, such as gallus soap, gloss-drying additives, cleaning boosters, antimicrobial agents or disinfectants, antistatics, preservatives, such as glutaraldehyde, bleach systems, perfumes, fragrances, dyes , Opacifiers or too Skin protection agent, wherein the amount of such additives is usually not more than 12 wt .-%, based on the total weight of the organic composition.
  • solubilizers such as, for example, sodium cumene sul
  • the functional component is a binder and the organic composition is an adhesive.
  • the chemical composition of the binder contained in the adhesive depends on how it is set by the adhesive.
  • it can be a physically setting adhesive, for example a hotmelt adhesive comprising, for example, ethylene-vinyl acetate copolymers, polyamides or polyesters as binders, a solvent-containing wet adhesive comprising, for example, polymeric vinyl compounds, polymethyl methacrylate or natural and synthetic rubber as a binder, a contact adhesive comprising, for example, polychloroprenes or butadiene-acrylonitrile rubber as a binder, a dispersion adhesive comprising, for example, polyvinyl acetate, vinyl acetate copolymers, polyacrylates, polyvinylidene chloride, styrene-butadiene copolymers, polyurethanes, polychloroprene or rubber latexes as binders, a water-based adhesive comprising, for example, glutinic glues, such as skin glue or fish glue, glues based on plant
  • the adhesive and a chemically curing adhesive for example a cyanoacrylate-based adhesive comprising, for example, cyanoacrylic acid ester as a binder, a methyl methacrylate-based adhesive containing, for example, methacrylic acid methylester as a binder, an anaerobic curing adhesive, including, for example Diacrylic esters of diols as binders, a radiation-curable adhesive comprising, for example, epoxy acrylates or polyester acrylates as binders, a phenol formaldehyde resin-based adhesive comprising, for example, phenols and formaldehyde as a binder, a silicone-based adhesive, including, for example, polyorganosiloxanes as a binder, a polyimide based adhesive containing, for example, aromatic tetracarboxylic anhydrides and aromatic diamines as binders, an epoxy resin adhesive containing, for example, oligomeric diepoxides and polyamines or polya
  • the concentration of binder in the adhesive is dependent on the type of adhesive used, but is usually in a range of 10 to 100 wt .-%, more preferably from 20 to 90 wt .-% and more preferably from 30 to 80 wt. -%, in each case based on the total weight of the adhesive.
  • the n-nonyl ester is preferably added to the adhesive in the function of a solvent, a condenser or else in the function of a surfactant, in which case it is preferred that the n-nonyl ester is present in an amount from 0.001 to 40% by weight, more preferably from 0.1 to 30% by weight
  • the concentration of the n-nonyl ester may optionally also be above the above-mentioned concentration ranges.
  • the additives which can be provided according to this third variant of the process according to the invention in process step ic) depend on the nature of the particular adhesive.
  • the amount of such additives depends on the nature of the particular adhesive and is usually not more than 50 wt .-%, based on the total weight of the organic composition.
  • the functional component is a paraffin, in particular a paraffin wax, and the organic composition is an antifoam.
  • the paraffin provided as a functional component in the fourth variant of the process according to the invention in process step ib) generally represents a complex substance mixture without a sharp melting point.
  • its melting range is usually determined by differential thermal analysis (DTA) as described in "The Analyst (1962),
  • paraffin waxes which appear solid at room temperature may contain different proportions of liquid paraffin.
  • the liquid fraction at 40 ° C. is as high as possible, even without being 100% at this temperature.
  • paraffin wax mixtures have at 40 ° C. a liquid fraction of at least 50% by weight, in particular from 55% by weight to 80% by weight, and at 60 ° C. a liquid fraction of at least 90% by weight. This has the consequence that the paraffins at temperatures down to at least 70 0 C, preferably down to at least 60 0 C are flowable and pumpable. It should also be ensured that the paraffins contain as far as possible no volatile components.
  • Preferred paraffin waxes contain less than 1% by weight, in particular less than 0.5 wt .-% at 110 0 C and atmospheric pressure vaporizable fractions.
  • Paraffin waxes which can be used according to the invention can be obtained, for example, under the trade names Lunaflex® from Guer and Deawax® from DEA Mineralöl AG.
  • the amount of paraffin in the defoaming organic composition preferably ranges from 50 to 99% by weight, more preferably from 60 to 95% by weight, and most preferably from 70 to 95% by weight. , in each case based on the total weight of the organic composition.
  • the proportion of paraffin can also be significantly below the abovementioned concentration ranges.
  • the n-nonyl ester is preferably added to the defoamer in the function of a solvent or else in the function of a surfactant, in which case it is preferred for the n-nonyl ester to be present in an amount of 0.001 to 20% by weight %, more preferably from 0.1 to 10% by weight, even more preferably from 1 to 8% by weight and most preferably from 2 to 7% by weight, based in each case on the total weight of the organic composition, is used.
  • the additives which can be provided in process step ic) according to this fourth variant of the process according to the invention may be, for example, silicone oils and their mixtures with hydrophobicized silica, or further defoaming compounds such as, for example, bisamides.
  • the defoamer may also contain carrier materials which preferably have a granular structure and consist of water-soluble or water-dispersible, surfactant-free compounds, in particular of inorganic and / or organic salts, which are suitable for use in washing and cleaning. are suitable.
  • water-soluble, inorganic support materials are in particular alkali metal carbonate, alkali metal borate, alkali aluminosilicate and / or alkali metal sulfate, while as organic support materials, for example acetates, tartrates, succinates, citrates, carboxymethylsuccinates and the alkali metal salts of aminopolycarboxylic acids, such as
  • EDTA Hydroxyalkanphosphonate and Aminoalkanpolyphosphonate in question, such as l-hydroxyethane-l, l-diphosphonate, ethylene diaminotetramethylene lenphosphonat and Diethylentriaminpentamethylenphosphonat can be used. It is also conceivable to use bulking polymers, such as, for example, polyethylene glycols, polyvinyl alcohol, polyvinylpyrrolidones, polyacrylates and cellulose derivatives as support materials. The amount of such additives is usually not more than 25% by weight, based on the total weight of the organic composition. However, carrier materials can also be used in a significantly higher concentration.
  • defoamer which can be prepared according to the fourth variant of the method according to the invention, mentioned in WO-A-1997/034983 defoamers may be mentioned, in particular, the disclosure of this document with respect to the method for
  • the functional component is an oil, preferably a hydrocarbon having 20 to 35 carbon atoms (lubricating oil), and the organic composition is a lubricant formulation.
  • the oil contained in the lubricant formulation may be a raffinate obtained by separating the hydrocarbons naturally present in petroleum with 20 to 35 carbon atoms to a hydrocracking oil (HC synthesis oil) obtained by cracking petroleum constituents have been obtained as 35 carbon atoms, or synthetic hydrocarbons obtained by cracking petroleum constituents of less than 12 carbon atoms into gases such as, in particular, ethene or butene and the subsequent synthesis of hydrocarbons having 20 to 35 carbon atoms from these gases become.
  • HC synthesis oil hydrocracking oil
  • bio-oils obtained from renewable raw materials may also be present in the lubricant formulation, in particular using bio-oils from the HETG, HEPG, HEPR or HEES group (VDMA 24568 ISO standard 15380).
  • the HETG group includes triglycerides, such as rapeseed oil, while the HEPG group comprises polyglycols.
  • the HEES group includes synthetic esters, in particular TMP esters (trimethylpropane esters, also called oleic esters or trioleate).
  • the HEPR group includes liquids consisting mainly of polyalphaolefins (PAO) and related hydrocarbons.
  • the amount of oil in the lubricant formulation is preferably in a range of 50 to 99% by weight, more preferably in a range of 60 to 95% by weight and most preferably in a range of 70 to 90% by weight, in each case based on the total weight of the organic
  • the lubricant formulation is also to be used for cooling, it can also have large amounts of water, in which case the oil content in the lubricant formulation can also be significantly below the above-mentioned concentration ranges.
  • the n-nonyl ester is added preferably in the function of a solvent or in the function of a surfactant of the lubricant formulation, in which case it is preferred that the n-nonyl ester in an amount of
  • the additives which can be provided in process step ic) according to this fifth variant of the process according to the invention may be, in particular, surface-active, oil-improving or oil-protecting additives.
  • Surface-active additives include detergents, dispersants, high-pressure or wear protection,
  • Corrosion and rust protection as well as friction value-changing additives change the properties of the oil in terms of viscosity, pour point and elastomers, for example of seals.
  • the oil-protecting additives cause the oil to age, deactivate metal particles and prevent the oil from foaming. Even finely ground solids, such as Teflon (PTFE), ceramic oxides or Molybdändisulf ⁇ d compounds can be added as an additive.
  • PTFE Teflon
  • the lubricant composition may also contain water in amounts of up to 95% by weight, more preferably in amounts of up to 90% by weight, in which case the lubricant composition is preferably in the form of an emulsion is present.
  • the functional component is a colorant and in the case of the ganic composition around a varnish or around a color.
  • a "parbe” is understood to mean a non-shiny, open-pore coating with a high proportion of dye and pigment, but only a low binder content, while a “jacket” is a composition for coating surfaces of wood, metal, plastic or mineral material, which has a higher binder content compared to a paint.
  • the colorant may be an inorganic or an organic colorant, which colorants may be water-soluble or water-insoluble.
  • inorganic or organic, preferably powdered pigments are suitable. Pigments differ from dyes in that they are insoluble in their application media. Suitable inorganic pigments and their methods of preparation can G. Buxbaum; Jndustrial Inorganic Pigments, "ed., Pp. 85-107; VCH Verlagsgesellschaft mbH, Weinheim, 1993, G. Buxbaum; Industrial Inorganic Pigments," 1st ed., Pp. 114-117; VCH Verlagsgesellschaft mbH, Weinheim, 1993 and G. Buxbaum; Jndustrial Inorganic Pigments ", 1st ed., Pp. 124-131; VCH Verlagsgesellschaft mbH, Weinheim,
  • colorants may be present in the paint or in the paint in amounts ranging from 0.001 to 40% by weight, more preferably in amounts ranging from 0.01 to 30% by weight, even more preferably in amounts ranging from 0.01 to 30 wt .-%, and most preferably in amounts ranging from 0.1 to 10 wt .-%, each based on the total weight of the organic composition, be contained.
  • the n-nonyl ester is preferably added to the paint or the paint in the function of a solvent or in the function of a surfactant, in which case it is preferred for the n-nonyl ester to be present in an amount of 0.001 to 40% by weight, more preferably from 0.1 to 30% by weight, even more preferably from 1 to 20% by weight and most preferably from 2 to 10% by weight, based in each case on the total weight of organic composition is used.
  • the additives which can be provided in process step ic) according to this sixth variant of the process according to the invention may in particular be binders, such as vegetable oils, coniferous gum rosin, casein from milk, alkyd resin, polyurethane resin or epoxy resin, solvents, such as water , Etha nol, citrus peel oil, white spirit, water or glycol ethers, thixotropic agents, antioxidants, viscosity regulators, skin and foam inhibitors, leveling agents, UV absorbers, extenders, preservatives or binders.
  • binders such as vegetable oils, coniferous gum rosin, casein from milk, alkyd resin, polyurethane resin or epoxy resin
  • solvents such as water , Etha nol, citrus peel oil, white spirit, water or glycol ethers, thixotropic agents, antioxidants, viscosity regulators, skin and foam inhibitors, leveling agents, UV absorbers, extenders, preservatives or binders.
  • the functional component is a hair or skin care substance and the organic composition is a cosmetic preparation.
  • hair and / or skin care substances are in particular 18-.beta.-glycyrrhetinic acid from liquorice root extract (Gylcyrrhiza glabra), preferably in a purity of> 99% pure substance in the extract, aescin in horse chestnut (Aesculus hippocastanum), allantoin, aloe vera ( containing mainly sugars, anthraquinones and minerals such as zinc), amino acids such as alanine, arginine, serine, lysine, ammonium glycyrrhizate from licorice root extract, preferably in a purity of almost 100% pure substance in the extract, apigenin from chamomile extract (Matri) caria recutita), Arnica, in particular Arnica montana or Arnica chamissonis, Asiaticoside and Madecassoside in Centella asiatica extract, Avenonaanthramide from oat extract (Avena sativa), Avocadol
  • Clover extract Trifolium pratense
  • St. John's wort extract St. John's wort extract (Hypericum perforatum)
  • jojoba oil lecithin, corn oil (Zea mays)
  • evening primrose oil niacinamide
  • oenotheine B in willowherb extract Epilobium angustifolium
  • oleuropein in olive -Extract Olea europea
  • phytocresin sodium beta-sitosterol sulphate
  • plankton extract tetraselmis suecica, spirulina and others
  • polyphenols catechins from grape seed extract (Vitis vinifera)
  • polyphenols green catechins Tea
  • marigold extract Calendula off ⁇ cinalis
  • rosemary acid in balm extract Melissa officinalis
  • sandorn oil oat glucans (Avena sativa)
  • Glycyrrhetinic acid Glycyrrhetinic acid
  • sterols sitosterol in stinging nettle extract (Urtica dioca)
  • sweet almond oil Prunus dulcis
  • vitamin C and its esters vitamin E and its esters
  • wheat germ oil zinc gluconate / magnesium aspartate / copper gluconate
  • zinc sulfate or zinc oxide as well as proteins or protein derivatives , such as protein hydrolysates (for example, collagen, keratin,
  • These hair and / or skin care substances may be present in the cosmetic preparations in amounts ranging from 0.001 to 40% by weight, more preferably in amounts ranging from 0.01 to 30% by weight, more preferably in Amounts in a range of 0.01 to 30 wt .-%, and most preferably in amounts ranging from 0.1 to 10 wt .-%, each based on the total weight of the organic composition, be contained.
  • the n-nonyl ester is added preferably in the function of a solvent or in the function of a surfactant of the cosmetic preparation, in which case it is preferred that the n-nonyl ester in an amount of 0.001 to 40 Wt .-%, particularly preferably from 0.1 to 30 wt .-%, more preferably from 1 to 20 wt .-% and most preferably from 2 to 10 wt .-%, each based on the total weight of the organic composition , is used.
  • Suitable additives which can be provided according to this seventh variant of the method according to the invention in method step ic) are, for example, Schrader, K., "Bases and Formulations of Cosmetics", 2nd edition, 1989, pages 728-737, Domsch, A. , J) ie cosmetic preparations ", Verlag für chemische Industrie (H. Ziolkowsky, Ed.), 4th edition, volume 2 pages 212-230, 1992 or Johnson, DH,, flair and
  • the additives can be used in the customary amounts known to the person skilled in the art, in particular in amounts of from 0.1 to 10.0% by weight, based on the total weight of the organic composition.
  • a contribution to the solution of the abovementioned objects is also provided by a method for producing a shaped body, comprising the method steps:
  • thermoplastic composition obtainable by the above-described process according to the first variant
  • thermoplastic composition II) heating the thermoplastic composition to the glass transition temperature of the thermoplastic polymer or to a temperature above the glass transition temperature of the thermoplastic polymer; III) the production of a shaped article from the heated, thermoplastic composition prepared in process step II).
  • step I) of the process according to the invention for the production of a shaped body initially a thermoplastic composition according to the invention is provided, this preparation preferably being carried out by a process according to the first variant of the process according to the invention.
  • the thermoplastic composition is heated to the glass transition temperature of the thermoplastic polymer or at a temperature above the glass transition temperature of the thermoplastic polymer.
  • the heating of the thermoplastic composition to a temperature in a range of 5 degrees below the glass transition temperature (T g ) to 100 0 C above the glass transition temperature of the thermoplastic polymer used, more preferably to a temperature in a range of 1 degree below the glass transition temperature (T g ) to 50 0 C above the glass transition temperature of the thermoplastic polymer used, and most preferably to a temperature in the range of 1 degree above the glass transition temperature (T g ) to 20 0 C is above the glass transition temperature of the thermoplastic polymer used, but here too the upper limit of the temperature range is essentially limited by the decomposition temperature of the thermoplastic polymer used.
  • the method steps I) and II) can be carried out simultaneously or in succession.
  • a simultaneous implementation of method steps I) and II) is useful, for example, if the thermoplastic composition is produced by means of a melt-blending method.
  • a successively carrying out the process steps I) and II), for example, makes sense if the thermoplastic composition is prepared by a dry mixing process or if the thermoplastic composition is indeed prepared by a melt mixing process, but not immediately after the preparation of the formation of a shaped body is subjected special rather, it is first cooled according to method step v).
  • a shaped body is produced from the heated, thermoplastic composition produced in process step II).
  • injection molding, extrusion molding, compression molding, layer molding, lamination molding, cavity molding, vacuum molding and transfer molding are considered as a method of producing a molded article, with injection molding being particularly preferred.
  • the mass cross-section is the cross-section of a region of the shaped body that consists of the thermoplastic molding composition of the invention.
  • the mass cross-section represents the thickness of a wall of these containers or containers.
  • the mass cross-section represents the thickness of these threads or strands.
  • the mass cross-section represents the strength of these two-dimensional structures.
  • all of those known to the person skilled in the art and known to those skilled in the art come to reduce the mass fraction suitable methods. This includes, for example, stretching in one or two directions, pulling in one or two directions, spinning or blowing, each preferably at elevated temperatures at which the thermoplastic composition of the invention is so soft or even liquid that stretching, pulling, spinning or Blisters can be done.
  • the partial region in which the cross-sectional reduction takes place preferably makes up at least 50% and particularly preferably at least 80% of the shaped article obtained in step III).
  • stretching or drawing takes place when a fiber is to be obtained from the shaped body obtained in step III).
  • drawing or stretching can take place in one or more dimensions.
  • the web running from an extruder can be drawn onto a roll at a speed which is higher than that from the extruder in comparison with the exit speed.
  • a container or container it is primarily the blowing in step IV) that is used, apart from stretching, pulling and spinning.
  • the mass cross-section reduction takes place by applying a gas pressure.
  • the gas pressure is generally chosen so that the usually heated to at least glass transition temperature thermoplastic composition of the molded article obtained in step III) can be stretched.
  • the elongation is limited by the use of a mold having the final shape of the molded article.
  • liquid containers such as freezers, trays and packaging for foods such as fruits, vegetables or meat and pharmaceuticals as tablets, capsules, suppositories or powders and containers for liquids produced.
  • These liquid containers can be used in addition to liquids of the cosmetic or pharmaceutical industry in the food industry, preferably in the beverage industry as reusable containers such as PET or PLA bottles.
  • two or more of the method steps I) to IV) to be supplemented by further method steps and / or to run at least overlapping in time. This applies in particular to process steps III) and IV).
  • These include disposable and reusable containers, such as plates, bowls, pots or cups, and cutlery such as knives, forks or spoons.
  • the biodegradable thermoplastic compositions according to the invention are particularly suitable for these applications.
  • the material provided in process step a) is preferably a pharmaceutical, a personal care product, an agricultural auxiliary, an adhesive, a building material, a dye or a foodstuff.
  • the at least partially surrounding the good can be done for example by the method described in DE-A-103 56 769.
  • a contribution to the solution of the abovementioned objects is also provided by a method for coating substances which can be consumed by living beings, including as method steps:
  • Nonyl alcohol component is able to react to form an n-nonyl ester;
  • n-nonyl ester is preferably carried out according to process step ia) of the process described above for the preparation of an organic composition.
  • the at least partial surrounding of the substance which can be consumed by living beings with the n-nonyl ester can take place, for example, in such a way that the consumable substance and the n-nonyl ester are mixed together in suitable mixing devices, in particular the Patterson-Kelley mixer, DRAIS turbulence mixer, Lödigemischer, Ruberg mixers, screw mixers, plate mixers and fluidized bed mixers as well as continuous vertical mixers in which the polymer structure is mixed by means of rotating knives in rapid frequency (Schugi mixer), as mixing devices into consideration.
  • suitable mixing devices in particular the Patterson-Kelley mixer, DRAIS turbulence mixer, Lödigemischer, Ruberg mixers, screw mixers, plate mixers and fluidized bed mixers as well as continuous vertical mixers in which the polymer structure is mixed by means of rotating knives in rapid frequency (Schugi mixer), as mixing devices into consideration.
  • the n-nonyl ester is not liquid at the mixing conditions, this component must be heated to a temperature above the melting point of the n-nonyl ester before or during mixing with the substance which can be consumed by living beings.
  • the at least partially surrounding the edible by living things substance with the n-nonyl ester also be done by, for example, presented by living beings in a fluidized bed mixer and submitted the n-nonyl ester in liquid form on by Living beings consumable substance is sprayed on.
  • n-nonyl ester which is obtainable by reaction, also contributes to the solution of the abovementioned objects an n-nonyl alcohol component having another component capable of reacting with the n-nonyl alcohol component to form an n-nonyl ester as an additive in a composition containing as a functional one
  • thermoplastic polymer wherein the composition is a thermoplastic composition; ⁇ ) an enzyme, the composition being a detergent; ⁇ ) a binder of an adhesive, the composition being an adhesive; ⁇ ) a paraffin, the composition being a defoamer; ⁇ ) an oil, the composition being a lubricant formulation; ⁇ ) a colorant, the composition being a lacquer or a color; or ⁇ ) a hair or skin care substance, the composition being a cosmetic preparation,
  • n-nonyl ester is preferably obtained by the process described above for preparing an n-nonyl ester, comprising the process steps ial), ia2), ia3) and optionally ia4).
  • n-nonyl ester described at the outset which is obtainable by reacting an n-nonyl alcohol component with a further component which reacts with the n-nonyl alcohol component to form an n-nonyl ester, also contributes to the solution of the abovementioned objects react as an additive in compositions used in drilling wells. It is according to the invention particularly preferred that the n-nonyl ester described above is used as an additive in drilling fluids or cleaning agents for drilling equipment.
  • the invention therefore also relates to a method for cleaning the surfaces of boreholes, in particular the walls of boreholes, conveyor or casing pipes or walls of casings, and for cleaning drilling equipment or cuttings, the surfaces initially comprising a cleaning agent including those described above n-nonyl ester in contact and optionally rinsed the surfaces then with water.
  • the cleaning agent is used in the form of an aqueous solution, an aqueous dispersion or an oil-in-water emulsion, including
  • (cc2) 0 to 50 wt .-%, particularly preferably 0.5 to 35 wt .-%, further preferably 1.0 to 15 wt .-% and most preferably 1.2 to 10 wt .-% further, from n-nonyl ester various additives, as well
  • (cc3) 1 to 99.9% by weight, more preferably 30 to 99% by weight, further preferably 70 to 98% by weight and most preferably 80 to 97.6% by weight of water,
  • the sum of the components ( ⁇ l) to ( ⁇ 3) is 100 wt .-% is used.
  • the amount of component ( ⁇ l) in the aqueous composition can vary and is adapted to the nature and extent of the contamination.
  • weighting agents such as weighting agents, fluid-loss additives, viscosity-regulating additives, wetting agents or salts come into consideration as additives (cc2) other than n-nonyl ester.
  • additives cc2
  • the general principles for the composition of the respective treatment fluids apply here.
  • organic polymer compounds of natural and / or synthetic origin may prove advantageous.
  • starch or chemically modified starches cellulose derivatives such as carboxymethylcellulose, guar gum, synthangum or purely synthetic water-soluble and / or water-dispersible polymer compounds, in particular of the type of high molecular weight polyacrylamide compounds with or without anionic or cationic modification.
  • drilling equipment such as the derrick, the drill string, in particular the drill pipe and the drill bit, cleaning equipment, plant for solids disposal, in particular shakers or centrifuges, pumps, motors or gearboxes, or the drilling platform or parts thereof.
  • the cleaning agent containing the n-nonyl ester is sprayed or applied to the surfaces of the objects or the objects to be cleaned are immersed in the aqueous compositions.
  • the contaminants dissolve away from the surfaces.
  • the surfaces are brought into contact with water so that the agents are removed together with the impurities, for example by the surface is sprayed with a jet of water.
  • the cleaning agent containing the n-nonyl ester can be used to clean up cuttings, the so-called cuttings, which accumulate during drilling and must be deposited on the bottom of the lake in the vicinity of the drilling platform in offshore drilling, resulting in a strong cuttings
  • the cuttings are cleaned beforehand and freed from the remains of the drilling fluid.
  • the cleaning agent containing the n-nonyl ester can be used in all cleaning processes known to the expert in the field of These include, but are not limited to, the removal of paraffin deposits from wellbore walls.
  • wellbores are cleaned by pumping a cleaning fluid under pressure through the wellbore and through the detergent removes the deposits of d in the walls of the borehole. Subsequently, the impurities are transported with the liquid from the borehole.
  • this includes the method steps
  • the cleaning agent containing the n-nonyl ester through the space between the outside of the Casing and the walls of the wellbore out, preferably in this space is circulated.
  • This circulation can be effected, for example, by the cleaning agent pumping down through the casing, preferably down the drill pipe, at the lower end of the casing, preferably on the drill bit or drill bit, and then through the space between the outside of the casing and the walls of the borehole rises again. If the cleaning agent is continuously pumped down through the casing, in this way both the walls of the wellbore and the outside of the casing can be cleaned.
  • the latter includes the step of drilling a borehole into the ground by means of a drill head driven by a drill string, wherein the cleaning agent containing the n-nonyl ester is passed through the boring head at least partially, preferably at least is partially circulated therethrough, this passage or circulation being at least partially during the presence of the drill bit in the wellbore.
  • drilling equipment whose surface can be cleaned with the cleaning agent
  • drilling equipment such as the derrick
  • the drill string in particular the drill string and the drill bit
  • cleaning equipment plant for solid disposal, in particular shakers or centrifuges, pumps, motors or gearbox, or but the drill bit form or parts thereof.
  • a contribution to the solution of the abovementioned objects is also made by a method for producing a borehole, including the method steps (ßl) drilling a borehole in the ground by means of a drill bit driven by a drill string,
  • the cleaning agent containing the n-nonyl ester is passed through the intermediate space between the outside of the casing and the walls of the borehole, preferably through this intermediate space.
  • sealing liquid which is introduced in step (ß5) in the space between the outside of the conveying tube and the inside of the casing, all known to the expert for this purpose Materia- be used. As an example, at this point those sealing liquids are mentioned, which are described in US 7,219,735.
  • a further contribution to the solution of the abovementioned objects is also provided by a process for producing an oil or a gas which, in addition to the abovementioned process steps ( ⁇ 1) to ( ⁇ 3) and optionally ( ⁇ 4) and ( ⁇ 5), also the process steps
  • the invention also relates to a method for the production of boreholes, in which a drilling fluid is pumped through a borehole, wherein a composition comprising the n-nonyl ester described in the introduction is used as the drilling fluid.
  • this composition is a water-in-oil emulsion.
  • composition I from 28.9 to 99% by weight, more preferably from 60 to 90% by weight and most preferably from 70 to 80% by weight, based in each case on the total weight of the composition, of a water-immiscible organic oil Phase, II) 1 to 48 wt .-%, preferably, more preferably 5 to 40 wt .-% and most preferably 10 to 30 wt .-%, each based on the total weight of the composition, water or aqueous phase,
  • the organic oil phase I) is wholly or partly selected from the group of a) paraffins having 5 to 22 carbon atoms and / or b) paraffins with 5 to 22 C atoms and / or c) internal Olef ⁇ ne having 12 to 30 C atoms in the molecule and / or d) carboxylic acid esters of the general formula R-COO-R, in the R for a linear or branched, saturated or unsaturated Alkyl radical having 15 to 25 carbon atoms and R 'is a saturated, linear or branched
  • this water-in-oil emulsion has a density of the liquid component in a range of 1.2 to 3.0 g / cm 3, and more preferably in a range of 1.5 to 3.0 g / cm 3 .
  • the oil phase of the systems according to the invention contains the components a) to e) alone or the components a), b), d) or e) together in admixture with esters c) and optionally in admixture with other suitable oil phases. There are also any mixtures of the oil phases a) to e) with each other possible.
  • linear or branched paraffins having 5 to 22 carbon atoms are used according to the invention.
  • Paraffins - more correctly referred to as alkanes - are known to be saturated hydrocarbons which, for the linear or branched representatives of the general empirical formula C n H 2n + ! consequences.
  • the cyclic alkanes follow the general empirical formula C n H 2n .
  • Particularly preferred are the linear and branched paraffins, whereas cyclic paraffins are less preferred.
  • branched paraffins are particularly preferred which are liquid at room temperature, ie those having 5 to 16 carbon atoms per molecule.
  • paraffins with 17 to 22 carbon atoms which have a waxy consistency.
  • mixtures of the different paraffins and it is particularly preferred if these mixtures are still liquid at 21 ° C.
  • Such mixtures can be formed, for example, from paraffins having 10 to 21 carbon atoms.
  • Paraffins are particularly preferred oil phases - alone or as a mixture component with other oil phases - in drilling fluids - preferably those of the invert type, in which the crosslinked glycerol or oligoglycerol esters according to the invention are used as thickeners.
  • IOs are likewise compounds known per se, which can be prepared by all methods known to the person skilled in the art.
  • EP 0 787 706 A1 describes e.g. a method for the synthesis of IOs by isomerization of alpha-olefins to sulfonic or persulfonic acids. It is characteristic that the IOs thus obtained are linear and contain at least one olefinic double bond that is not in the alpha position of the alkyl chain.
  • such IO or 10 mixtures are used which contain IO having 12 to 30 C atoms in the molecule, preferably having 14 to 24 C atoms and in particular having up to 20 C atoms in the molecule.
  • esters of the general formula R-COO-R ' in which R is a linear or branched, saturated or unsaturated alkyl radical having 15 to 25 carbon atoms, and R' is a saturated, linear or branched alkyl radical having 6 to 22 C atoms Atoms means part of the oil phases according to the invention.
  • esters are known chemical compounds. Their principal use in drilling fluids is z.
  • B. Subject of EP 0374 672 Al or EP 0374 671 Al. Particularly preferred is the use of such esters whose radical R is a saturated or unsaturated alkyl radical having 15 to 25 and R 'is a saturated alkyl radical having 3 to 10 carbon atoms.
  • the saturated compounds are particularly preferred.
  • Mineral oils are a collective term for the liquid distillation products obtained from mineral raw materials (petroleum, lignite and hard coal, wood or peat), which essentially consist of mixtures of saturated hydrocarbons.
  • the mineral oils contain only small amounts of aromatic hydrocarbons, preferably less than 3 wt .-%. Preference is given at 21 0 C liquid mineral oils based on petroleum.
  • the mineral oils preferably have boiling points of 180 to 300 0 C.
  • LAO Linear alpha-olefins
  • alpha-C-atom Linear alpha-olefins
  • Natural-based LAOs are synthesized by dehydration
  • they owing to their volatility, they generally have at least 10, preferably at least 12 to 14 C atoms in the molecule
  • the upper limit of the LAO which is free-flowing at room temperature lies in the range from C 8 to C 20.
  • carbonates are understood as meaning carbonic acid esters of fatty alcohols having 8 to 22 C atoms, preferably the diesters of carbonic acid.
  • Such compounds and their use as oil phase for Bohr Hughesstoff are described in DE 40 18 228 Al.
  • esters of Ci_ 5 monocarboxylic acids and 1- and / or polyhydric alcohols radicals of 1-valent alcohols having at least 6, preferably at least 8 C atoms and the polyhydric alcohols preferably 2 to 6 C atoms in the molecule have,
  • the oil phase I) of the composition used as a drilling fluid in the form of a water-in-oil emulsion preferably have pour points below 0 0 C, preferably below -5 0 C (measured according to DIN ISO 3016: 1982-10) on.
  • the Brookf ⁇ eld- viscosity of the oil phase is at most 50 mPas at 0 0 C.
  • compositions used as drilling fluids when formed as oil-based drilling mud of the W / O type, have a plastic viscosity (PV) in the range of 10 to 70 mPas and a yield point YP of 5 to 60 lb / 100 ft 2 , each determined at 50 0 C, on.
  • PV plastic viscosity
  • the kinematic viscosity of the oil phase measured according to Ubbelohde at 20 0 C should preferably be at most 12 mm 2 / sec.
  • the aqueous phase of the compositions according to the invention preferably has a pH in the range from 7.5 to 12, preferably from 7.5 to 11 and in particular from 8 to 10.
  • the composition used as the drilling fluid preferably comprises aqueous salt solutions, preferably saturated salt solutions, it being possible to use as salts all alkali metal or alkaline earth halides known to the person skilled in the art.
  • suitable salts are, in particular, KCl, NaCl, LiCl, KBr, NaBr, LiBr, CaCl 2 , and MgCl 2 , among which CaCl 2 , NaCl and KCl or mixtures of these salts are particularly preferred.
  • additives which may be present in the composition used as drilling mud according to component IV) are, in particular, additives selected from the group consisting of surfactants as admixing component for the crosslinked glycerol or oligoglycerol ester, weighting agents, fluid loss additives, pH modifiers, other viscosity modifying additives, wetting agents, salts, biocides, agents for inhibiting unwanted water exchange between drilled formations - e.g. B water swellable clays and / or salt layers - and the z. Water-based rinsing liquid, wetting agents for better coating of the emulsified oil phase on solid surfaces, z. B. to improve the lubricity, but also to improve the oleophilic closure exposed rock formations, or rock surfaces, corrosion inhibitors, alkali reserves and emulsifiers into consideration.
  • surfactants as admixing component for the crosslinked glycerol or oligoglycerol ester
  • weighting agents fluid loss additive
  • the additives may be water-soluble, oil-soluble and / or water or oil-dispersible.
  • anionic, nonionic zwitterionic or cationic surfactants can be used. However, preferred are the nonionic and anionic surfactants.
  • anionic surfactants are soaps, alkyl benzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfonates, glycerol ether sulfonates, methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, fatty acid ether sulfates, mixed hydroxy ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether ) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotrig
  • nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol glycol polyethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty alcohol polyglycol ethers, alkoxylated triglycerides, mixed ethers or mixed formals, optionally partially oxidized alk (en) yloligoglycosides or glucuronic acid derivatives, fatty acid N-glycerides. alkyl glucamides, polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides.
  • nonionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution.
  • the surfactants are an optional ingredient in the additives. They are preferably used in amounts of 0.01 to 2 wt .-%, in particular from 0.1 to 1.5 wt .-% and preferably from 0.2 to 0.5 wt .-% used, each based on the total water-in-oil emulsion used.
  • Suitable emulsifiers are preferably nonionic emulsifiers, which in particular are assigned to one of the following classes of substances: (oligo) alkoxylates, in particular lower alkoxylates, where corresponding ethoxylates and / or propoxylates are of particular importance - containing lipophilic radicals and for alkoxylation capable of basic molecules of natural and / or synthetic origin.
  • Alkoxylates of the type indicated are known per se as non-ionic emulsifiers, ie with terminal free hydroxyl group on the alkoxy latrest, but the corresponding compounds may also be end-capped, for example by esterification and / or etherification.
  • nonionic emulsifiers for the purposes of the invention are partial esters and / or partial ethers of polyfunctional alcohols having in particular 2 to 6 C atoms and 2 to 6 OH groups and / or their oligomers with acids and / or alcohols containing lipophilic radicals .
  • compounds of this type which additionally contain (oligo) -alkoxy radicals and in particular corresponding oligo-ethoxy radicals in their molecular structure.
  • the polyfunctional alcohols having 2 to 6 OH groups in the base molecule or the oligomers derived therefrom may in particular be diols and / or triols or their oligomerization products, whereby the glycol and the glycerol or their oligomers may be of particular importance.
  • the range of partial ethers of polyfunctional alcohols also includes known nonionic emulsifiers of the type of ethylene oxide / propylene oxide / butylene oxide block polymers.
  • Another example of corresponding emulsifier components are alkyl (poly) glycosides of long-chain alcohols and also the already mentioned fatty alcohols of natural and / or synthetic origin or alkylolamides, amine oxides and lecithins.
  • Emulsifier components in the sense of the invention may be of particular interest, inter alia, because this is an emulsifier class of particularly pronounced eco-compatibility.
  • partial esters and / or partial ethers of polyhydric alcohols are in particular the corresponding partial esters with fatty acids, for example of the type of glycerol mono- and / or diesters, glycol monoesters, corresponding partial esters of oligomerized polyhydric alcohols, sorbitan partial esters and the like, and corresponding compounds with ether groups.
  • organic polymer compounds of natural and / or synthetic origin may be of considerable importance in this context.
  • starch or chemically modified starches cellulose derivatives such as carboxymethylcellulose, guar gum, synthangum or purely synthetic water-soluble and / or water-dispersible polymer compounds, in particular of the type of high molecular weight polyacrylamide compounds with or without anionic or cationic modification.
  • Thinner for viscosity regulation The so-called diluents can be of organic or inorganic nature, examples of organic thinners are tannins and / or quebracho extract. Further examples of these are lignite and lignite derivatives, in particular lignosulfonates.
  • fluid-loss additive is in particular organophilic lignite
  • preferred pH modifiers for example, EP 0 382 701 Al
  • EP 0 382 701 Al can be removed.
  • the invention described in EP 0 382 701 A1 is based on the recognition that additives should be used in ester-based drilling flushes of the water-in-oil type, which ensure that the rheological properties of the drilling fluid do not even then change when released by partial ester hydrolysis increasing amounts of free carboxylic acids. If possible, these free carboxylic acids should be converted into compounds which have stabilizing and emulsifying properties.
  • EP 0 382 701 A1 proposes to add alkaline amines with high oleophilicity and the lowest possible water solubility which are able to form salts with the free acids.
  • Typical examples of such amine compounds are primary, secondary and / or tertiary amines, which are predominantly water-insoluble and which moreover can be at least partially alkoxylated and / or substituted by hydroxyl groups.
  • Further examples include aminoamides and / or heterocycles containing nitrogen as the ring atom.
  • Suitable examples are basic amines which have at least one long-chain hydrocarbon radical having 8 to 36 carbon atoms, preferably having 10 to 24 carbon atoms, where these hydrocarbon radicals can also be monounsaturated or polyunsaturated.
  • component IV) preferably a weighting agent, such as BaSO 4 , wherein in the case of a low added composition, the component IV) is preferably in an amount of up to 20 wt .-% is used. For more heavily weighted compositions, the component IV) is preferably used in an amount of 20 to 50 wt .-%, while in heavily weighted compositions 50 to 70 wt .-% of component IV) can be used.
  • a weighting agent such as BaSO 4
  • the composition if it is present as a water-in-oil emulsion, is a nanoemulsion or a microemulsion which preferably contains water droplets or drops of an aqueous phase having a droplet size of less than 1000 .mu.m, preferably a droplet size in a range from 5 nm to 1000 ⁇ m, more preferably with a drop size in a range from 10 nm to 850 ⁇ m, even more preferably with a drop size in a range from 20 nm to 700 ⁇ m, even more preferably with one drop size Drop size in a range of 50 nm to 500 microns includes.
  • microemulsion and sicone emulsion are empirically defined emulsions which contain drops in the micrometer or nanometer range, whereby there can be some distinction between these two ranges and thus also between these two terms.
  • microemulsions are preferably understood to mean those emulsions which form spontaneously with a combination of the emulsion components, whereas the formation of nanoemulsions usually involves the supply of energy, for example in the form of homogenization. especially in the form of high-pressure homogenization.
  • a water-in-oil emulsion as a drilling fluid composition, it may be prepared by any method known to those skilled in the art for making such a water-in-oil emulsion.
  • a water-in-oil emulsion it may be prepared by any method known to those skilled in the art for making such a water-in-oil emulsion.
  • first to prepare the base emulsion from the organic oil phase as the continuous phase and the water droplets emulsified therein and only then to prepare the starting n-nonyl ester and optionally the further additives. To add.
  • this is an aqueous solution or an oil-in-water emulsion.
  • composition is particularly preferred that the composition
  • organic oil phase aqueous phase and other additives
  • those organic oil phases, aqueous phases and other additives are preferred already mentioned above in connection with the water-in-oil emulsion.
  • an oil-in-water emulsion as a drilling mud composition it can be prepared by any method known to those skilled in the art for making such an oil in water emulsion.
  • this comprises the method steps:
  • composition according to the invention in particular the composition according to the invention in the form of a water-in-oil
  • Emulsion an aqueous solution or an oil-in-water emulsion
  • step (cc3) introducing, preferably circulating, the composition provided in step ( ⁇ l) at least partially into or into the wellbore;
  • composition of the invention thus acts as a drilling fluid when drilling holes in the ground, preferably when drilling oil or natural gas.
  • composition used as a drilling fluid in particular the composition used as drilling fluid in the form of a water-in-oil emulsion, an aqueous solution or an oil-in-water emulsion;
  • a contribution to the solution of the objects mentioned at the outset is also provided by a cleaning agent and a drilling mud, preferably a drilling mud in the form the above-described water-in-oil emulsion or the above-described oil-in-water emulsion.
  • n-nonanol prepared analogously to Example 1
  • 409 g of technical stearic acid EDENOR STI
  • 0.38 g of tin (II) oxalate Fluka
  • PET SP04 polyethylene terephthalate
  • the mixing wall temperature was 40 0 C.
  • 0.5 wt .-% of n-nonyl ester prepared in Example 2 From added as release agents.
  • the material was granulated on a granulator (ZSK 26Mcc) with a screw conveyor.
  • thermoplastic composition For the production of moldings from the thermoplastic composition, a fully hydraulic injection molding machine with a hydraulic clamping unit type Battenfeld HM800 / 210 was used. The maximum closing force is 800 kN, the screw diameter is 25 mm. As a trial tool a tool with a tapered, rectangular core was used. To determine the demolding force, a load cell with a maximum measuring range of 2 kN was attached to the ejector rod. The pre-drying of the molding compound was carried out at about 225 ° C for about 4 hours. A significantly improved demolding with respect to a mold release agent-free molding composition was observed with the thermoplastic composition according to the invention.
  • a polyol mixture for a standard polyurethane hot melt adhesive QR 6202, Henkel
  • a hot melt adhesive was prepared.
  • 5% by weight of the n-nonyl ester prepared in Example 2 was added.
  • Ci 2 H 26 (mixture of isomers), 10 g of nitrobenzenesulfonate sodium, 5 g of tetrasodium salt of ethylenediaminetetraacetic acid, 100 g of urea, 25 g of sodium bicarbonate, 100 g of D-Ll, 20 g of Fluorescent Brightener CI. 230 submitted. 5 g of the n-nonyl ester obtained in Example 1 were added as a defoamer and stirred for 60 seconds with a high-speed stirrer at 2000 rpm. EXAMPLE 10: Preparation of a cosmetic formulation
  • composition thus obtained was 5 wt .-% of im
  • a conventional lime mud was prepared from 7.6 g prehydrated bentonite, 1.15 g ferrochromolignosulfonate, 2.3 g slaked lime, 0.38 g starch and 0.76 g NaOH. 5% by weight of the n-nonyl ester obtained in Example 1 were added to this lime rinse.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Animal Behavior & Ethology (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Epidemiology (AREA)
  • Birds (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Emergency Medicine (AREA)
  • Dermatology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Cosmetics (AREA)
  • Detergent Compositions (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un procédé de production d'une composition organique comprenant un composant fonctionnel choisi dans le groupe formé par un polymère thermoplastique, une enzyme, un agent de durcissement, une paraffine, une huile, un colorant et une substance de soin pour les cheveux ou la peau. Le procédé comprend les étapes qui consistent i) à préparer ia) un n-nonylester en tant qu'adjuvant, obtenu par réaction d'un composant n-nonylalcool avec un autre composant qui peut réagir avec le composant n-nonylalcool de manière à former un n-nonylester, ib) les composants fonctionnels et éventuellement ic) au moins un autre additif; puis ii) à mélanger le n-nonylester, les composants fonctionnels et éventuellement le ou les autres additifs. L'invention concerne également un procédé de production d'un corps moulé, un procédé de production d'un produit d'emballage, l'utilisation d'au moins un n-nonylester, l'utilisation d'un corps moulé, un procédé de nettoyage des surfaces de trous de forage, de dispositifs de forage ou de déblais de forage, des procédés pour pratiquer un trou de forage et des procédés de production d'une huile ou d'un gaz.
EP08852584A 2007-11-20 2008-11-20 Procédé de production d'une composition organique comprenant un n-nonylester Withdrawn EP2212376A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102007055595A DE102007055595A1 (de) 2007-11-20 2007-11-20 Verfahren zur Herstellung einer organischen Zusammensetzung beinhaltend einen N-Nonylester
DE200810009369 DE102008009369A1 (de) 2008-02-14 2008-02-14 Verfahren zur Herstellung einer organischen Zusammensetzung beinhaltend einen N-Nonylester
PCT/EP2008/065933 WO2009065903A2 (fr) 2007-11-20 2008-11-20 Procédé de production d'une composition organique comprenant un n-nonylester

Publications (1)

Publication Number Publication Date
EP2212376A2 true EP2212376A2 (fr) 2010-08-04

Family

ID=40568541

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08852584A Withdrawn EP2212376A2 (fr) 2007-11-20 2008-11-20 Procédé de production d'une composition organique comprenant un n-nonylester

Country Status (3)

Country Link
US (1) US20100294501A1 (fr)
EP (1) EP2212376A2 (fr)
WO (1) WO2009065903A2 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2053111B1 (fr) 2007-10-24 2016-12-07 Emery Oleochemicals GmbH Composition de forage, procédé de préparation et ses applications
FR2928934B1 (fr) 2008-03-20 2011-08-05 Total France Lubrifiant marin
DE102008026263A1 (de) * 2008-06-02 2009-12-03 Emery Oleochemicals Gmbh Antibeschlagmittel auf Basis von Polyglycerin und nativen Ölen
DE102008044706A1 (de) * 2008-08-28 2010-03-04 Emery Oleochemicals Gmbh Viskositätsreduzierer für Polyetherpolyole
US8770287B2 (en) * 2012-10-16 2014-07-08 Halliburton Energy Services, Inc. Defoaming agent compositions and methods of making and using same
CA2924253C (fr) 2013-10-31 2018-06-19 Amril Ag Fluides de traitement de puits respectueux de l'environnement comprenant un ester
JP6447983B2 (ja) 2014-07-08 2019-01-09 エメリー オレオケミカルズ ゲーエムベーハー ３ｄ印刷デバイス用の焼結可能な供給原料
MX2017007238A (es) 2015-01-07 2018-02-16 Emery Oleochemicals Gmbh Nuevos aditivos para aplicaciones en campos petroleros e industrial.
EP3242919B1 (fr) 2015-01-07 2019-03-13 Emery Oleochemicals GmbH Acides carboxyliques d'éther hydrophiles en tant que lubrifiant pour systèmes de forage à base de sel
US10876026B2 (en) * 2017-05-02 2020-12-29 M-I L.L.C. Wellbore fluids and methods of use thereof

Family Cites Families (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2813113A (en) * 1953-05-07 1957-11-12 Emery Industries Inc Method of making azelaic acid
EP0002329A1 (fr) * 1977-11-30 1979-06-13 Imperial Chemical Industries Plc Compositions du chlorure de polyvinyl plastifié
US4612340A (en) * 1983-03-09 1986-09-16 Yoshinori Ohachi Medical device
JPS62199641A (ja) * 1986-02-26 1987-09-03 Chisso Corp ポリ塩化ビニル樹脂組成物
JPS63120254A (ja) * 1986-11-10 1988-05-24 Terumo Corp 血液保存容器
JPH0218496A (ja) * 1988-07-06 1990-01-22 New Japan Chem Co Ltd 水溶性金属加工油剤用基剤
USRE36066E (en) * 1988-12-19 1999-01-26 Henkel Kgaa Use of selected ester oils in drilling fluids and muds
DE4010606A1 (de) * 1990-04-02 1991-10-10 Henkel Kgaa Verwendung von hydrophobierten hydrotalciten als katalysatoren fuer die ethoxylierung bzw. propoxylierung
DE4018228A1 (de) * 1990-06-07 1991-12-12 Henkel Kgaa Fliessfaehige bohrlochbehandlungsmittel auf basis von kohlensaeurediestern
EP0603172B1 (fr) * 1991-09-09 1995-06-21 Henkel Corporation Procede catalyse utilise pour oxyder des ozonides d'insatures afin de produire des acides carboxyliques
DE4204035A1 (de) * 1992-02-12 1993-08-19 Cognis Bio Umwelt Verbessertes verfahren zur trocknung von wertstoffen fuer wasch- und reinigungsmittel mit ueberhitztem wasserdampf
US6498261B1 (en) * 1995-06-07 2002-12-24 Cognis Corporation Process for improving color and color stability of oleic acid
JP2000001681A (ja) * 1998-06-12 2000-01-07 New Japan Chem Co Ltd 潤滑油基油
DE10104815A1 (de) * 2001-02-01 2002-08-08 Cognis Deutschland Gmbh Verfahren zur Herstellung von epoxidierten Glyceridacetaten
CA2455191C (fr) * 2001-09-26 2011-03-15 Oxeno Olefinchemie Gmbh Melanges de phthalate d'alkyl avec controle de la viscosite
DE10212528A1 (de) * 2002-03-21 2003-10-02 Cognis Deutschland Gmbh Ölphasen für kosmetische Mittel
ATE316114T1 (de) * 2002-04-05 2006-02-15 Dsm Ip Assets Bv Thermoplastische zusammensetzung enthaltend aromatische polycarbonate und/oder polyester mit verbessertem formtrennverhalten
CA2447306C (fr) * 2002-11-01 2009-05-12 Ecl Group Of Companies Ltd. Fluide de packer
DE10321100A1 (de) * 2003-05-09 2004-12-02 Basf Ag Kosmetische Zusammensetzungen enthaltend Cyclohexanpolycarbonsäurederivate
DE102004009895B3 (de) * 2004-02-26 2005-07-21 Cognis Deutschland Gmbh & Co. Kg Gleitmittelkombinationen
DE102004029732A1 (de) * 2004-06-21 2006-01-19 Basf Ag Hilfsmittel enthaltend Cyclohexanpolycarbonsäurederivate
DE102004038980A1 (de) * 2004-08-10 2006-02-23 Cognis Deutschland Gmbh & Co. Kg Antibeschlagmittel für Kunststoffe
EP1881025B1 (fr) * 2006-07-20 2010-02-17 Cognis Oleochemicals GmbH Utilisation d esters d acides gras de polyethylenglycol ent tant que lubrifiant pour plastiques thermoplastiques
DE102007027371A1 (de) * 2007-06-11 2008-12-18 Cognis Oleochemicals Gmbh Verfahren zur Herstellung einer Verbindung aufweisend mindestens eine Ester-Gruppe
DE102007043753A1 (de) * 2007-09-13 2009-03-19 Cognis Oleochemicals Gmbh Eine thermoplastische Zusammensetzung beinhaltend ein Formtrennmittel basierend auf einem Ester aus Di- oder Polyglycerinen und mindestens einer Carbonsäure
DE102007043755A1 (de) * 2007-09-13 2009-03-19 Cognis Oleochemicals Gmbh Eine thermoplastische Zusammensetzung beinhaltend ein Formtrennmittel basierend auf gehärteten vegetabilen Estern
EP2036963A1 (fr) * 2007-09-14 2009-03-18 Cognis Oleochemicals GmbH Lubrifiants pour fluides de forage
EP2036962A1 (fr) * 2007-09-14 2009-03-18 Cognis Oleochemicals GmbH Additifs pour fluides de forage à base d'eau
EP2036964A1 (fr) * 2007-09-14 2009-03-18 Cognis Oleochemicals GmbH Epaissisant pour fluides de forage à base d'huile
EP2053111B1 (fr) * 2007-10-24 2016-12-07 Emery Oleochemicals GmbH Composition de forage, procédé de préparation et ses applications
WO2009065906A2 (fr) * 2007-11-20 2009-05-28 Cognis Oleochemicals Gmbh Procédé de fabrication d'une composition organique contenant un n-nonyléther

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2009065903A2 *

Also Published As

Publication number Publication date
WO2009065903A3 (fr) 2010-02-18
US20100294501A1 (en) 2010-11-25
WO2009065903A2 (fr) 2009-05-28

Similar Documents

Publication Publication Date Title
EP2215200A2 (fr) Procédé de fabrication d'une composition organique contenant un n-nonyléther
EP2212376A2 (fr) Procédé de production d'une composition organique comprenant un n-nonylester
EP0935700B1 (fr) Utilisation de produits d'alcoxylation biodegradables pour le nettoyage de trous de forage, d'equipements de forage ou de deblais de forage
EP2411483A2 (fr) Composition nettoyante à base d'une émulsion pour des applications sur les champs pétroliers
EP0386636B1 (fr) Ester d'acides carboxyliques à chaîne moyenne, comme composants de la phase huile d'émulsion de forage inverses
EP2201081B1 (fr) Additifs pour fluides de forage à base d'eau
EP0386638B2 (fr) Utilisation d'huiles d'esters sélectionnées, d'acides carboxyliques inférieurs dans des fluides de forage
EP0374671B1 (fr) Utilisation d'huiles d'esters sélectionnées, dans les fluides de forage, en particulier pour l'exploitation off-shore du pétrole ou du gaz
WO2009098308A1 (fr) Esters de glycérine ou d'oligoglycérine réticulés et leur utilisation comme additifs dans des agents de nettoyage de forage
EP0391252B1 (fr) Alcools oléophiles comme composants d'émulsions de forage inverses
DE102009060851A1 (de) Esterherstellung mit Nachbehandlung
EP0374672B1 (fr) Utilisation d'esters gras sélectionnés dans les fluides de forage, en particulier pour l'exploitation off-shore du pétrole ou du gaz naturel
EP0472558B1 (fr) Utilisation d'alcools oleophiles selectionnes dans des fluides de lavage de puits a base d'eau du type d'une emulsion d'huile dans de l'eau, et fluides de lavage de puits moins nuisibles pour l'environnement
DE102009060881A1 (de) Wärmetauscher in Verfahren und Vorrichtung zur Herstellung eines Esters
EP2036963A1 (fr) Lubrifiants pour fluides de forage
EP2201083A1 (fr) Épaississants pour fluides de forage à base d'huile
DE102009060813A1 (de) Katalysatorsystem zur Herstellung eines Esters und diesen Ester einsetzende Verfahren
EP0512501B1 (fr) Utilisation d'acétales
WO1998018882A1 (fr) Procede pour faciliter l'evacuation de fluides actifs a base d'emulsions inversees eau dans l'huile
WO2004103542A1 (fr) Melange comprenant un tensio-actif et un co-tensio-actif
DE102007043753A1 (de) Eine thermoplastische Zusammensetzung beinhaltend ein Formtrennmittel basierend auf einem Ester aus Di- oder Polyglycerinen und mindestens einer Carbonsäure
DE102007055595A1 (de) Verfahren zur Herstellung einer organischen Zusammensetzung beinhaltend einen N-Nonylester
EP0370273B2 (fr) Ethoxylates d'alcools gras à caractéristiques modifiées à basse température
JP2010528827A (ja) 表面活性成分組成物
DE102007055594A1 (de) Verfahren zur Herstellung einer organischen Zusammensetzung beinhaltend einen N-Nonylether

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: 20100514

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA MK RS

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20110217

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

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20120601