DE10361466A1 - Neutralizing agent for gas odorants - Google Patents

Abstract

Described are neutralizing agents for the odorless neutralization of at least one acrylic acid C ₁ -C ₆ alkylester or at least one methacrylic acid C ₁ -C ₆ alkylester comprising gas odorant, the use of the neutralizing agent according to the invention for the neutralization of such odorants and a method for neutralizing these odorants. A neutralizing agent according to the invention contains:
a) 15 to 50 wt .-% of one or more emulsifiers
b) 15 to 55 wt .-% of one or more water-miscible organic solubilizers
c) 3 to 25 wt .-% of a fragrance mixture from
a. three or more different individual fragrances or
b. one or more essential oils and two or more different individual fragrances and
d) from 5 to 35% by weight of water,
wherein the sum of the weight proportions of the components a), b), c) and d) is at least 70 wt .-%.

Description

The present invention relates to neutralizing agents for odor neutralization of at least one acrylic acid C ₁ -C ₆ alkyl ester or at least one methacrylic acid C ₁ -C ₆ alkylester comprising gas odorant, the use of the neutralizing agent according to the invention for the neutralization of such odorants and a method for neutralizing them odorants.

Under Gas odorization is the addition of odor-intensive, as warning or alarm materials active substances (gas odorants or, in short, odorants), to otherwise odorless gases.

Out security Natural gas is odorized by the addition of odorous substances. For example, in Germany it is required that all gases, which do not possess a sufficient odor and in public Gas supply to be distributed, odorized. These odorizers are still in great dilution perceptible and call because of their exceptionally unpleasant odor as desired, an alarm association in humans. So far, mainly tetrahydrothiophene has been used for odorization used by natural gas.

In EP 1 109 881 describes the odorization of natural gas with sulfur-free odorants. Natural gas, which consists mainly of methane (typical methane contents are in the range 50 to 99 wt .-%) is odorized with an odorant based on acrylic acid C ₁ -C ₁₂ alkyl esters. Under the name Gasodor ^TM S-Free ^™ , the company Symrise GmbH & Co. KG markets a gas odorizer which comprises about 60% by weight of ethyl acrylate, 37% by weight of methyl acrylate and 3% by weight of 2,3-ethylmethylpyrazine consists.

The previously available on the market Neutralizing agents act primarily against sulfur-containing odorants, especially against tetrahydrothiophene. There are, for example the product "O-Scent THT ", according to manufacturer statement (WVT Industries) eliminated by oxidation odors.

The previously known neutralizing agents show no satisfactory action against odorants based on acrylic acid C ₁ -C ₆ -alkyl esters and / or methacrylic acid-C ₁ -C ₆ -alkyl esters.

It is now the object for odorants based on acrylic acid C ₁ -C ₆ -alkyl esters and / or methacrylic acid C ₁ -C ₆ -alkyl esters, for example for the sulfur-free odorant Gasodor ^TM S-Free ^TM , to provide an odor neutralizing agent ,

The neutralizing agent should be used in particular if, in the event of unintentional release of small amounts of liquid, an odorant covering of the strong odor of the odorizing agent on the basis of acrylic acid C ₁ -C ₆ -alkyl esters and / or methacrylic acid C ₁ -C ₆ -alkyl esters is effected should.

• a) 15 bis 50 Gew.-% eines oder mehrerer Emulgatoren
• b) 15 bis 55 Gew.-% eines oder mehrerer mit Wasser mischbarer organischer Lösungsvermittler
• c) 3 bis 25 Gew.-% einer Riechstoffmischung aus (i) drei oder mehr unterschiedlichen Einzelriechstoffen oder (ii) einem oder mehreren ätherischen Ölen sowie zwei oder mehr unterschiedlichen Einzelriechstoffen und
• d) 5 bis 35 Gew.-% Wasser,

wobei die Summe der Gewichtsanteile der Komponenten a), b), c) und d) zumindest 70 Gew.-%, vorzugsweise zumindest 90 Gew.-%, weiter vorzugsweise zumindest 99 Gew.-% und noch weiter vorzugsweise 100 Gew.-% beträgt. Sämtliche Gewichtsprozentangaben sind dabei auf die Gesamtmasse des Neutralisationsmittels bezogen.The primary object of the present invention are neutralizing agents for the odorous (complete or almost complete) neutralization of a gas odorant comprising at least one acrylic acid C ₁ -C ₆ -alkyl ester or at least one methacrylic acid C ₁ -C ₆ -alkyl ester, comprising:

• a) 15 to 50 wt .-% of one or more emulsifiers
• b) 15 to 55 wt .-% of one or more water-miscible organic solubilizers
• c) 3 to 25 wt .-% of a fragrance mixture of (i) three or more different individual fragrances or (ii) one or more essential oils and two or more different individual fragrances and
• d) from 5 to 35% by weight of water,

wherein the sum of the weight proportions of components a), b), c) and d) at least 70 wt .-%, preferably at least 90 wt .-%, more preferably at least 99 wt .-% and still more preferably 100 wt .-% is. All weight percentages are based on the total mass of the neutralizing agent.

Surprisingly, the neutralizing agents according to the invention are suitable for completely odorizing gas odorizers based on acrylic acid C ₁ -C ₆ -alkyl esters or methacrylic acid-C ₁ -C ₆ -alkyl esters or almost completely neutralize.

• a) 15 bis 50 Gew.-%, bevorzugt 25 bis 40 Gew.-%, des Emulgators oder der Emulgatoren und/oder
• b) 20 bis 50 Gew.-%, bevorzugt 30 bis 45 Gew.-%, des Lösungsvermittlers oder der Lösungsvermittler und/oder
• c) 5 bis 20 Gew.-%, bevorzugt 7 bis 15 Gew.-%, der Riechstoffmischung, und/oder
• d) 5 bis 25 Gew.-%, bevorzugt 10 bis 25 Gew.-%, Wasser.

Preferred neutralizing agents according to the invention comprise:

• a) 15 to 50 wt .-%, preferably 25 to 40 wt .-%, of the emulsifier or emulsifiers and / or
• b) 20 to 50 wt .-%, preferably 30 to 45 wt .-%, of the solubilizer or the solubilizer and / or
• c) 5 to 20 wt .-%, preferably 7 to 15 wt .-%, of the perfume mixture, and / or
• d) 5 to 25 wt .-%, preferably 10 to 25 wt .-%, water.

The invention also relates to the use of a neutralizing agent according to the invention or a spray formulation according to the invention (for spray formulation, see below) for odor neutralization of a gas odoriser comprising at least one acrylic acid C ₁ -C ₆ alkyl ester or at least one methacrylic acid C ₁ -C ₆ alkyl ester.

The invention further relates to a process for the odor neutralization of a gas odorizer comprising at least one acrylic acid C ₁ -C ₆ -alkyl ester or at least one methacrylic acid C ₁ -C ₆ -alkylester, comprising the following step: contacting the gasodoriser with a neutralizing amount of a novel inventive Neutralizing agent or a spray formulation according to the invention.

Of the Term "neutralization" is - as is from the foregoing already results - not in the present text equate to a neutral pH after treatment with the neutralizing agent according to the invention, but with the odor neutralization (covering, masking) of the Odorizer by the neutralizing agent, wherein a full or almost complete odor neutralization is effected.

at the emulsifier as component a) of the neutralizing agent according to the invention it is preferably a nonionic emulsifier, thereby again preferred are ethoxylates. These are the ethoxylates to interface-active, nonionic surfactants which have emulsifying activity. Ethoxylates are Ether, usually by (poly) addition of ethylene oxide to other alcohols and therefore as (poly) ethers or (poly) ethylene glycols are. The degree of ethoxylation is generally determined by the molar equivalents of ethylene oxide per mole of substrate (EO). Depending on the type and Structure of the hydrophobic end group is the degree of ethoxylation usually in the range of 3 to 60 EO. These emulsifiers are commercial available and well available.

Preferably the emulsifier is chosen from the group of alkylphenol ethoxylates or fatty alcohol ethoxylates (Fatty alcohol polyglycol ether). It can also be mixtures of the above Emulsifiers are used, preferred are fatty alcohol ethoxylates.

at the alkylphenol ethoxylates are octyl, decyl and nonylphenol ethoxylates preferably, in addition Tributylphenolethoxylate (here preferably tri-sec-butylphenolpolyglykolether). Octyl, decyl and nonylphenol ethoxylates can be straight chain or branched-chain Alkylphenolethoxylate act, mostly acts branched-chain alkylphenolethoxylates, such as in the case of isononylphenol ethoxylate. Often, mixtures of alkylphenol ethoxylates used, for example, by ethoxylation of nonylphenol technical quality technical nonylphenol contains about 85% of para-nonylphenol, contains about 10% ortho-nonylphenol and about 4% decylphenol.

Of the Degree of ethoxylation in the alkylphenol ethoxylates is preferably in the range of 5 to 16 EO, preferably in the range of 8 to 13 EO.

In the case of the fatty alcohol ethoxylates, the ethoxylates of the C ₁₂ - to C ₁₈ -fatty alcohols are advantageous, preferably those of the C ₁₂ - to C ₁₅ -fatty alcohols. The fatty alcohols are usually linear or simply branched. Mixtures of Fet taloholethoxylaten can be used, such as mixtures of ethoxylated C ₁₂ - to C ₁₅ fatty alcohols (CAS number 68131-39-5, eg INCI name: C12-C15 Pareth-12) or ethoxylated (hydrogenated) Rinzinusöl (hydrogenated) castor oil, CAS No. 61788-85-0)].

Of the Degree of ethoxylation in the fatty alcohol ethoxylates is preferably in the range of 5 to 60 EO, preferably in the range of 10 to 40 EO.

The emulsifier may optionally contain a minor amount (typically 5 to 20% by weight) of a diluent, such as water or 1,2-propanediol. This optionally in Emulga In the calculation of the proportions by weight in the neutralizing agent according to the invention, the diluent contained in the neutralizing agent is not considered to be a constituent of the emulsifier.

at the solubilizer as component b) of the neutralizing agent according to the invention it is a water-miscible organic solvent, preferably, the solubilizer with water in every ratio miscible.

preferred solubilizers are diethylene glycol derivatives, in particular diethylene glycol monoalkyl ethers, wherein the alkyl radical again preferably 1 to 6, preferably 1 to 4, carbon atoms. Advantageous solubilizers are diethylene glycol monomethyl ether [2- (2-methoxyethoxy) ethanol], diethylene glycol monoethyl ether [2- (2-ethoxyethoxy) ethanol] and diethylene glycol monobutyl ether [2- (2-butoxyethoxy) ethanol], very particular preference is given to diethylene glycol monomethyl ether.

The The perfume mixture to be used is preferably one or more Contain terpenes.

It is advantageous, at least one of the three or more fragrances the alternative (i) as component c) of the neutralizing agent according to the invention To be used fragrance mixture from the group of terpenes choose.

Prefers comprises component c) according to alternative (ii) at least one essential oil, preferably contains one or more terpenes.

The perfume mixture preferably comprises at least one perfume selected from
the group of the following essential oils: basil oil, bergamot oil, lemon oil, lavandin oil, lemongrass oil, lime oil, litsea cubeba oil, orange oil, patchouli oil, petitgrain oil, tangerine oil, cinnamon oil; or
the group of the following individual odoriferous substances: aniseed alcohol, citral, coumarin, cuminaldehyde, allyl cyclohexyloxyacetate, gamma-decalactone, n-decanal, n-dodecanal, ethyl-2-methylpentanoate, eucalyptol, cis-3-hexenylacetate, isoamylacetate, isobornylacetate, limonene, linalool, Menthol, 2-methyldecanal, 2-methylundecanal, alpha-methylcinnamaldehyde, phenylethyl alcohol, para-tolualdehyde, n-undecanal.

Include particularly advantageous fragrance mixtures
at least one essential oil from the group bergamot oil, lemon oil, lavandin oil, lemongrass oil, lime oil, patchouli oil, petitgrain oil, tangerine oil; and or
at least one compound from the group of individual fragrances comprising citral, eucalyptol, isobornyl acetate, limonene, linalool, menthol, 2-methyl undecanal, phenylethyl alcohol.

preferred Components c) comprise according to alternative (ii) at least one essential oil and additionally at least two, more preferably at least three or four, individual fragrances.

In Alternative (ii) is the weight ratio of the sum of the essential oils to the Sum of the individual fragrances preferably in the range 3: 1 to 1 : 15, preferably in the range 1: 1 to 1:10, particularly preferred in the range 1: 2 to 1: 7.

at the water as component d) of the neutralizing agent according to the invention it may be demineralized or distilled water, usually enough drinking water quality out.

The neutralizing agents according to the invention is preferably used in the form of a spray formulation according to the invention (i.e. with propellant) or in spray form (without additional propellant) by means of Fine sprayer with brought into contact with the neutralizing odorant. To that neutralizing agents according to the invention aerosol, this may be used together with a propellant, such as butane, are placed in a spray can (spray formulation according to the invention). Alternatively and preferred, however, is the propellant-free use as a pump spray. In the case of a spray, it is beneficial if the Viscosity, measured at 20 ° C according to the ball drop method, the neutralizing agent according to the invention at the most 75 mPas, preferably at most 50 mPas, more preferably at most 40 mPas.

Entspechend In the aspect discussed above, the present invention relates also a spray formulation comprising a neutralizing agent according to the invention and a propellant.

It is recommended that the weight ratio of inventive neutralizing agent to the total amount of acrylic acid-C ₁ -C ₆ -alkyl esters and methacrylic acid-C ₁ -C ₆ -alkyl esters to be neutralized in Odorant in the range 1: 1 to 10: 1 to choose. Advantageously, the neutralizing agent according to the invention is used in excess, preferably the ratio is in the range from 1: 1 to 7: 1, more preferably in the range from 2: 1 to 5: 1.

The acrylic acid C ₁ -C ₆ -alkyl esters to be neutralized may be, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, iso-butyl acrylate, acrylic acid tert. butyl ester, acrylic acid-n-pentyl ester, acrylic acid iso-pentyl ester or acrylic acid n-hexyl ester act, preferred are acrylic acid C ₁ -C ₄ alkyl esters, in particular methyl acrylate and ethyl acrylate.

The methacrylic acid-C ₁ -C ₆ -alkyl esters to be neutralized may be, for example, methyl methacrylate, ethyl methacryloate, n-propyl methacryloate, isopropyl methacrylate, n-butyl methacyrylate, isobutyl methacrylate, methacrylic acid tert. butyl ester, methacrylic acid n-pentyl ester, methacryloyl-iso-pentyl ester or methacryloyl-n-hexyl ester act.

Particularly effectively neutralize odorant can be based on Acyrlsäure-C ₁ -C ₆ alkyl esters and / or methacrylic acid-C ₁ -C ₆ alkyl esters, the alkyl esters contain at Acyrlsäure-C1-C ₆ and / or C-Methacyrlsäure C ₁ -C ₆ -alkyl esters of at least 60 wt .-%, preferably one of at least 70 wt .-%, more preferably one of at least 80 wt .-%, most preferably one of at least 90 wt .-%.

to Stability increase included the odorants usually very small amounts of antioxidants, such as tert-butylhydroxytoluene (BHT, Jonol), tert-butylhydroxyanisole and hydroquinone monomethyl ether. The presence of antioxidants showed in own investigations no influence on the effect of the Neutralizing agent.

Further preferred aspects of the present invention will be apparent from the attached Claims.

The following examples illustrate the invention:
Unless otherwise indicated, all data are by weight.

Example 1:

The investigated neutralizing agent comprised 12.5% water, 37.5% diethylene glycol monomethyl ether (component b)) 10% fragrance (component c)) and 40% emulsifier Mulsifan ^® RT 203/80 (Zschimmer & Schwarz GmbH & Co. Chemical factories , ethoxylated C ₁₂ to C ₁₅ fatty alcohols, CAS number 68131-39-5). Mulsifan ^® RT 203/80 consists of 80% ethoxylated C ₁₂ - to C ₁₅ fatty alcohols and 20% water. This results in a total content of water (component d)) of 20.5% and an emulsifier content (component a)) of 32% for the tested neutralizing agent. The fragrances were used in perfumery quality.

at Room temperature (about 20 ° C) were in two separate glasses (300 ml) each 100 mg of an odorant consisting of 59.9 % By weight of ethyl acrylate, 37% by weight of methyl acrylate, 3% by weight of 2,3-ethylmethylpyrazine and 0.1 wt .-% tert-butylhydroxytoluene presented. In the one glass were 300 mg of the neutralizing agent to be tested sprayed (as a pump spray), the other served as a reference. Both glasses were at intervals 10 and 30 minutes of six trained examiners in direct comparison odorily evaluated. The glasses were not covered to prevent the leakage of the odorant in open clear or to simulate odorizing stations.

Rating Scale: 0 = no smell change to 6 = complete olfactory coverage / neutralization; 5 = almost complete olfactory coverage / neutralization.

table Figure 1 shows the results of studies on non-inventive neutralizing agents with essential oils or Single fragrances as component (c), for comparison purposes each used individually:

Table 1

Example 2

The Composition of the neutralizing agent corresponded to that in Example 1, only the composition of component c) were varied. Table 2 shows the results for investigations Neutralizing agents with fragrance mixtures to be used according to the invention as component (c). The implementation and odor assessment was as described in Example 1.

Table 2

Example 3

The Composition of the neutralizing agent corresponded to that in Example 1, only the composition of component c) was varied. Table 3 shows the results to be used according to the invention Fragrance mixtures. The implementation and odor assessment was as described in Example 1.

Table 3

Prefers includes the invention to be used Component c) consequently patchouli oil and limonene and linalool and / or citral.

Example 4

The Composition of the neutralizing agent corresponded to that in Example 1, only the composition of component c) was varied. Table 4 shows the results with fragrance mixtures to be used according to the invention. The implementation and odor assessment was as described in Example 1.

Table 4

The component c) to be used according to the invention therefore particularly preferably comprises patchouli oil, citral, isobornyl acetate, limonene, in this case preferably d-limonene, and linalool.

Claims (12)

Neutralizing agent for odor neutralization of a gas odorizer comprising at least one acrylic acid C ₁ -C ₆ -alkyl ester or at least one methacrylic acid C ₁ -C ₆ -alkyl ester, comprising: a) 15 to 50% by weight of one or more emulsifiers b) 15 to 55% by weight of one or more water-miscible organic solubilizers c) 3 to 25% by weight of a fragrance mixture of (i) three or more different individual fragrances or (ii) one or more essential oils and two or more different individual fragrances and d ) 5 to 35 wt .-% water, wherein the sum of the weight fractions of components a), b), c) and d) is at least 70 wt .-%. Neutralizing agent according to claim 1, comprising: a) 15 to 50 wt .-%, preferably 25 to 40 wt .-%, of the emulsifier or the emulsifiers and / or b) 20 to 50% by weight, preferably 30 to 45 wt .-%, of the solubilizer or the solubilizer and / or c) 5 to 20 wt .-%, preferably 7 to 15 wt .-%, of the perfume mixture, and / or d) 5 to 25 wt .-%, preferably 10 to 25 wt .-%, water. Neutralizing agent according to one of the preceding Claims, wherein the emulsifier is a nonionic emulsifier. Neutralizing agent according to one of the preceding Claims, wherein the solubilizer is a water-miscible organic solvent. Neutralizing agent according to one of the preceding Claims, wherein the perfume mixture contains one or more terpenes. Neutralizing agent according to one of the preceding Claims, wherein the fragrance mixture comprises one or more fragrances, the selected are made the group of the following essential oils: basil oil, bergamot oil, lemon oil, lavandin oil, lemongrass oil, lime oil, litsea Cubebaöl, Orange oil, patchouli oil, Petitgrain oil, Tangerineöl, cinnamon or the group of the following individual fragrances: aniseed alcohol, Citral, coumarin, cuminaldehyde, allyl cyclohexyloxyacetate, gamma-decalactone, n-decanal, n-dodecanal, ethyl 2-methyl pentanoate, eucalyptol, cis-3-hexenyl acetate, isoamyl acetate, Isobornyl acetate, limonene, linalool, menthol, 2-methyldecanal, 2-methylundecanal, alpha-methylcinnamaldehyde, Phenylethyl alcohol, para-tolualdehyde, n-undecanal. Neutralizing agent according to one of the preceding Claims, wherein the fragrance mixture comprises one or more fragrances, the selected are made the group of the following essential oils: bergamot oil, lemon oil, lavandin oil, lemongrass oil, lime oil, patchouli oil, petitgrain oil, tangerine oil; and or of the Group of the following individual fragrances: citral, eucalyptol, isobornyl acetate, Limonene, linalool, menthol, 2-methylundecanal, phenylethylalcohol. Spray formulation comprising a neutralizing agent according to one of the preceding claims and a propellant gas. Use of a neutralizing agent according to any one of claims 1-7 or a spray formulation according to claim 8 for the odor neutralization of a gas odorant comprising at least one C ₁ -C ₆ alkyl acrylate or at least one methacrylic acid C ₁ -C ₆ alkyl ester. A process for the odor neutralization of a gas odorant comprising at least one C ₁ -C ₆ alkyl acrylate or at least one methacrylic acid C ₁ -C ₆ alkyl ester, comprising the step of contacting the gas odorizer with a neutralizing agent of a neutralizing agent as claimed in any one of claims 1 -7 or a spray formulation according to claim 8. A fragrance mixture for use in a neutralizing agent according to any one of claims 1-7, comprising: (i) three or more different individual fragrances or (ii) one or more essential oils and two or more different individual fragrances, wherein the one or more essential oils are selected from the group consisting of: bergamot oil, lemon oil, lavandin oil, lemongrass oil, lime oil, patchouli oil , Petitgrain oil and tangerine oil and the individual fragrances are selected from the group consisting of: citral, eucalyptol, isobornyl acetate, limonene, linalool, menthol, 2-methylundecanal and phenylethyl alcohol. A fragrance mixture according to claim 11, wherein Patchouli oil as essential oil and / or limonene and linalool and / or citral used as individual fragrances become.