• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Alkoxylated polycarboxylic acid esters are provided obtainable by first reacting an aromatic polycarboxylic acid containing at least three units of carboxylic acid or anhydrides derived therefrom, preferably an aromatic polycarboxylic acid containing three or four units of carboxylic acid or anhydrides derived from it, more preferably one aromatic polycarboxylic acid containing three units of carboxylic acid or anhydrides derived therefrom, still more preferably trimellitic acid or trimellitic acid anhydride, more preferably trimellitic acid anhydride, with an alcoholic alkoxylate and in a second step reacting the resulting product with an alcohol or an mixture of alcohols, preferably with an alcohol.
    公开号:BR112020000040A2
    申请号:R112020000040-0
    申请日:2018-06-11
    公开日:2020-07-21
    发明作者:Kevin Mutch；Steffen Romanski；Carsten Schaefer；Catherine Breffa；Jan DIEDERICHS；Stephen Norman Batchelor
    申请人:Clariant International Ltd.；
    IPC主号:
    专利说明:

    [001] [001] The present invention relates to the field of esters of alkoxylated aromatic polycarboxylic acids and a method for their preparation. Esters of alkoxylated aromatic polycarboxylic acids can advantageously be used as anti-breakdown agents in washing applications.
    [002] [002] Anti-reposition agents used in laundry detergents help prevent dirt from reinstalling on a fabric after it has been removed during washing. This can, for example, be achieved by dispersing the dirt in the washing liquid.
    [003] [003] Washing soiled fabrics with a laundry detergent composition is essentially a two-step process. In the first stage, the detergent must remove dirt from the fabric and put it in suspension in the washing liquid. In the second stage, the detergent composition must prevent dirt and other insoluble materials from re-depositing on clothing before the fabric is removed from the washing liquid or rinsing liquid. Polymers are known to assist both processes. For example, dirt-release polymers enhance the removal of dirt from the fabric although anti-reposition polymers prevent the dirt removed from re-depositing on the fabric.
    [004] Examples of suitable anti-reposition agents include fatty acid amides, fluorocarbon surfactants, complex phosphate esters, styrene and maleic anhydride copolymers and cellulosic derivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose and the like.
    [005] [005] US 4,240,918 for example, describes polymers having anti-dust and anti-reposition properties, for example hydrophilic polyurethanes, certain copolyesters and mixtures thereof.
    [006] [006] However, many of the known anti-reposition agents have the disadvantage that their performance and bleaching effect in washing or laundry applications are insufficient.
    [007] [007] Therefore, the problem to be solved by the present invention is to provide new anti-reposition agents that perform favorably and lead to enhanced "whiteness" when used in washing or laundry applications.
    [008] [008] Surprisingly it was discovered that this problem can be solved by specific alkoxylated polycarboxylic acid esters obtainable by first reacting an aromatic polycarboxylic acid containing at least three units of carboxylic acid or an anhydride derived from it, with an alcoholic alkoxylate and in a second step by reacting the resulting product with an alcohol or a mixture of alcohols, preferably with an alcohol.
    [009] [009] Consequently, the invention provides specific alkoxylated polycarboxylic acid esters obtainable by first reacting an aromatic polycarboxylic acid containing at least three units of carboxylic acid or an anhydride derived therefrom, preferably an aromatic polycarboxylic acid containing three or four units of carboxylic acid or an anhydride derived from it, more preferably an aromatic polycarboxylic acid containing three units of carboxylic acid or an anhydride derived from it, even more preferably trimellitic acid or trimellitic acid anhydride, more preferably trimellitic acid anhydride, with an alcoholic alkoxylate and in a second step by reacting the resulting product with an alcohol or a mixture of alcohols, preferably with an alcohol.
    [0010] [0010] The specific alkoxylated polycarboxylic acid esters of the invention exhibit favorable performance as anti-reposition agents in washing or laundry applications. They also show favorable performance as dispersants and in washing or laundry applications they lead to enhanced "whiteness". In addition, the alkoxylated polycarboxylic acid esters of the invention exhibit favorable stability and furthermore exhibit favorable biodegradability. Polycarboxylic acid component
    [0011] [0011] The aromatic polycarboxylic acid containing at least three units of carboxylic acid or an anhydride derived therefrom is preferably an aromatic polycarboxylic acid containing three or four units of carboxylic acid or an anhydride derived from it, more preferably an aromatic polycarboxylic acid containing three units of carboxylic acid or an anhydride derived therefrom, even more preferably trimellitic acid or trimellitic acid anhydride, more preferably trimellitic acid anhydride.
    [0012] [0012] Examples of aromatic polycarboxylic acids containing at least three units of carboxylic acid or anhydrides derived from them are trimellitic acid, trimellitic acid anhydride, pyromelitic acid, pyromelitic acid dianhydride, trimethic acid, melitic acid and melitic anhydride.
    [0013] [0013] Trimellitic acid anhydride has the following structure: o o o o Alcoholic alkoxylate component
    [0014] [0014] In a preferred embodiment of the alkoxylated polycarboxylic acid esters of the invention, the alcoholic alkoxylate is described by formula (1),
    [0015] [0015] The n + m value is the average molar number of alkoxy groups. The values of nor can be determined using NMR and the value of n + m is from 4 to 100, preferably from 8 to 70, more preferably from 10 to 60 and even more preferably from 12 to 50. Within this preferred embodiment, the value of n + m can be 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24,25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50.
    [0016] [0016] In a preferred embodiment, m is 0 and n is a number from 4 to 100.
    [0017] [0017] In another preferred embodiment, both m and n are> O.
    [0018] [0018] In another preferred embodiment, n is 0 and m is a number from 4 to 100.
    [0019] [0019] In another preferred embodiment of the invention, R2 and R3 of the formula (1) are both hydrogen, n is a number from 4 to 100 in is 0 or a number from 1 to 50, preferably n is from 8 to 70 and is 0 or from 1 to 30, more preferably n is from 10 to 60 in is O or from 1 to 25 and even more preferably n is from 12 to 50 in is 0 or from 1 to 20e when m> O, the ratio of n to m is greater than 1 , preferably at least 2, more preferably at least 3 and even more preferably at least 4.
    [0020] [0020] In another preferred embodiment of the invention, R4 and R5 of formula (1) are both hydrogen, m is a number from 4 to 100 and n is O or a number from 1 to 50, preferably m is 8 to 70 and n is O or from 1 to 30, more preferably m is from 10 to 60 and right O or from 1 to 25 and even more preferably m is from 12 to 50 and n is O or from 1 to 20e when n> O, the ratio of m to n is greater than 1 , preferably at least 2, more preferably at least 3 and even more preferably at least 4.
    [0021] [0021] In another preferred embodiment of the invention, three of R2, R3, R4 and R5 of formula (1) are hydrogen and the other is methyl and the values of both n and m are different from zero. The groups denoted by n and m are distributed in blocks, alternating, periodically and / or statistically.
    [0022] [0022] In a preferred embodiment, the substituted or unsubstituted alkyl or alkenyl residue R1 is unsubstituted and is preferably methyl.
    [0023] [0023] In another preferred embodiment, the substituted alkyl or alkenyl residue R1 is substituted with one or more halogen atoms, a carbonyl group, a carboxyl group, an ester function or an ether function.
    [0024] [0024] In another preferred embodiment, the substituted or unsubstituted alkyl or alkenyl residue R1 has a straight or branched carbon chain, preferably a linear carbon chain.
    [0025] [0025] In another preferred embodiment of the invention, the alcoholic alkoxylate is an ethoxylated alcohol or an ethoxylated and propoxylated alcohol, preferably of the formula (|), wherein the ratio of ethylene oxide units to propylene oxide units is greater than 1, preferably at least 2, more preferably at least 3 and even more preferably at least 4 and is preferably an ethoxylated and propoxylated alcohol.
    [0026] [0026] In another preferred embodiment of the invention, the alcoholic alkoxylate of formula (1) is a polyethylene glycol monomethyl ether! or an alcohol-terminated methyl-ethoxylated-propoxylated polyether with an Mn molecular weight of 252 to 4900, preferably with an Mn molecular weight of 350 to 4000, even more preferably with an Mn molecular weight of 450 to 3000 and particularly and preferably with a molecular weight Mn of 500 to 2500 and is preferably a monomethyl ether of polyethylene glycol with a molecular weight of 252 to 4400, preferably with a molecular weight of 350 to 4000, even more preferably with a molecular weight of 450 to 3000 and particularly and preferably with an Mn molecular weight of 500 to 2500.
    [0027] [0027] The molecular mass Mn is the numerical average molecular mass. The average molecular weight (Mn) of the alcoholic alkoxylate can be determined by CPG (gel permeation chromatography) in analogy to the method disclosed in WO 2016/075178 A1 (pages 7/8), preferably as detailed below: 10 ul sample they are injected on a PSS Suprema column of dimensions 300 x 8 mm with porosity of 30 À and particle size of 10 µm. Detection is monitored at 235 nm on a multiple wavelength detector. The eluent used is 1.25 g / l of disodium hydrogen phosphate in a 45/55% (v / v) water / acetonitrile mixture. The separations are conducted at a flow rate of 0.8 ml / min. Quantification is performed by externally calibrating standard polyethylene-
    [0028] [0028] In the alkoxylated polycarboxylic acid esters of the invention, the alcohol or at least one alcohol of the alcohol mixture used in step 2 of the reaction is generally an alkyl aryl alcohol having 7 to 13 carbon atoms or a substituted alkyl or alkenyl unsubstituted alcohol having 2 to 20 carbon atoms, preferably an alkyl aryl alcohol having 7 to 10 carbon atoms, a substituted or unsubstituted alkyl or alkenyl alcohol having 12 to 18 carbon atoms or a substituted alkyl alcohol having 2 to 4 atoms carbon, more preferably an alkyl aryl alcohol having 7 to 10 carbon atoms, an unsubstituted alkyl or alkenyl alcohol having 12 to 18 carbon atoms, which is preferably straight chain, or an alkyl alcohol having 2 or 3 carbon atoms which is substituted with an ether function, more preferably an unsubstituted alkyl alcohol having 12 to 18 carbon atoms, or an alkyl alcohol with 2 carbon atoms which is substituted with a phenoxy or ethoxyphenoxy group, where the phenyl ring in said phenoxy groups can be further substituted.
    [0029] [0029] In the case where alcohol is an alkyl aryl substituent having 7 to 13 carbon atoms, the number of specific carbon atoms includes the aromatic ring.
    [0030] [0030] In a preferred embodiment of the invention, the substituted alkylene or alkenyl alcohol is replaced with one or more halogen atoms, a carbonyl group, a carboxyl group, an ester function or an ether function.
    [0031] [0031] In another preferred embodiment of the invention, the substituted or unsubstituted alkyl or alkenyl alcohol has a straight or branched carbon chain, preferably a linear carbon chain.
    [0032] [0032] In another preferred embodiment of the invention, the alkyl or alkenyl alcohol substituted with an ether function is a substituted or unsubstituted ethoxylated aromatic alcohol, preferably having 8 to 16 carbon atoms, more preferably 8 to 12 carbon atoms.
    [0033] [0033] In another preferred embodiment of the invention, the alkyl or alkenyl alcohol substituted with an ether function is an etherified glycol or oliglycol, for example ethylene glycol phenyl ether (phenoxyethanol) or an ethylene glycol ether and a substituted phenol , for example, a methylated, halogenated or methoxylated phenol.
    [0034] [0034] In a preferred embodiment of the invention, the alcohol or at least one alcohol of the alcohol mixture used in step 2 of the reaction is an alkyl aryl alcohol having 7 to 13, preferably 7 to 10, in particular 7 (i.e., benzyl alcohol), carbon atoms, or is an unsubstituted alkyl alcohol having 2 to 20, preferably 2 to 18 carbon atoms, which has a linear or branched carbon chain, preferably linear, or is a substituted alkyl alcohol having 2 to 4, preferably 2, carbon atoms, which is substituted with an ether function, where the second part of the ether is derived from an unsubstituted or substituted phenol, which is preferably unsubstituted and, if substituted, is preferably a methylated phenol , halogenated or methoxylated, or an unsubstituted or substituted ethoxylated phenol, which is preferably unsubstituted and, if substituted, is preferably a methylated, halogenated or methoxylated phenol.
    [0035] [0035] In a particularly preferred embodiment of the invention, the alcohol or at least one alcohol of the alcohol mixture used in step 2 of the reaction is selected from the group consisting of lauryl alcohol (dodecanol), myristyl alcohol (tetradecanol), a mixture of lauryl alcohol and myristyl alcohol, cetearyl alcohol (a mixture of hexadecanol and octadecanol), stearyl alcohol (octadecanol) and coconut fatty alcohol (a mixture of C6 to C18 alcohols), phenoxyethanol, alcohol! phenethyl and benzyl alcohol and is preferably selected from the group consisting of phenoxyethanol, alcohol! phenethyl and benzyl alcohol.
    [0036] [0036] In a particularly preferred embodiment of the invention, the alkoxylated polycarboxylic acid esters of the invention are obtained by first reacting with trimellitic acid anhydride, with a monomethyl ether of polyethylene glycol with a molecular mass Mn of 500 to 1500 and in a second step by reacting the resulting product with benzyl alcohol, phenoxyethanol or a mixture of benzyl alcohol and phenoxyethanol.
    [0037] [0037] In another particularly preferred embodiment of the invention, the alkoxylated polycarboxylic acid esters of the invention are obtainable by first reacting with trimellitic acid anhydride, with a polyethylene glycol monomethyl ether with a molecular mass Mn of 500 to 1500 and in a second step by reacting the resulting product with an unsubstituted alkyl alcohol having 12 to 18 carbon atoms.
    [0038] [0038] In another preferred embodiment of the invention, the alkoxylated polycarboxylic acid esters of the invention are compounds or mixtures of compounds of the formula (Il), the [9] “OC (11) R10 Oo where R8, R9 and R10 are selected from (a) and (b) such that at least one of R8, R9 and R10 is (b) and at least one of R8, R $ and R10 is (a), preferably R8 is (a) and one or both of R9 and R10 are (b), more preferably R8 is (a) and one of R9 or RIO is (another one is (a), where: (a) is alkylaryloxy having 7 to 13 carbon atoms or substituted alkoxy or alkenyloxy or unsubstituted having 2 to 20 carbon atoms, preferably alkylaryloxy having 7 to 10 carbon atoms, alkoxy or substituted alkenyloxy having 12 to 18 carbon atoms or substituted alkoxy having 2 to 4 carbon atoms, more preferably alkylaryloxy having 7 to 10 carbon atoms or alkoxy or unsubstituted alkenyloxy having 12 to 18 carbon atoms, which is preferably straight chain, or alkoxy having 2 or 3 carbon atoms which is substituted with an ether group, more preferably an unsubstituted alkyl alcohol having 12 to 18 carbon atoms, or alkoxy with 2 carbon atoms which is substituted with a phenoxy or ethoxyphenoxy group, where the phenyl ring in said phenoxy groups can be further substituted, and (b) is an alcoholic alkoxylate group of the formula (1) R7 R4 R3 NE ro k gi R6 R5 R2 (D) where R1 to R /, men have the same preferred meanings and meanings as in Formula (|) and Yéo.
    [0039] [0039] The preferred meanings of (a) follow from the preferred alcohols of the alcohol component.
    [0040] [0040] In another preferred embodiment of the invention, R8 of formula (11) is equal to one of R9 or R10 and is an alkylaryloxy having 7 to 13 carbon atoms or substituted or unsubstituted alkyloxy or alkenyloxy having 2 to 20 atoms carbon, preferably alkylaryloxy having 7 to 10 carbon atoms or substituted or unsubstituted alkyloxy or alkenyloxy having 12 to 18 carbon atoms, more preferably an alkylaryloxy group having 7 to 10 carbon atoms, in particular benzyloxy, or unsubstituted alkyloxy having 12 to 18 carbon atoms, in particular lauryloxy, myristyloxy, a mixture of lauryloxy and myristyloxy, palmityloxy, stearyloxy, or a mixture of palmylethyl and stearyloxy (cetearyloxy).
    [0041] [0041] In another preferred embodiment of the invention, R8 of formula (II) is equal to one of R9 or R10 and is a substituted or unsubstituted ethoxylated aromatic alcohol residue having 8 to 16 carbon atoms, preferably 8 to 12 atoms carbon, in particular phenoxyethoxy.
    [0042] [0042] In another preferred embodiment of the invention, formula (1 ') is a residue of polyethylene glycol monomethyl ether with an Mn molecular weight of 251 to 4400, preferably with an Mn molecular weight of 350 to 4000, even more preferably with an Mn molecular mass of 450 to 3000 and particularly and preferably with an Mn molecular mass of 500 to 2500.
    [0043] [0043] Other preferred embodiments of the invention may arise from the combination of the preferred embodiments described above. Preparation process
    [0044] [0044] In another aspect of the invention there is provided a process for producing the alkoxylated polycarboxylic acid esters of the invention, preferably those of formula (ll), comprising the steps of first reacting an aromatic polycarboxylic acid containing at least three units of carboxylic acid or an anhydride derived therefrom with an alcoholic alkoxylate and secondly reacting the resulting product with an alcohol or a mixture of alcohols, preferably with an alcohol.
    [0045] [0045] In the preparation of the alkoxylated polycarboxylic acid esters of the invention, reaction step 1 is carried out in the presence or absence of an additional solvent, preferably in the absence of an additional solvent.
    [0046] [0046] Solvents suitable for the reaction of an alcohol with an aromatic acid anhydride are known to persons skilled in the art. These solvents include but are not limited to aromatic hydrocarbons, for example but not limited to benzene, toluene, or xylene, non-protic polar solvents, for example but not limited to anisole, aromatic ethers, high boiling alkyl ethers, dimethylformamide and dimethyl sulfoxide.
    [0047] [0047] In a preferred embodiment, the alcoholic alkoxylate used as a reagent, preferably the alcoholic alkoxylate of formula (1), can serve as a solvent at the reaction temperature.
    [0048] [0048] In the preparation of alkoxylated polycarboxylic acid esters of the invention, reaction step 1 is generally carried out with 0.7 to 1.5 molar equivalents of alcoholic alkoxylate, preferably 0.8 to 1.4 molar equivalents, more preferably 0.9 to 1.3 molar equivalents and more preferably 1.0 to 1.2 molar equivalents.
    [0049] [0049] Molar equivalents are defined here in relation to aromatic polycarboxylic acid.
    [0050] [0050] In the preparation of the alkoxylated polycarboxylic acid esters of the invention, reaction step 1 is carried out in the presence or absence of a catalyst, preferably in the absence of a catalyst.
    [0051] [0051] Catalysts for the reaction of an alcohol with an anhydride acid are known to persons skilled in the art. These catalysts include, but are not limited to, Lewis acids such as zinc chloride and ferric chloride, Bronstedt acids such as sulfuric acid, perchlorhydric acid and trifluoroacetic acid and tertiary amines such as 4-dimethyl amino pyridine.
    [0052] [0052] In the preparation of the alkoxylated polycarboxylic acid esters of the invention, reaction step 1 is generally carried out at a temperature of 50 to 150 ° C, preferably at a temperature of 60 to 140 ° C even more preferably at a temperature of 70 to 130 ° C and more preferably at a temperature of 80 to 120ºC.
    [0053] [0053] In the preparation of the alkoxylated polycarboxylic acid esters of the invention, reaction step 2 is carried out in the presence or absence of an additional solvent, preferably in the absence of an additional solvent.
    [0054] [0054] Solvents suitable for the esterification of an alcohol or mixture of alcohols with a carboxylic acid are known to persons skilled in the art. These solvents include but are not limited to aromatic hydrocarbons, for example benzene, toluene, or xylene, non-protic polar solvents, for example anisol, aromatic ethers, high boiling alkyl ethers, dimethylformamide and dimethyl sulfoxide.
    [0055] [0055] In a preferred embodiment, the solvent used in the second reaction step is the same as the solvent used in the first reaction step.
    [0056] [0056] In another preferred embodiment, the alcohol or mixture of alcohols used as reagents in the second step of the reaction serves as a solvent.
    [0057] [0057] In another preferred embodiment, the reaction is carried out in a pot without changing the solvent or reaction vessel between the first and the second reaction stage.
    [0058] [0058] In the preparation of the alkoxylated polycarboxylic acid esters of the invention, reaction step 2 is carried out in the presence or absence of a catalyst, preferably in the presence of a Bronstedt acid or Lewis acid catalyst.
    [0059] [0059] Suitable catalysts for esterification reactions are well known to those skilled in the art. These catalysts include, but are not limited to, sulfonic acids such as methane sulfonic acid, acid for toluene sulfonic, disodium acids
    [0060] [0060] In the preparation of the alkoxylated polycarboxylic acid esters of the invention, reaction step 2 is generally carried out with 1.8 to 3.5 molar equivalents of the alcohol or mixture of alcohols, preferably 1.9 to 3.0 equivalents molars and more preferably 2.0 to 2.8 molar equivalents.
    [0061] [0061] Molar equivalents are defined here in relation to aromatic polycarboxylic acid.
    [0062] [0062] In the preparation of the alkoxylated polycarboxylic acid esters of the invention, reaction step 2 is generally carried out at a temperature of 130 to 250 ° C, preferably at a temperature of 150 to 220 ° C, even more preferably at a temperature of 160 to 200 ° C and more preferably at a temperature of 170 to 200ºC.
    [0063] [0063] The alkoxylated polycarboxylic acid esters of the invention, in particular those of the formula (Il)) are used as anti-replenishing agents in particular in laundry or laundry washing compositions and applications.
    [0064] [0064] The alkoxylated polycarboxylic acid esters of the invention have other uses as dispersants, in particular in laundry or laundry washing compositions and applications. EXAMPLES
    [0065] [0065] The examples below are intended to illustrate the invention in detail without, however, limiting it to these.
    [0066] [0066] Trimellitic acid was used as purchased from ACROS
    [0067] [0067] Lauryl / myristyl alcohol and cetearyl alcohol were used in technical grade quality and their molecular masses were determined before use by measuring the hydroxyl value (OH value) and subsequently calculating the molecular mass (by hydroxyl function) , "Gebrauchsmol"). In this case, the OH value can be measured according to DIN 53240.
    [0068] [0068] The acid number (acid value) can be measured according to DIN EN ISO 2114.
    [0069] [0069] Polyglycols M are monomethyl ethers of polyethylene glycol! monohydro-functional (M-PEG, CAS-Nr. 9004-74-4).
    [0070] [0070] Polyglycol M 500 is a linear, monohydro-functional polyethylene glycol monomethyl ether (M-PEG) that has a molecular weight of 470 to 530 g / mol.
    [0071] [0071] Polyglycol M 750 is a monomethyl ether of polyethylene glycol | monohydro-functional, linear (M-PEG) that has a molecular mass of 720 to 780 g / mol.
    [0072] [0072] Polygonal! M 1000 is a monohydro-functional, monohydroxy polyethylene glycol ether (M-PEG) which has a molecular weight of 970 to 1060 g / mol.
    [0073] [0073] Polyglycol M 1250 is a monohydro-functional, monohydroxy polyethylene glycol ether (M-PEG) that has a molecular weight of 1125 to 1375 g / mol.
    [0074] [0074] Polyglycol! M 2000 is a linear, monohydroxy-functional polyethylene glycol monomethyl ether (M-PEG) that has a molecular weight of 1800 to 2200 g / mol.
    [0075] [0075] The degree of alkoxylation of the methyl polyglycols used can be verified using NMR spectroscopy, for example using * H NMR spectroscopy in analogy to the method described in R. Stevanova, D. Rankoff, S. Panayotova, SL Spassov, J Am. Oil Chem. Soc., 65, 1516-1518 (1988). For this purpose, the samples are derived by reacting them with trichloro acetyl isocyanate and measured as deuterated chloroform solutions containing 1% by weight (1% by weight) of tetramethyl silane as an internal standard.
    [0076] [0076] The esterification reactions were controlled by determining the residual alcohol content (for example, benzyl alcohol, phenoxyethanol, lauryl / myristyl alcohol and cetearyl alcohol) by GC-FID. Calibration was performed with pure starting materials. Gas chromatography (GC) was performed using a Hewlett Packard GC 6890 with self-sampling, coupled with a flame ionization detector (DIC).
    [0077] [0077] For the quantification of benzyl alcohol, samples were separated in a column of 50 m x 0.2 mm, with a 0.33 µm film. The column temperature was initially maintained at 50ºC, then the temperature was raised to 175ºC at a rate of 5ºC per minute and from 175ºC to 300ºC at a rate of 25ºC per minute. The injector temperature was maintained at 250ºC and the injection volume was 1.0 ul in the split mode. Helium was used as a carrier gas with a constant pressure of 1.8 bar. The samples were prepared by diluting 500 mg of sample (duplicate analysis) with 5 ml of methanol.
    [0078] [0078] For the quantification of phenoxyethanol, cetearyl alcohol and lauryl / myristyl alcohol, samples were separated in a column of 25 m x 0.32 mm, with a film of 0.52 µm. The column temperature was initially maintained at 50ºC, then the temperature was raised to 250ºC at a rate of 10ºC per minute and maintained for 6.5 minutes. The injector temperature was kept at 250ºC and the injection volume was 1.0 uL in the split mode. Helium was used as a carrier gas with a constant pressure of 0.9 bar. Samples were prepared by diluting 500 mg of sample (duplicate analysis) with 5 ml of methanol.
    [0079] [0079] Thin layer chromatography (TLC) was performed using TLC Silica Gel 60 F254 plates from Merck. The aromatic compounds were detected by UV light (254 and 366 nm simultaneously).
    [0080] [0080] Examples 1 to 22 were performed according to a standard procedure. All reagents and quantities are listed in Table |
    [0081] [0081] The alcoholic alkoxylate of choice was heated to 80ºC with stirring under nitrogen. The polycarboxylic acid or acid anhydride of choice was then added in portions over 5 minutes. The reaction mixture was then stirred for 2.5 hours at 80 ° C. The product, hereinafter called the precursor, was isolated and the number of acid determined - these are listed in the Table | in column AN1.
    [0082] [0082] Some amount of the precursor (listed in the "PC" column of Table 1) was mixed with the alcohol and catalyst of choice and heated to the temperature listed in the Table | while stirring under nitrogen. The reaction mixture was stirred at the temperature listed for the time shown in Table | and water was distilled. For all examples except examples 10 and 11, the product was then isolated after cooling and the acid number of the final product determined - listed as AN2 in Table |
    [0083] [0083] In the cases of examples 10 and 11, a vacuum of 500 mbar was applied at 180ºC for 3 h under agitation after the completion of agitation for the time listed in Table |
    [0084] [0084] In the case of comparative example C1, polyglycolic alcohol! 1 M750 was heated to 80ºC with stirring under nitrogen. Trimellitic acid anhydride was then added in portions over 5 minutes. The reaction mixture was then stirred for 2.5 hours at 80 ° C. The product was isolated and the acid number determined.
    [0085] [0085] In the case of examples 23 to 27, the alcoholic alkoxylate of choice was mixed with the polycarboxylic acid of choice, the alcohol and catalyst of choice and heated to the temperature listed in the Table | while stirring under nitrogen. The reaction mixture was stirred at the temperature listed for the time shown in Table | and water was distilled. In the cases of examples 25 to 27, the product was then isolated after cooling and the acid number of the final product determined - listed as AN2 in Table | In the case of examples 23 to 24, a vacuum of 500 mbar was applied at 180 ° C for 3 h under agitation after completion of the agitation for the time listed in Table | Subsequently, the product was isolated after cooling and the acid number of the final product determined - listed as AN2 in Table |
    [0086] [0086] The abbreviations used in the Table | are as follows: AA alcoholic alkoxylate PCA polycarboxylic acid PC precursor BA benzyl alcohol PE phenoxyethane! C16 / 18 alcohol! cetearyl C12 / C14 lauryl alcohol / myristyl AN1 acid number of precursor AN2 acid number of final product MB50O polyglycic! M 500 M750 polygonal! M 750 M1000 polygonal! M 1000 M1250 polyglycol M 1250
    [0087] [0087] The formulations in Table II were used to wash eight 5x5 cm cotton knitted garments in a Tergotometer set at 200 rpm (revolutions per minute). An hour-long wash was carried out in 800 ml of water with French 26º hardness at 20ºC, with 2.3 g / l of the formulation shown in Table II. To simulate the particulate dirt that can reposition, 0.04 g / | 100% compressed carbon black (ex Alfa Aesar) was added to the washing liquid. To simulate oily sebaceous dirt, 7.2 g of a strip with dirt SBL2004 (ex Warwick Equest) was added to the washing liquid.
    [0088] [0088] Once the wash was completed, the cotton samples were rinsed once in 400 ml of clean water, removed, dried and the color measured on a reflectometer and expressed as the CIE values L * a * b *. The benefit of antiredeposition was expressed as the value of AL: AL = L * (dispersant) - L * (control)
    [0089] [0089] The higher the AL value, the greater the inhibition of dirt deposition by carbon black. 95% confidence limits based on the 8 separate cotton samples were calculated. Formulations were manufactured with and without the addition of 8.7% by weight of the dispersants in Table | The results are provided in Table Ill. Table Ill: Benefit of antiredeposition Example 10 Example 18 Example 22 Example C1
    [0090] [0090] The alkoxylated polycarboxylic acid esters of the invention enhance anti-repositioning.
    权利要求:
    Claims (13)
    [1]
    1. Alkoxylated polycarboxylic acid esters, characterized by the fact that they are obtained by first reacting an aromatic polycarboxylic acid containing at least three units of carboxylic acid or an anhydride derived therefrom, preferably an aromatic polycarboxylic acid containing three or four units of acid carboxylic acid or an anhydride derived therefrom, more preferably an aromatic polycarboxylic acid containing three units of carboxylic acid or an anhydride derived from it, even more preferably trimellitic acid or trimellitic acid anhydride, more preferably trimellitic acid anhydride, with an alcoholic alkoxylate and in an second step reacting the resulting product with an alcohol or a mixture of alcohols, preferably with an alcohol, wherein the alcohol or at least one alcohol of the alcohol mixture is an alkyl aryl alcohol having 7 to 10 carbon atoms, an alkyl alcohol or unsubstituted alkenyl having 12 to 18 carbon atoms, which is p referring to a straight chain, or an alkyl alcohol having 2 or 3 carbon atoms which is replaced with an ether function, preferably an unsubstituted alkyl alcohol having 12 to 18 carbon atoms, or an alkyl alcohol with 2 carbon atoms which is substituted with a phenoxy or ethoxyphenoxy group, where the phenyl ring in said phenoxy groups can be further substituted.
    [2]
    2. Alkoxylated polycarboxylic acid esters according to claim 1, characterized by the fact that the alcoholic alkoxylate is described by the formula (!), R3 R4 R7 RA od The R2 R5 R6 where R1 is a substituted alkyl or alkenyl group or unsubstituted having 1 to 20 carbon atoms, an aryl or alkyl aryl group having 6 to 20 carbon atoms, or H, preferably a substituted or unsubstituted alkyl or alkenyl group having 1 to 12 carbon atoms or an aryl group or alkyl aryl having 6 to 13 carbon atoms, more preferably a substituted or unsubstituted alkyl or alkenyl group having 1 to 6 carbon atoms and more preferably a methyl group,
    R2 to R5 are independently of each other hydrogen or an alkyl group having 1 to 4 carbon atoms, preferably hydrogen or methyl,
    where the substituents R2 to R5 are chosen such that both of R2 and R3 or R4 and R5 are hydrogen and at least one of the other substituents is different from hydrogen, preferably such that three of the substituents R2 to R5 are hydrogen and even more preferably such that three of the substituents R2 to R5 are hydrogen and the other substituent is a methyl group,
    nor are they independently of each other, based on a molar average, numbers from 0 to 100 such that n + m is from 4 to 100, preferably from 8 to 70, more preferably from 10 to 60 and even more preferably from 12 to 50 ,
    where in the case where R2 and R3 are both hydrogen, n is a number from 4 to 100 and m is a number from O to 50, preferably n is from 8 to 70 and 0 to a30, more preferably n is from 10 to 60 and from 0 to 25 and even more preferably n is from 12 to 50 and is from 0 to 20 and when m> O, the ratio of n to m is greater than 1, preferably at least 2, more preferably at least 3 and even more preferably at least 4,
    where in the case where R4 and R5 are both hydrogen, m is a number from 4 to 100 and n is a number from O to 50, preferably m is 8a70enéde0oOa30, more preferably m is 10a60ené from O to 25 and even more preferably m is 12 to 50 and n is 0 to 20 and when n> O, the ratio of m to n is greater than 1, preferably at least 2, more preferably at least 3 and even more preferably at least 4, where in the case where both n and m are> 0, the units are distributed in blocks, alternating periodically and / or statistically, R6 and R7 are independently of each other hydrogen or an alkyl group having 1 to 4 carbon atoms, preferably hydrogen or methyl and at least minus one of R6 and R7 is methyl, and Yé OH.
    [3]
    3. Alkoxylated polycarboxylic acid esters according to claim 1 or 2, characterized by the fact that the alcoholic alkoxylate is an ethoxylated alcohol or an ethoxylated and propoxylated alcohol, in which the ethylene oxide unit ratio to propylene oxide units is greater than 1, preferably at least 2, more preferably at least 3 and even more preferably at least 4 and is preferably an ethoxylated and propoxylated alcohol.
    [4]
    Alkoxylated polycarboxylic acid esters according to any one of claims 1 to 3, characterized in that the alcoholic alkoxylate of formula (1) is a monomethyl ether of polyethylene glycol or a methyl-ethoxylated-propoxylated polyether ending in alcohol with an Mn molecular mass of 252 to 4900, preferably with an Mn molecular mass of 350 to 4000, even more preferably with an Mn molecular mass of 450 to 3000 and particularly and preferably with an Mn molecular mass of 500 to 2500 and it is preferably a polyethylene glycol monomethyl ether! with an Mn molecular mass of 252 to 4400, preferably with an Mn molecular mass of 350 to 4000, even more preferably with an Mn molecular mass of 450 to 3000 and particularly and preferably with an Mn molecular mass of 500 to 2500.
    [5]
    5. Alkoxylated polycarboxylic acid esters according to any one of claims 1 to 4, characterized in that the alcohol or at least one alcohol of the alcohol mixture used in step 2 of the reaction is selected from the group consisting of lauryl alcohol ( dodecanol), myristyl alcohol (tetradecanol), a mixture of lauryl alcohol and myristyl alcohol, cetearyl alcohol (a mixture of hexadecanol and octadecanol), stearyl alcohol (octadecanol) and coconut fatty alcohol (a mixture of C6 to C18 alcohols), phenoxyethanol , phenethyl alcohol and benzyl alcohol and is preferably selected from the group consisting of lauryl / myristyl alcohol, cetearyl alcohol and phenoxyethanol and is most preferably selected from the group consisting of alcohol! lauryl / myristyl and cetearyl alcohol.
    [6]
    6. Alkoxylated polycarboxylic acid esters according to claim 1, characterized by the fact that they have the formula (11) Oo “O (11) R10 Oo in which R8, R9 and R10 are selected from (a) and ( b) such that at least one of R8, R9 and R10 is (b) and at least one of R8, R9 and R10 is (a), preferably R8 is (a) and one or both of R9 and R10 are (b) , more preferably R8 is (a) and one of R9 or R10 is (b) and the other is (a), where: (a) is alkylaryloxy having 7 to 10 carbon atoms or alkoxy or unsubstituted alkenyloxy having 12 to 18 carbon atoms, which is preferably straight-chained, or alkoxy having 2 or 3 carbon atoms which is substituted with an ether group, more preferably an unsubstituted alkyl alcohol having 12 to 18 carbon atoms, or alkoxy with 2 carbon atoms which is replaced with a phenoxy or ethoxyphenoxy group, where the phenyl ring in said phenoxy groups can be further substituted and (b) is an alcoholic alkoxylate group of the formula (1), R7 R4 R3 NE rod Rg R6 R5 R2 (D)
    wherein R1 is a substituted or unsubstituted alkyl or alkenyl group having 1 to 20 carbon atoms, an aryl or alkyl aryl group having 6 to 20 carbon atoms, or H, preferably a substituted or unsubstituted alkyl or alkenyl group having 1 to 12 carbon atoms or an aryl or alkyl aryl group having 6 to 13 carbon atoms, more preferably a substituted or unsubstituted alkyl or alkenyl group having 1 to 6 carbon atoms and more preferably a methyl group,
    R2 to R5 are independently of each other hydrogen, or an alkyl group having 1 to 4 carbon atoms, preferably hydrogen or methyl,
    where the substituents R2 to R5 are chosen such that both of R2 and R3 or R4 and R5 are hydrogen and at least one of the other substituents is different from hydrogen, preferably such that three of the substituents R2 to R5 are hydrogen and even more preferably such that three of the substituents R2 to R5 are hydrogen and the other substituent is a methyl group,
    nor are they independently of each other, based on a molar average, numbers from 0 to 100 such that n + m is a number from 4 to 100, preferably from 8 to 70, more preferably from 10 to 60 and even more preferably from 12 to 50,
    where in the case where R2 and R3 are both hydrogen, n is a number from 4 to 100 and m is a number from O to 50, preferably n is from 8ga70eméde0O to30, more preferably n is from 10 to 60 and is from 0 to 25 and even more preferably n is 12 to 50 and is 0 to 20 and when m> O, the ratio of n to m is greater than 1, preferably at least 2, more preferably at least 3 and even more preferably at minus 4, where in the case where R4 and R5 are both hydrogen, m is a number from 4 to 100 and n is a number from O to 50, preferably m is from 8 to 70 and 0 to 0, more preferably m is 10 to 60 and from 0 to 25 and still more preferably m is 12 to 50 and n is 0 to 20 and when n> O, the ratio of m to n is greater than 1, preferably at least 2, more preferably at least 3 and even more preferably at least 4, where in the case where both n and m are> 0, the units can be distributed in blocks, alternating, periodically and / or statistically, R6 and R7 are independently a on the other hydrogen, or an alkyl group having 1 to 4 carbon atoms, preferably hydrogen or methyl and at least one of R6 and R7 is methyl, and Yéo, are preferably in the form of mixtures and are preferably obtainable by the reaction steps described as defined in any one of claims 1 to 6.
    [7]
    7. Alkoxylated polycarboxylic acid esters according to claim 6, where formula (II) is characterized by the fact that Rô is equal to one of R9 or R10 and is an alkylaryloxy having 7 to 10 carbon atoms.
    [8]
    8. Alkoxylated polycarboxylic acid esters according to claim 6 or 7, characterized by the fact that R8 is equal to one of R9 or R10 and is a substituted or unsubstituted ethoxylated aromatic alcohol residue having 8 to 16 carbon atoms , preferably 8 to 12 carbon atoms.
    [9]
    9. Alkoxylated polycarboxylic acid esters according to any one of claims 6 to 8, wherein formula (Il) is characterized by the fact that (b) is a residue of polyethylene glycol monomethyl ether of formula (I ') with a Mn molecular weight from 251 to 4400, preferably with an Mn molecular weight from 350 to 4000, even more preferably with an Mn molecular weight from 450 to 3000 and particularly and preferably with an Mn molecular weight from 500 to 2500.
    [10]
    10. Process for producing alkoxylated polycarboxylic acid esters, as defined in any one of claims 1 to 9, characterized in that it comprises the steps of first reacting an aromatic polycarboxylic acid containing at least three units of carboxylic acid or an anhydride derived therefrom with an alcoholic alkoxylate and secondly reacting the resulting product with an alcohol or a mixture of alcohols, preferably with an alcohol, wherein the alcohol or at least one alcohol of the alcohol mixture is an alkyl aryl alcohol having 7 to 10 carbon atoms, an unsubstituted alkyl or alkenyl alcohol having 12 to 18 carbon atoms, which is preferably straight chain, or an alkyl alcohol having 2 or 3 carbon atoms which is substituted with an ether function, more preferably an alkyl alcohol unsubstituted having 12 to 18 carbon atoms, or an alkyl alcohol with 2 carbon atoms that is replaced with a phenoxy or ethoxyphenoxy group, where the phenyl ring in said phenoxy groups can be further substituted.
    [11]
    11. Process, according to claim 10, characterized by the fact that the reaction of step 1 is carried out with 0.7 to 1.5 molar equivalent of alcoholic alkoxylate, preferably 0.8 to 1.4 molar equivalent, more preferably 0.9 to 1.3 molar equivalent and more preferably 1.0 to 1.2 molar equivalent.
    [12]
    12. Process according to claim 10 or 11,
    characterized by the fact that the reaction of step a is carried out at a temperature of 50 to 150 ° C, preferably at a temperature of 60 to 140 ° C, even more preferably at a temperature of 70 to 130 ° C and more preferably at a temperature of 80 to 120 ° C.
    [13]
    13. Process according to any of claims 10 to 12, characterized by the fact that the reaction in step 2 is carried out with 1.8 to 3.5 molar equivalents of the alcohol or mixture of alcohols, preferably 1.9 to 3.0 molar equivalents and more preferably 2.0 to 2.8 molar equivalents.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112020000040A2|2020-07-21|alkoxylated polycarboxylic acid esters
    CA2702824C|2013-04-30|Cleaning compositions with alkoxylated polyalkanolamines
    JPH08508022A|1996-08-27|Peroxy acid
    US10240107B2|2019-03-26|Laundry detergents containing soil release polymers
    CN103492428A|2014-01-01|Continuous process for esterifying polymers bearing acid groups
    EA024706B1|2016-10-31|Laundry detergents based on compositions derived from natural oil metathesis
    EP2174941A1|2010-04-14|Isosorbide-derivatives
    CN103328622A|2013-09-25|Use of optionally oxidized thioethers of polyalkylene glycols in detergents and cleaning agents
    BR112019027477A2|2020-07-07|stamina or salt of the same, process for preparation of stamina or salt of the same, use of stamina and salt of the same, and composition of personal care
    BR112019028222A2|2020-07-07|alkoxylated carboxylic acid amides
    EP3218465B1|2019-07-31|Laundry detergents containing soil release polymers
    US20210189290A1|2021-06-24|Alkoxylated phenol derivatives
    EP3416938B1|2019-10-16|Alkoxylated hydroxybenzoic acid esters or amides
    US10266649B2|2019-04-23|Polyetheramines with low melting point
    JP2009155606A|2009-07-16|Liquid cleaner composition
    US20210348085A1|2021-11-11|Fabric care composition with silicone
    EP3847228A1|2021-07-14|Fabric care composition
    KR100409087B1|2003-12-11|Surfactant system
    SU1541201A1|1990-02-07|Method of producing synthetic base for detergents
    KR20030012692A|2003-02-12|Surfactant system
    JPH09255990A|1997-09-30|Liquid detergent composition
    同族专利:
    公开号 | 公开日
    JP2020526602A|2020-08-31|
    MX2020000101A|2020-02-17|
    WO2019007636A1|2019-01-10|
    CN110832005A|2020-02-21|
    EP3424976A1|2019-01-09|
    AR112326A1|2019-10-16|
    US20200207910A1|2020-07-02|
    EP3661992A1|2020-06-10|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    FR2407980B1|1977-11-02|1980-08-22|Rhone Poulenc Ind|
    SE8001698L|1980-03-05|1981-09-06|Eka Ab|Antiredeposition FUNDS|
    CN103649153B|2011-07-08|2015-04-15|三洋化成工业株式会社|Polyurethane resin for moisture-permeable water-proof materials, and polyurethane resin composition|
    DE102012016462A1|2012-08-18|2014-02-20|Clariant International Ltd.|Use of polyesters in detergents and cleaners|
    US10240107B2|2014-11-11|2019-03-26|Clariant International Ltd.|Laundry detergents containing soil release polymers|CN114008183A|2019-06-28|2022-02-01|联合利华知识产权控股有限公司|Detergent composition|
    WO2020259948A1|2019-06-28|2020-12-30|Unilever Plc|Detergent composition|
    CN114008184A|2019-06-28|2022-02-01|联合利华知识产权控股有限公司|Detergent composition|
    WO2020260006A1|2019-06-28|2020-12-30|Unilever Plc|Detergent compositions|
    CN113993981A|2019-06-28|2022-01-28|联合利华知识产权控股有限公司|Detergent composition|
    BR112021023398A2|2019-06-28|2022-01-04|Unilever Ip Holdings B V|Detergent composition, home method of treating a textile and use of an ether sulfate alcohol|
    WO2021043764A1|2019-09-02|2021-03-11|Unilever Global Ip Limited|Detergent composition|
    WO2021069516A1|2019-10-07|2021-04-15|Unilever Ip Holdings B.V.|Detergent composition|
    WO2022043045A1|2020-08-28|2022-03-03|Unilever Ip Holdings B.V.|Detergent composition|
    WO2022042989A1|2020-08-28|2022-03-03|Unilever Ip Holdings B.V.|Surfactant and detergent composition|
    WO2022043042A1|2020-08-28|2022-03-03|Unilever Ip Holdings B.V.|Detergent composition|
    WO2022043138A1|2020-08-28|2022-03-03|Unilever Ip Holdings B.V.|Surfactant and detergent composition|
    WO2022042977A1|2020-08-28|2022-03-03|Unilever Ip Holdings B.V.|Detergent composition|
    CN113292716A|2021-05-24|2021-08-24|山东瑞捷新材料有限公司|Preparation method of self-emulsifying ester based on meta-phenyl ester|
    法律状态:
    2021-04-20| B08F| Application dismissed because of non-payment of annual fees [chapter 8.6 patent gazette]|Free format text: REFERENTE A 3A ANUIDADE. |
    2021-08-10| B08K| Patent lapsed as no evidence of payment of the annual fee has been furnished to inpi [chapter 8.11 patent gazette]|Free format text: REFERENTE AO DESPACHO 8.6 PUBLICADO NA RPI 2624 DE 20/04/2021. |
    2021-11-03| B350| Update of information on the portal [chapter 15.35 patent gazette]|
    优先权:
    申请号 | 申请日 | 专利标题
    EP17180301.8A|EP3424976A1|2017-07-07|2017-07-07|Alkoxylated polycarboxylic acid esters|
    EP17180301.8|2017-07-07|
    PCT/EP2018/065373|WO2019007636A1|2017-07-07|2018-06-11|Alkoxylated polycarboxylic acid esters|
    [返回顶部]