• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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    • 专利摘要:
      ACTIVE COMPOSITION OF TISSUE SOFTENER.The present invention relates to an active fabric softener composition, comprising from 65 to 95% by weight of a bis- (2-hydroxyethyl) -dimethylammonium fatty acid ester chloride containing a molar ratio of fatty acid portions to amine plots of 1.80 to 1.96, an average chain length of the fatty acid plots of 16 to 18 carbon atoms, and an iodine value of 0 to 50, 2 to 8% by weight of a triglyceride of fatty acid with an average chain length of the fatty acid portions of 10 to 14 carbon atoms, and an iodine value of 0 to 15, and 3 to 12% by weight of an alcohol selected from ethanol, 1-propanol and 2-propanol showing a low melting viscosity, a high melt stability and a low flammability.
    公开号:BR112012025002A2
    申请号:R112012025002-7
    申请日:2011-03-22
    公开日:2020-09-01
    发明作者:Hans-Jürgen Köhle；Matthias Schöppner；Axel Euler；Harald Jakob；Saji John Meledathu；Todd L KURTH；Delbert G Young；Ingo Hamann；Georg Schick
    申请人:Evonik Degussa Gmbh；
    IPC主号:
    专利说明:

    It is the Invention Patent Descriptive Report for "ACTIVE COMPOSITION OF TISSUE SOFTENER".
    DESCRIPTION The present invention relates to active fabric softener compositions containing a low content of flammable solvents, a low melt viscosity and a high melt stability.
    Quaternary ammonium salts that carry two portions of hydrophobic long chain hydrocarbon have been widely used as active fabric softeners. Quaternary ammonium salts of average esterified alkanolamines with two portions of fatty acid per molecule, normally. referred to as quat esters, they largely substituted quaternary alkyl ammonium compounds, used until then, due to their biodegradability. 'Bis- (2-hydroxyethyl) -dimethylammonium acid diester chlorides that have had commercial use are difficult to handle in a pure state, as the solid tends to lump and the melt has a high viscosity at low melting temperatures and stability unsatisfactory at higher melting temperatures. Therefore, bis- (2-hydroxyethyl) -dimethylammonium fatty acid diester chlorides are normally supplied as a molten composition containing at least 13% by weight of ethanol or 2-propanol, which has a viscosity at temperatures of 65 to 75 ° C which is low enough to allow it to be pumped. However, such compositions have a low flash point below 30ºC and are therefore subject to regulatory restrictions and require additional safety measures in handling.
    WO 2007/026314 proposes to replace the flammable solvent of such compositions with 2 to 40% by weight of a diluent selected from alkyl esters or polyesters, alkyl amides or polyamides, fatty acids, non-ionic or combinations thereof and specifically discloses fat from hydrogenated tallow, hydrogenated tallow fatty acid, hydrogenated coconut oil, hydrogenated palm stearin, hydrogenated soybean oil, ethylene glycol distearate, hard soy sucrose ester, cetyl palmitate and pentaerythritol tetracaprilate / tetracaprate as appropriate diluents. WO
    : 2007/026314 also proposes to use an additional binding agent, selected from polyhydric alcohols, partial esters of polyhydric alcohols from nonionic surfactants, in an amount of 0.1 to 15% by weight.
    However, the taught compositions of WO 2007/026314 have the disadvantage of having a low melt stability, regarding the dealkylation of the quaternary ammonium salt, which leads to an increase in the free amine ester content during transportation and handling in a molten state.
    Therefore, there is a need for active fabric softening compositions that have a low and a high melt viscosity. stability in a molten state and at the same time have low flammability. õ It has now been found that active fabric softening compositions based on a bis- (2-hydroxyethyl) -dimethylammonium acid ester chloride, prepared from fatty acids with a specific chain length and a degree specific unsaturation and containing a particular proportion of fatty acid parcels to amine parcels, which comprises a specific amount of a fatty acid triglyceride, with a shorter specific chain length of the fatty acid parcels, as well as a specific amount of an alcohol, selected from ethanol, 1-propanol and 2-propanol, shows an unexpected combination of low melt viscosity, high stability in the case of melt dealkylation and low flammability.
    The present invention is therefore directed to an active fabric softener composition, comprising a) from 65 to 95% by weight of a fatty acid bis- (2-hydroxyethyl) -dimethylammonium ester chloride containing a molar ratio of fatty acid loops for amine plots from 1.80 to 1.96, an average chain length number of fatty acid plots of 16 to 18 carbon atoms and an iodine value, calculated for free fatty acid, from 0 up to 50, b) from 2 to 8% by weight of a fatty acid triglyceride containing
    : having an average chain length of the fatty acid portions of 10 to 14 carbon atoms and an iodine value, calculated for the free fatty acid, from 0 to 15, and c) from 3 to 12% by weight of a selected alcohol ethanol, 1-propanole 2-propanol.
    The invention is further directed to a process for preparing such compositions, comprising the steps of a) reacting a mixture comprising 78 to 95% by weight bis- (2-hydroxyethyl) -methylamine fatty acid ester containing a molar ratio of fatty acid plots for 1.80 amine plots. up to 1.96, an average chain length number of the fatty acid portions of 16 to 18 carbon atoms and an iodine value, calculated for the free fatty acid, from 0 to 50, from 2 to 9% in weight of a fatty triglyceride acid containing an average chain length of 10 fatty acid portions up to 14 carbon atoms and an iodine value, calculated for free fatty acid, from 0 to 15, and from 3 to 13% by weight an alcohol selected from ethanol, 1-propanol and 2-propanol with an excess of methyl chloride at a temperature of 60 to 120ºC to provide a reaction mixture, and b) separation of unreacted methyl chloride from the mixture reaction step a) by distillation of a mixture of methyl chloride and said alcohol, condensation of the alcohol from said mixture of methyl chloride and alcohol and return of the condensed alcohol to said reaction mixture to supply an alcohol content of 3 to 12% by weight.
    The invention is also directed to an alternative process of preparing such compositions, comprising the steps of a) reacting a mixture comprising from 88 to 98% by weight of fatty acid bis- (2-hydroxyethyl) -methylamine ester containing a molar ratio of fatty acid plots to amine plots of 1.80 to 1.96, an average chain length number of the fatty acid plots of 16 to 18 carbon atoms and an iodine value, calculated from the acid free fat, from 0 to 50, from 2 to 9% by weight of a4no triglyceride acid | fatty acid containing an average chain length of the fatty acid portions of 10 to 14 carbon atoms and an iodine value, calculated for free fatty acid, from 0 to 15, and from 0 to 3% by weight of a selected alcohol. ethanol, 1-propanol and 2-propanol with an excess of methyl chloride at a temperature of 60 to 120ºC to provide a reaction mixture, b) adding more alcohol to the reaction mixture from step a) to provide a content of alcohol of 3 to 12% by weight, and c) separation of unreacted methyl chloride from the mixture of step b) by distillation of a mixture of methyl chloride and said alcohol, condensation of the alcohol from said mixture of methyl chloride and alcohol e. return of condensed alcohol to said reaction mixture to provide an alcohol content of 3 to 12% by weight. | The active fabric softener composition of the invention comprises from 65 to 95% by weight of the bis- (2-hydroxyethyl) -dimethylammonium acid ester chloride. The composition preferably comprises from 80 to 90% by weight of said ester.
    Bis- (2-hydroxyethyl) -dimethylammonium fatty acid ester chloride comprises at least one diester of formula (CH3) N + (CHCH; OC (= O) R), CI- and at least one monoester of formula (CH3) N + (CHCHZOH) (CH2CH2OC (= O) R) CI-, where R is the hydrocarbon group of a RCOO fatty acid portion. Bis- (2-hydroxyethyl) -dimethylammonium acid ester chloride has a molar ratio of fatty acid portions to amine portions from 1.80 to 1.96 and preferably from 1.85 to 1.94. The specified molar ratio provides high performance in fabric softening in a rinsing cycle.
    The fatty acid portion of the bis- (2-hydroxyethyl) -dimethylammonium fatty acid ester chloride can be derived from a pure fatty acid or from a mixture of fatty acids of formula RCOOH, where R is a hydrocarbon group. The hydrocarbon group can be branched or unbranched, preferably it is unbranched.
    The fatty acid portion has an average chain length of 16 to 18 carbon atoms and an iodine value, calculated for the free fatty acid, from 0 to 50. The average chain length is preferably 16.5 to 17 , 8 carbon atoms.
    Preferably, the fatty acid portion has an iodine value of 1.0 to 50, more preferably 2 to 50, even more preferably 5 to 40, and even more preferred 15 to 35. The average chain length is calculated on the basis of the weight fraction of individual fatty acids in the fatty acid mixture.
    For branched chain fatty acids in the mixture the chain length refers to the longest consecutive chain of carbon atoms.
    The iodine value is the amount of iodine in g consumed by the reaction of the 100 g fatty acid double bonds, determined by the ISO 3961 method. To provide the required average chain length and iodine value, the fatty acid portion may be derived from a mixture of fatty acids comprising | both saturated and unsaturated fatty acids.
    Unsaturated fatty acids are preferably monounsaturated fatty acids.
    Bis- (2-hydroxyethyl) -dimethylammonium fatty acid ester chloride preferably comprises less than 6% by weight of multiple unsaturated fatty acid portions.
    Examples of suitable saturated fatty acids are palmitic acid and stearic acid.
    Examples of suitable monounsaturated fatty acids are oleic acid and elaidic acid.
    The cis-trans ratio of the double bonds of the unsaturated fatty acid portions is preferably greater than 55:45, and more preferably greater than 65:35. The fraction of the multiple unsaturated fatty acid portions can be reduced by selective touch hydrogenation, which is a hydrogenation that selectively hydrogenates a double bond in a substructure -CH = CH-CH2-CH = CH- but does not hydrogenate double group bonds monounsaturated hydrocarbons.
    The specified average chain length and iodine values are essential to achieve both a high softening performance and a low melting point of the composition.
    If the average chain length is less than 16 carbon atoms or the iodine value is greater than 50, the softening performance will be unsatisfactory, while the melting point of the composition can be very high if the average chain length
    day is greater than 18 carbon atoms.
    : The fatty acid portion can be derived from fatty acids of natural or synthetic origin and is preferably derived from fatty acids of natural origin, more preferably from tallow fatty acid. The required iodine value can be supplied using a mixture of naturally occurring fatty acid that already has such an iodine value, for example a tallow fatty acid. Alternatively, the required iodine value can be provided by partial hydrogenation of a fatty acid mixture or a triglyceride mixture containing a higher iodine value. In another and more preferred mode of execution, the required iodine value is provided by mixing a fatty acid mixture containing a higher iodine value with a mixture of saturated fatty acids. The mixture of saturated fatty acids can be obtained either by hydrogenating a mixture of: fatty acids containing unsaturated fatty acids or a mixture of hydrogenated triglycerides, such as a hydrogenated vegetable oil.
    The active fabric softener composition of the present invention further comprises from 2 to 8% by weight, and preferably from 3 to 6% by weight, of a fatty triglyceride acid containing an average chain length of the acid portions fat from 10 to 14 carbon atoms and an iodine value, calculated for free fatty acid, from 0 to 15. The average chain length of the fatty acid portions is preferably from 12 to 13.8 carbon atoms . The fatty acid triglyceride is preferably a coconut oil or a hydrogenated coconut oil, and more preferably a refined coconut oil. The specified amount of fatty acid triglyceride and the average chain length of the fatty acid portions is essential to acquire simultaneously a low melting point and low flammability of the active fabric softener composition. Surprisingly, the specified amount of the fatty acid triglyceride also enhances the softening efficacy of a rinse cycle softener prepared from the active fabric softener composition of the present invention.
    The active fabric softener composition of the present invention also comprises from 3 to 12% by weight, and preferably from 6 to 12% by weight.
    7no: 10% by weight of an alcohol! selected from ethanol, 1-propanol and 2-propanol. The alcohol is preferably ethanol or 2-propanol, and more preferably 2-propanol. The specified amount of alcohol is essential to simultaneously acquire a low flammability of an active tissue-softening composition and high stability of the composition in the molten state with respect to the dealkylation of bis- (2-hydroxyethyl acid) chloride - fatty dimethylammonium. The improvement in stability that can be achieved by the specified amount of alcohol appears to be specified for the chloride salt and has not been recognized in the prior art. The combined amount of fatty acid triglyceride and the alcohol is preferably 10 to 15% by weight.
    The active fabric softener compositions of the present invention show a combination of high melt stability for dealkylation, low melt viscosity and low flammability. An active fabric softener composition comprising 86% by weight of fatty tallow bis- (2-hydroxyethyl) -dimethylammonium ester chloride, 3% by weight of coconut oil and 9% by weight of 2-propanol has a point 38ºC core determined according to DIN 53213.
    The active fabric softener composition of the present invention can be prepared by mixing bis- (2-hydroxyethyl) -dimethylammonium acid chloride, fatty acid triglyceride and alcohol in the specified amounts. However, the active fabric softener composition is preferably prepared by one of the two processes of the invention, which share the quaternization of an bis- (2-hydroxyethyl) - — fatty methylamine ester with excess methyl chloride in the presence of fatty acid triglyceride and the subsequent separation of excess methyl chloride in the presence of alcohol.
    The first method of the invention comprises two steps.
    In the first stage, a mixture comprising from 78 to 95% by weight of bis- (2-hydroxyethyl) -methylamine fatty acid ester, from 2 to 9% by weight of a fatty acid triglyceride and from 3 to 13% by weight of an alcohol selected from ethanol, 1-propanol and 2-propanol are reacted with a
    : excess of methyl chloride at a temperature of 60 to 120ºC, and preferably from 90 to 110ºC. The molar amount of methyl chloride is greater than the molar amount of bis- (2-hydroxyethyl) -methylamine fatty acid, and the molar ratio of methyl chloride to bis- (2-hydroxyethyl) -methylamine ester fatty is preferably from 1.1 to 1.5. The bis- (2-hydroxyethyl) -methylamine fatty ester has a molar ratio of fatty acid moieties to amine portions of 1.80 to 1.96, preferably from 1.82 to 1.92, a number average chain length of the fatty acid portions of 16 to 18 carbon atoms, preferably 16.5 to 17.8 carbon atoms, and an iodine value, calculated for the free fatty acid, from 0 to 50, preferably from 1.0 to 50, more preferably from 2 to 50, even more preferably from 5 to 40, and most preferably from 15 to 35. The fatty acid triglyceride has an average chain length number of fatty acid portions of 10 to 14 carbon atoms, preferably 12 to 13.8 carbon atoms, and an iodine value, calculated for free fatty acid, of 0 to 15 and is preferably a coconut oil or a hydrogenated coconut oil. The reaction is preferably carried out in a pressure vessel at a total pressure of 1 to 10 bar, preferably 3 to 8 bar. Methyl chloride is preferably added to the mixture of bis- (2-hydroxyethyl) -methylamine fatty acid, fatty acid triglyceride and alcohol at a rate that prevents an increase in pressure above the specified upper limit. The reaction is preferably carried out until more than 80%, preferably more than 85% of the bis- (2-hydroxyethyl) -methylamine fatty acid ester has reacted. Appropriate reaction times are in the range of 2 to 8 h depending on the reaction temperature and pressure.
    In the second step, unreacted methyl chloride is separated from the reaction mixture from step a) by distilling a mixture of methyl chloride and the alcohol, condensing the alcohol from the mixture of methyl chloride and distilling alcohol, and returning the alcohol condensate to the reaction mixture to provide an alcohol content of 3 to 12% by weight in the reaction mixture. The mixture of methyl chloride and alcohol is preferably distilled at a
    Ú total pressure of (0.2 to 1 bar). The alcohol is preferably condensed from the mixture of methyl chloride and alcohol in a partial condenser at a temperature between the boiling points of methyl chloride and alcohol at the pressure used for distillation. All or part of the condensed alcohol can be returned to the reaction mixture, depending on the alcohol content that is desired for the resulting mixture.
    The second method of the invention comprises three steps and differs from the first method of the invention in that the initial mixture comprises from 88 to 98% by weight of bis- (2-hydroxyethyl) -methylamine fatty acid and from (0 to 3% by weight of the alcohol and the fact that in an additional step more alcohol is added to the reaction mixture from the first step to provide an alcohol content of 3 to 12% by weight, before the separation of unreacted methyl chloride from the mixture.
    The two processes of the invention have the advantage of providing an active fabric softener composition containing a low content of non-quaternized fatty acid bis- (2-hydroxyethyl) -methylamine ester in short reaction times. The second method of the invention has the additional advantage of the low by-product formation of the alcohol alkylation and an even shorter alkylation time.
    The invention is illustrated by the following examples, which in the meantime are not intended to limit the scope of the invention in any way.
    EXAMPLES Active fabric softening compositions were prepared from coconut oil, 2-propanol and a fatty tallow bis- (2-hydroxyethyl) -dimethylammonium ester chloride with an iodine value of 20, calculated from free fatty acid, containing a molar ratio of fatty acid portions to amine portions of 1.89 and containing 0.044 mmol / g of bis- (2-hydroxyethyl) -methylamine fatty ester, 0.041 mmol / g of chloride bis- (2-hydroxyethyl) -methylammonium fatty ester and 0.111mmol / g of fatty acid by mixing quaternary ammonium salt equipped with powdered solvents in the quantities given in table 1 and the melting temperatures of the mixtures.
    : Storage stability was determined for active fabric softening compositions that were stored for 5 days at 100ºC in closed glass bottles.
    Was the melting viscosity measured at 90ºC with a SESSAGE Tech rheometer from REOLOGICA Instruments using 50 mm parallel plates, a plate distance of 1 mm and shear rates of 1, 10 and 100s *. Table 1 Properties of the active fabric softener compositions.
    Coconut area: 92: 0: 8 96: 4: 0 88: 4: 8 2-propanol in% by weight | Melt viscosity at 1 s * melt iscosity at 1 s 272 13200 262 in mPa * s melt iscosity at 10 s * in mPa * s Melt viscosity: b and MITO 219 2290 194 in mPa * s Quat deallated fraction after 5 days of storage at 78 10.0 79 100ºC in% * Not according to the invention.
    权利要求:
    Claims (8)
    [1]
    1. Active fabric softener composition, comprising a) from 65 to 95% by weight of a fatty acid bis- (2-hydroxyethyl) -dimethylammonium ester chloride containing a molar ratio of fatty acid partners to amine portions of 1 , 80 to 1.96, an average chain length number of the fatty acid portions of 16 to 18 carbon atoms and an iodine value, calculated for the free fatty acid, from 0 to 50, b) up to 8% in weight of a fatty acid triglyceride with an average chain length of the fatty acid portions of 10 to 14 Å. carbon atoms and an iodine value, calculated for free fatty acid, from 0 to 15, and c) from 3 to 12% by weight of an alcohol selected from ethanol, 1-propanol and 2-propanol.
    [2]
    Active fabric softener composition according to claim 1, comprising from 3 to 6% by weight of the respective fatty acid triglyceride and from 6 to 10% by weight of said alcohol.
    [3]
    Active fabric softener composition according to claim 1 or 2, wherein the combined amount of said acid triglyceride and said alcohol is 10 to 15% by weight.
    [4]
    Active fabric softener composition of any one of claims 1 to 3, wherein in the fatty acid triglyceride there is a coconut oil or a hydrogenated coconut oil.
    [5]
    Active fabric softener composition according to any one of claims 1 to 4, wherein the fatty acid portions of the bis- (2-hydroxyethyl) -dimethylammonium fatty acid ester chloride have an iodine value, calculated for free fatty acid, from 15 to 35.
    [6]
    Process for preparing an active amaranth composition according to claim 1, comprising the steps of a) reacting a mixture comprising from 78 to 95% by weight of bis- (2-hydroxyethyl) ester - fatty methylamine containing a molar ratio of fatty acid plots to amine plots from 1.80 to
    '1.96, an average chain length number of the fatty acid portions of 16 to 18 carbon atoms and an iodine value, calculated for the free fatty acid, from 0 to 50, from 2 to 9% by weight of a fatty acid triglyceride containing an average fatty acid chain length of 10 to 14 carbon atoms and an iodine value, calculated for free fatty acid, from 0 to 15, and from 3 to 13% by weight of an alcohol selected from ethanol, 1-propanol and 2-propanol with an excess of methyl chloride at a temperature of 60 to 120ºC until providing a reaction mixture, and b) separation of unreacted methyl chloride from the re- mixture. action of step a) by distillation of the mixture of methyl chloride and the respective alcohol, condensation of the alcohol! of said mixture of methyl chloride and: alcohol and return of condensed alcohol to said reaction mixture to provide an alcohol content of 3 to 12% by weight.
    [7]
    Process for preparing an active fabric softener composition according to claim 1, comprising the steps of a) reaction of the mixture comprising from 88 to 98% by weight of bis- (2-hydroxyethyl) ester -fatty methylamine containing a ratio —mold out plots of fatty acid to amine plots from 1.80 to 1.96, an average chain length number of plots of fatty acid from 16 to 18 carbon atoms and an iodine value, calculated for free fatty acid, from 0 to 50, from 2 to 9% by weight of a fatty acid triglyceride with an average chain length of the fatty acid portions of 10 to 14 carbon atoms and an iodine value, calculated for free fatty acid, from O to 15, and from O to 3% by weight of an alcohol selected from ethanol, 1-propanol and 2-propanol with an excess of methyl chloride at a temperature of 60 to 120ºC until supply a reaction mixture, b) adding more alcohol to the reaction mixture from step a) until it reaches a alcohol of 3 to 12% by weight, and c) separation of unreacted methyl chloride from the mixture of step b) by distillation of a mixture of methyl chloride and said alcohol,
    | condensation of alcohol from said mixture of methyl chloride and alcohol and return of condensed alcohol to said reaction mixture until it reaches an alcohol content of 3 to 12% by weight.
    [8]
    A process according to claim 6 or claim 7, wherein the methyl chloride and alcohol are distilled at a total pressure of (0.2 to 1 bar).
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    同族专利:
    公开号 | 公开日
    WO2011120836A1|2011-10-06|
    IL220908A|2015-07-30|
    AU2011234658B2|2014-12-04|
    EP2553067B1|2015-02-18|
    EP2553067A1|2013-02-06|
    KR101425294B1|2014-07-31|
    DK2553067T3|2015-05-26|
    RU2526035C1|2014-08-20|
    EG27007A|2015-03-30|
    US8563499B2|2013-10-22|
    CA2795152A1|2011-10-06|
    KR20130019387A|2013-02-26|
    MX2012011005A|2012-10-15|
    JP5460919B2|2014-04-02|
    SG184397A1|2012-11-29|
    UA106790C2|2014-10-10|
    ZA201207287B|2013-06-26|
    CN102803456B|2014-06-11|
    MA34103B1|2013-03-05|
    JP2013525615A|2013-06-20|
    CA2795152C|2014-03-18|
    AP2012006438A0|2012-08-31|
    US20110245139A1|2011-10-06|
    CN102803456A|2012-11-28|
    ES2536849T3|2015-05-29|
    PL2553067T3|2015-07-31|
    AU2011234658A1|2012-08-09|
    MY159502A|2017-01-13|
    AP4034A|2017-02-12|
    BR112012025002B1|2021-02-23|
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    法律状态:
    2020-09-24| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-10-20| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-10-27| B25D| Requested change of name of applicant approved|Owner name: EVONIK OPERATIONS GMBH (DE) |
    2021-01-05| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-02-23| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 22/03/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US31999710P| true| 2010-04-01|2010-04-01|
    US61/319,997|2010-04-01|
    PCT/EP2011/054282|WO2011120836A1|2010-04-01|2011-03-22|Fabric softener active composition|
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