Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3723—Polyamines or polyalkyleneimines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/02—Polyamines
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/62—Quaternary ammonium compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/001—Softening compositions
  • C11D3/0015—Softening compositions liquid

Definitions

• the present invention relates to ethoxylated amino-functional polymers which have low malodour and good colour characteristics, and process thereof.
• odor free starting materials are highly desirable.
• perfumes are optionally added to detergent formulations to impart a desirable fragrance, but some consumers desire a "fragrance free” material.
• the presence of malodorous materials in laundry starting materials limits the usefulness of these materials in fragrance sensitive formulations.
• modified polyamines have as their starting materials in many cases polyalkyleneimine backbones. Many forms of polyalkyleneamines have been known to those skilled in the laundry art and are obtainable in low odor forms. However, recent discoveries reveal that modifications of these polyalkyleneamines produce a class of materials having unique surface active and fabric substantive properties as well as novel metal chelation properties. In addition, these modified polyamines provide care to the colours of fabrics.
• Hemiacetals of acetaldehyde or higher unsaturated aldehydes is one of the possible form for "hidden" aldehydes.
• a hemiacetal of acetaldehyde itself is illustrated below:
• Hemiacetals such as this should, however, be in equilibrium with the alcohol and the aldehyde under both basic and acidic conditions so it is believed that it should not require acidification to release aldehyde. However, release might be faster in a strongly acidic system.
• hydroxyl of a hemiacetal would likely be the most acidic alcohol in the system and hence under mildly basic conditions may be easier to ethoxylate than one of the more abundant hydroxyethyl groups. If this occurs, an acetal would form that would be locked in until acidified.
• these ethoxylated amino-functional polymers can have their content of malodorous compounds reduced or removed by several direct or undirect methods so that the content of total aldehydes expressed as acetaldehyde within the raw material is present in less than 100ppm after contact with an acidic medium.
• One method includes contacting the modified polyamines with sodium sulfite prior to acidification in such a way that the acidified solution contains about 0.5 to 1 % w/w of added sodium sulfite.
• Another suitable method includes contacting the polyamines prior to any acidification with borohydride salt either during the ethoxylation or after ethoxylation.
• Another suitable method includes underhydroxyethylation involving hydroxyethylation to less than one equivalent per reactive NH group and then using the modified amine as such or by adding strongly basic catalyst and ethoxylating to the desired degree.
• One aspect of the present invention is an ethoxylated amino-functional polymer, characterised in that said polymer comprises less than 100ppm of total aldehyde compounds expressed as acetaldehyde after contact with an acidic medium.
• a process for obtaining a polymer as defined hereinbefore which comprises the steps of treating the ethoxylated polyamino-functional polymer with sodium sulfite prior to acidification such that the acidified polymer contains from 0.5 to 1 % w/w of added sodium sulfite.
• composition comprising said modified polyamine.
• Still a further aspect of the invention is the use of said modified amino-functional polymer with reduced discoloration and malodour arising from the contacting of said polymer with an acidic medium
• the essential component of the invention is an ethoxylated amino-functional polymer with less than 100ppm, preferably less than 50ppm, and more preferably less than 25 ppm of total aldehyde compounds expressed as acetaldehyde after contact with an acidic medium.
• the above mentioned aldehydes are by-product of the amino-functional polymer as a raw material and which are produced while the making of the polymer and upon acidic conditions. It is not intended to include the aldehydes of the fully formulated composition in which the polymer is used.
• acidic medium any particular medium having an acidic pH, that is less than 7, preferably less than 6, more preferably from 2.0 to 5, most preferably from 2.5 to 4.5, and even most preferably from 2.5 to 3.5.
• Typical of this acidic medium can be a fabric softening composition, or even acidic processing steps that could be involved whilst processing the ethoxylated amino-functional polymer into fully formulated compositions or processing of the fully formulated composition comprising said polymer. Indeed, as soon as the untreated ethoxylated polymer is in contact with an acidic medium irrespective of whether it is in raw material form or even incorporated into fully-formulated compositions, aldehyde by-products will be produced. However, the resulting fully-formulated compositions do not need to be acidic.
• contacting it is meant that the ethoxylated polymer is present in an acidic medium for at least a comparable time for that of untreated ethoxylated polymers to form the aldehydes by-products.
• the rate of formation of the by-product will of course depend on the nature of the impurity, its quantity, as well as the pH value of its medium.
• the amino-functional polymers for use herein have a molecular weight between 200 and 10 ⁇ , preferably between 600 and 20,000, most preferably between 1000 and 10,000.
• These polyamines comprise backbones that can be either linear or cyclic.
• the polyamine backbones can also comprise polyamine branching chains to a greater or lesser degree.
• the polyamine backbones described herein are modified in such a manner that at least one, preferably each nitrogen of the polyamine chain is thereafter described in terms of a unit that is substituted, quaternized, oxidized, or combinations thereof.
• linear or non-cyclic polyamine backbones that comprise the amino-functional polymer have the general formula:
• cyclic polyamine backbones that comprise the amino-functional polymer have the general formula:
• primary amine nitrogens comprising the backbone or branching chain once modified are defined as V or Z "terminal" units.
• V or Z "terminal" units when a primary amine moiety, located at the end of the main polyamine backbone or branching chain having the structure
• H 2 N-R]- is modified according to the present invention, it is thereafter defined as a V "terminal" unit, or simply a V unit.
• V terminal unit
• some or all of the primary amine moieties can remain unmodified subject to the restrictions further described herein below. These unmodified primary amine moieties by virtue of their position in the backbone chain remain “terminal” units.
• a primary amine moiety located at the end of the main polyamine backbone having the structure
• -NH 2 is modified according to the present invention, it is thereafter defined as a Z "terminal" unit, or simply a Z unit. This unit can remain unmodified subject to the restrictions further described herein below.
• secondary amine nitrogens comprising the backbone or branching chain once modified are defined as W "backbone" units.
• W backbone
• H — [N-R]- is modified according to the present invention, it is thereafter defined as a W "backbone” unit, or simply a W unit.
• W backbone
• some or all of the secondary amine moieties can remain unmodified. These unmodified secondary amine moieties by virtue of their position in the backbone chain remain "backbone” units.
• tertiary amine nitrogens comprising the backbone or branching chain once modified are further referred to as Y "branching" units.
• Y branch point of either the polyamine backbone or other branching chains or rings, having the structure
• [N-R]- is modified according to the present invention, it is thereafter defined as a Y "branching" unit, or simply a Y unit.
• some or all or the tertiary amine moieties can remain unmodified. These unmodified tertiary amine moieties by virtue of their position in the backbone chain remain “branching" units.
• the R units associated with the V, W and Y unit nitrogens which serve to connect the polyamine nitrogens, are described herein below.
• V(n-k+1)WmYnY'kZ for cyclic amino-functional polymer.
• [N-R]— serves as a branch point for a backbone or branch ring.
• Y' unit there is a Y unit having the formula
• the polyamine backbone has the formula
• the polyamine backbones of the present invention comprise no rings.
• the ratio of the index n to the index m relates to the relative degree of branching.
• a fully non-branched linear modified polyamine according to the present invention has the formula
• VW m Z that is, n is equal to 0.
• n the lower the ratio of m to n
• m ranges from a minimum value of 2 to 700, preferably 4 to 400, however larger values of m, especially when the value of the index n is very low or nearly 0, are also preferred.
• Each polyamine nitrogen whether primary, secondary or tertiary, once modified according to the present invention, is further defined as being a member of one of three general classes; simple substituted, quaternized or oxidized. Those polyamine nitrogen units not modified are classed into V, W, Y, Y' or Z units depending on whether they are primary, secondary or tertiary nitrogens. That is unmodified primary amine nitrogens are V or Z units, unmodified secondary amine nitrogens are W units or Y' units and unmodified tertiary amine nitrogens are Y units for the purposes of the present invention.
• Modified primary amine moieties are defined as V "terminal" units having one of three forms: a) simple substituted units having the structure:
• Modified secondary amine moieties are defined as W "backbone" units having one of three forms: a) simple substituted units having the structure: -N-R—
• R b quaternized units having the structure:
• modified secondary amine moieties are defined as Y' units having one of three forms: a) simple substituted units having the structure:
• R b quaternized units having the structure:
• Modified tertiary amine moieties are defined as Y "branching" units having one of three forms: a) unmodified units having the structure:
• Certain modified primary amine moieties are defined as Z "terminal" units having one of three forms: a) simple substituted units having the structure:
• a primary amine unit comprising one R' unit in the form of a hydroxyethyl moiety is a V terminal unit having the formula (HOCH 2 CH2)HN-.
• V and Z units there are two types of chain terminating units, the V and Z units.
• the Z "terminal" unit derives from a terminal primary amino moiety of the structure -NH2.
• Non-cyclic polyamine backbones according to the present invention comprise only one Z unit whereas cyclic polyamines can comprise no Z units.
• the Z "terminal" unit can be substituted with any of the R' units described further herein below, except when the Z unit is modified to form an N-oxide.
• the Z unit nitrogen is oxidized to an N-oxide, the nitrogen must be modified and therefore R' cannot be a hydrogen.
• the polyamines of the present invention comprise backbone R "linking" units that serve to connect the nitrogen atoms of the backbone.
• R units comprise units that for the purposes of the present invention are referred to as “hydrocarbyl R” units and “oxy R” units.
• the "hydrocarbyl" R units are C2-C12 alkylene, C4-C12 alkenylene, C3-C12 hydroxyalkylene wherein the hydroxyl moiety may take any position on the R unit chain except the carbon atoms directly connected to the polyamine backbone nitrogens; C4-C12 dihydroxyalkylene wherein the hydroxyl moieties may occupy any two of the carbon atoms of the R unit chain except those carbon atoms directly connected to the polyamine backbone nitrogens; C ⁇ - C12 dialkylarylene which for the purpose of the present invention are arylene moieties having two alkyl substituent groups as part of the linking chain.
• a dialkylarylene unit has the formula
• the unit need not be 1 ,4-substituted, but can also be 1 ,2 or 1 ,3 substitutedC2-Ci2 alkylene, preferably ethylene, 1 ,2-propylene, and mixtures thereof, more preferably ethylene.
• the "oxy" R units comprise -
• Preferred R units are selected from the group consisting of C2-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene, C8-C12 dialkylarylene, -(R 1 O) x Rl-, CH 2 CH(OR 2 )CH 2 -, -(CH 2 CH(OH)CH2 ⁇ ) z (R 0) y R (OCH2CH-(OH)CH2) w -, - (R 1 0) x R 5 (OR 1 ) x -, more preferred R units are C2-C12 alkylene, C3-C-12 hydroxy-alkylene, C4-C12 dihydroxyalkylene, -(R 0) x R 1 -, -(R 0) x R 5 (OR 1 ) x -, - (CH2CH(OH)CH2 ⁇ ) z (R 1 O) y R 1 (OCH2CH-(OH)CH2) w -, and mixtures
• amino-functional polymers of the present invention are selected from a)-linear or non-cyclic polyamines having a backbone of the formula:
• R' is - (CH 2 CH 2 O) x H, and the other is selected from R' units selected from hydrogen, 1-C22 a 'kyl, C3-C22 alkenyl, C7-C22 arylalkyl, C2-C22 hydroxyalkyl, - (CH 2 ) p C0 2 M, -(CH 2 )qSO 3 M, -CH(CH 2 C0 2 M)CO 2 M, -(CH 2 ) p PO 3 M, - (R O) m B, -C(0)R3, wherein the backbone linking R units are selected from the group consisting of C2-C12 alkylene, C4-C12 alkenylene, C3-C-12 hydroxyalkylene, C4
• x has a value lying in the range of from 1 to 20, preferably from 1 to 10.
• R is selected from the group consisting of C2-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene, C8-C12 dialkylarylene, -(R 1 O) x Rl-, -(R1 O) X R 5 (OR1 ) X -, -(CH 2 CH(OH)CH 2 O) z (R 0) y R 1 -(OCH 2 CH(OH)CH 2 ) w -, - CH2CH(OR 2 )CH2-, and mixtures thereof, more preferably R is selected from the group consisting of C2-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene, -(R 0) x R 1 -, -(Rl ⁇ ) x R 5 -(OR 1 ) x -,
• R is selected from the group consisting of C2-C5 alkylene, C3 hydroxyalkylene and mixtures thereof.
• a most preferred R group is C2-CQ alkylene.
• R1 is selected from the group consisting of C2-C6 alkylene, C3-C6 alkyl substituted alkylene, and mixtures thereof, more preferably R1 is ethylene.
• R 2 is hydrogen
• R3 is selected from the group consisting of C1-C12 alkyl, C7-C12 alkylarylene, and mixtures thereof, more preferably R3 is selected from the group consisting of C1-C12 alkyl and mixtures thereof, most preferably R is selected from the group consisting of C1-C6 alkyl and mixtures thereof.
• a most preferred group for R3 is methyl.
• R 4 is selected from the group consisting of C2-C12 alkylene, C8-C12 arylalkylene, and mixtures thereof, more preferably R 4 is selected from the group consisting of C2-C5, most preferably R 4 is ethylene or butylene.
• R ⁇ is selected from the group consisting of ethylene, -C(O)-, C(O)NHR6NHC(O)-, -R 1 (OR 1 ) y -, -(CH2CH(OH)CH 2 O) z (Rl ⁇ ) y R 1 -
• R' units are selected from the group consisting of hydrogen, C3-C22 hydroxyalkyl, benzyl, C1-C22 alkyl, -(R 0) x B, -C(0)R3, -(CH 2 )pCO 2 -M + , - (CH2)qS03"M + , -CH(CH2CO2M)C02M and mixtures thereof, more preferably R' units are selected from the group consisting of hydrogen, C1-C22 alkyl, - (R 1 O) x B, -C(0)R 3 , and mixtures thereof, most preferably R' units are -(R 1 O) x B.
• B units are selected from the group consisting of hydrogen, Ci-C ⁇ alkyl, -(CH 2 )qSO 3 M, -(CH2)q(CHSO 3 M)CH 2 SO3M, -(CH 2 ) q (CHSO2M)- CH2SO3M, and mixtures thereof, more preferably B is selected from the group consisting of hydrogen, -(CH2) q S03M, -(CH2) q (CHS ⁇ 3M)CH2S ⁇ 3M, - ( CH 2)q( C S0 2 M )- CH 2 S0 3 M . and mixtures thereof, most preferably B is selected from the group consisting of hydrogen, wherein q has the value from 0 to 3.
• M is hydrogen or a water soluble cation in sufficient amount to satisfy charge balance.
• a sodium cation equally satisfies -(CH2) p CO2M, and "(CH2) q S03M, thereby resulting in -(CH2) p CO2Na, and -(CH2) q SO3Na moieties.
• More than one monovalent cation, (sodium, potassium, etc.) can be combined to satisfy the required chemical charge balance.
• more than one anionic group may be charge balanced by a divalent cation, or more than one mono-valent cation may be necessary to satisfy the charge requirements of a poly-anionic radical.
• a -(CH2) p PO3M moiety substituted with sodium atoms has the formula -(CH2) p P ⁇ 3Na3.
• Divalent cations such as calcium (Ca 2+ ) or magnesium (Mg 2+ ) may be substituted for or combined with other suitable mono-valent water soluble cations.
• Preferred cations are sodium and potassium, more preferred is sodium.
• X is a water soluble anion such as chlorine (Cl-), bromine (Br) and iodine (I-) or X can be any negatively charged radical such as sulfate (SO4 2" ) and methosulfate (CH3SO3-).
• the preferred "oxy" R units are further defined in terms of the R1 , R 2 , and R 5 units.
• Preferred "oxy" R units comprise the preferred R1 , R 2 , and R ⁇ units.
• the preferred agents of the present invention comprise at least 50% R1 units that are ethylene.
• Preferred R1 , R 2 , and R ⁇ units are combined with the "oxy” R units to yield the preferred "oxy” R units in the following manner. i) Substituting more preferred R 5 into -(CH2CH2 ⁇ ) x R 5 (OCH2CH2) x - yields -(CH2CH2O) x CH2CHOHCH2(OCH 2 CH2) x -.
• R' units do not comprise hydrogen atom when the V, W or Z units are oxidized, that is the nitrogens are N-oxides.
• the backbone chain or branching chains do not comprise units of the following structure:
• R' units do not comprise carbonyl moieties directly bonded to a nitrogen atom when the V, W or Z units are oxidized, that is, the nitrogens are N- oxides.
• the R' unit -C(0)R 3 moiety is not bonded to an N-oxide modified nitrogen, that is, there are no N-oxide amides having the structure
• indices have the following values: p has the value from 1 to 6, q has the value from 0 to 6; r has the value 0 or 1 ; w has the value 0 or 1 , x has the value from 1 to 100; y has the value from 0 to 100; z has the value 0 or 1 ; m has the value from 2 to 700, preferably from 4 to 400, n has the value from 0 to 350, preferably from 0 to 200; m + n has the value of at least 5.
• x has a value lying in the range of from 1 to 20, preferably from 1 to 10.
• the compounds of the present invention comprise polyamines having a ratio of m : n that is at least 0.5:1 but may include linear polymers (n equal to 0) as well as a range as high as 10:1 , preferably the ratio is 1 :1 to 2:1.
• the ratio of m:n is 2:1
• the ratio of primary:secondary:tertary amine moieties, that is the ratio of -RNH2, -RNH, and -RN moieties is 1 :2:1.
• R units are preferably selected from the group consisting of ethylene, 1 ,2- propylene, 1 ,3-propylene, and mixtures thereof, more preferably ethylene. R units serve to connect the amine nitrogens of the backbone.
• the preferred polyamines of the present invention comprise backbones wherein less than 50% of the R groups comprise more than 3 carbon atoms.
• the use of two and three carbon spacers as R moieties between nitrogen atoms in the backbone is advantageous for controlling the fabric appearance enhancement properties of the molecules.
• More preferred embodiments of the present invention comprise less than 25% moieties having more than 3 carbon atoms.
• Yet more preferred backbones comprise less than 10% moieties having more than 3 carbon atoms.
• Most preferred backbones comprise 100% ethylene moieties.
• the amino-functional polymers of the present invention comprise homogeneous or non-homogeneous polyamine backbones, preferably homogeneous backbones.
• homogeneous polyamine backbone is defined as a polyamine backbone having R units that are the same (i.e., all ethylene). However, this sameness definition does not exclude polyamines that comprise other extraneous units comprising the polymer backbone that are present due to an artifact of the chosen method of chemical synthesis.
• ethanolamine may be used as an "initiator" in the synthesis of polyethyleneimines, therefore a sample of polyethyleneimine that comprises one hydroxyethyl moiety resulting from the polymerization "initiator” would be considered to comprise a homogeneous polyamine backbone for the purposes of the present invention.
• non-homogeneous polymer backbone refers to polyamine backbones that are a composite of one or more alkylene or substituted alkylene moieties, for example, ethylene and 1 ,2- propylene units taken together as R units
• Other polyamines that comprise the backbone of the compounds of the present invention are generally polyalkyleneimines (PAI's), preferably polyethyleneimines (PEI's).
• PAI's polyalkyleneimines
• PEI's polyethyleneimines
• the PEI's which comprise the preferred backbones of the polyamines of the present invention can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc.
• the present invention also includes the cyclic amines that are typically formed as artifacts of synthesis. The presence of these materials may be increased or decreased depending on the conditions chosen by the formulator.
• alkoxylated amino-functional polymer suitable for use herein are hydroxyethylated poly(ethyleneimine) from Polysciences, with a MW2000, and 80% hydroxyethylated poly(ethyleneimine) from Aldrich.
• Typical methods for the removal of aldehydes in order to obtain an ethoxylated amino-functional polymer with good color and odor is by either preventing the quaternary form or aldehydes from forming or by the removal of the formed aldehyde.
• the first step in the process of ethoxylating polyamines is conducted without the need of a base catalyst This fact is due primarily to the higher reactivity of primary and secondary amines relative to alcohols.
• the more reactive primary amino moieties react with ethylene oxide and are subsequently converted to "hydroxyethylamines" the remaining occluded and lesser reactive secondary amines require more residence time to undergo successful hydroxyethylation.
• this critical time when essentially 80% to 90% of the amino N-H hydrogens are hydroxyethylated, the undesirable side reactions described herein above, increase in frequency.
• one means for limiting the amount of malodorous aldehydes and aldehyde precursors formed in the first step is to limit the degree of hydroxyethylation of the polyamine prior to addition of a base catalyst. Therefore, the formulator can insure the minimization of malodor causing aldehydes by charging to the polyamine at least about 5% of the amount of ethylene oxide necessary to hydroxyethylate all or the polyamine backbone N- H hydrogens.
• the amount of ethylene oxide added is less than about 75%, more preferably less than about 85%, most preferably less than about 90%.
• the formulator can effectively truncate the addition of ethylene oxide to the polyamine nitrogens by using less than a stoichiometric amount of ethylene oxide in the first, non-base catalyzed step of the process of the present invention.
• Formation of ethoxylated polyamines having an average ethoxylation of at least about Erj.6 > preferably at least about En.75, more preferably at least about Erj.85- most preferably at least about En g, as the first step of the process of the present invention is a suitable method for controlling the formation of aldehydes which lead to malodor and color formation.
• One method is to treat a solution of alkoxylated PEI with sulfite salt or equivalent, preferably sodium, prior to acidification in such a way that the acidified solution contains around 0.5 to 1% w/w of added sodium sulfite. That particular method is useful for all pH, in particular for acidic pH.
• a solution of the amino-functional polymer is made at a concentration higher than the desired final concentration such that the latter is achieved at the end of the operation.
• An aliquot of a stock solution of sodium sulfite is added to this solution of polymer, and the mixture is slowly acidified with concentrated HCI while controlling the heat dissipation with a coolant (water flow in jacketed beaker or ice pillow) until the desired pH is obtained.
• a further method for ameliorating the formation of aldehydes involves treatment of the crude reaction mixture at any stage with borohydride reducing agents.
• the initial hydroxyethylation is typically conducted without the aid of a catalyst due to the nucleophilic character of the amino moieties, however, as the number of more reactive primary amino units decreases relative to the less reactive secondary amino units, the rate of hydroxyethylation decreases and the opportunity for aldehyde formation increases.
• the formulator may include in the reaction process admixture in step (a) a suitable amount of a borohydride reagent.
• borohydride reagents include sodium borohydride, lithium borohydride and the like.
• a borohydride reagent can also be added after the hydroxyethylation stage as a post-treatment, or may be added at the point of addition of strong base catalyst if further ethoxylation is to be done.
• Addition of a borohydride can be also be done at any later stage of ethoxyation, including after completion of any strong base-catalyzed ethoxylation step and may be done before or after neutralization of the strong base catalyst. Multiple additions of borohydride at different points in the synthesis is also included in the invention.
• Borohydride may also be used in continuous processes and may be used on a fixed support or inert, filterable solid support.
• the formulator may suitably combine any of the above techniques for using borohydride salts to ameliorate malodor and color.
• methods not specifically described herein above for contacting a borohydride salt with an ethoxylated polyamine during the formation or purification of said ethoxylated polyamine are considered to be included in the present process.
• a further process for removing the malodorous compounds from ethoxylated polyamines such as those described hereinbefore involves the use of up to one weight equivalent of liquid water which is converted in situ to steam This process can be operated in a continuous, semi-continuous or batchwise manner. When the water is introduced in a particular way and/or in a particular form, the removal of undesirable volatile impurities in the ethoxylated polyamine is also found to be improved. The level of impurities which are formed in the process of ethoxylating the polyamine, however, may dictate the operating conditions of the deodorization process.
• Severe operating conditions may be necessary as the impurities level in hydroxyethylated polyamine increases, especially in the case of a continuous or semi-continuous process.
• the amount of water that is used in the present process is typically less than one weight equivalent of the ethoxylated polyamine, preferably less than 0.5 weight equivalent.
• 500 gm of water is normally sufficient to deodorize 1000 gm of ethoxylated polyamine.
• the original polyamines, partially hydroxyethylated polyamines and fully hydroxyethylated polyamine are typically highly water soluble materials and the formulator may select a final product that is not void of all deodorization water and therefore more than the theoretical amount of water can be used in processes of this type.
• the modified malodorous ethoxylated polyamine in the form of a solid, gel, viscous syrup, or liquid is charged to a vessel.
• the vessel in which the hydroxyethylation was conducted can also serve as a suitable reaction vessel.
• the vessel may be open to the atmosphere but typically is a closed system adapted for gas sparging, vacuum, pressurization, and other typical processing aids compatible with the deodorization of ethoxylated polyamines.
• the present water vaporization process provides some degree of agitation, the formulator may find it advantageous to provide an external source of mechanical agitation. This is especially true for lower temperature processes or for processes that involve highly water absorbing ethoxylated polyamines.
• a source of heat is used to increase the temperature of the ethoxylated polyamine to greater than the boiling point of water.
• the term "above the boiling point of water” is taken to be the temperature at which injected liquid water is vaporized to steam.
• the temperature must be sufficiently high whereby the vaporization of injected water does not sufficiently cool the surrounding heat transfer media (typically the ethoxylated polyamine being deodorized) in a manner sufficient to interrupt the deodorization rate or cause a change in the rate of incoming water.
• the observed boiling point of water at standard atmospheric conditions is taken to be 100° C. However, processes conducted at higher altitudes or under reduced pressure will obviously have an adjusted "boiling point of water”.
• Heating can be accomplished by jacketing the vessel, by immersion of either steam or electrical heating coils, or by any other means wherein the temperature can be suitably controlled. It is necessary that uniform dispersion of the heat takes place to insure that the material is maintained at a steady temperature. Once the desired temperature is achieved, water is introduced at such a rate that the liquid water is completely vaporized to steam by the surrounding medium. This water, now in the form of steam, serves to extract the volatile aldehyde malodor compounds as it passes out of the solution. The rate at which the liquid water is introduced into the vessel must not cool the polyamine to such a degree that there is an accumulation of liquid water.
• a pre-determined amount of water may be added to a vessel containing the ethoxylated polyamine to be deodorized.
• the vessel may be at room temperature or at any temperature below the boiling point of water.
• the vessel is then heated to a temperature above the boiling point of water.
• the formulator may choose to remove all of the water present or the formulator may choose to leave any water still present beyond the amount necessary to deodorize the ethoxylated polyamine.
• 0.5 weight equivalent of water may be necessary to remove the malodorous materials from a sample of ethoxylated polyamine yet the formulator may add an excess of 0.5 weight equivalents of water. After removing 0.5 weight equivalents of water, the now deodorized polyamine contains 0.5 weight equivalents of water.
• This water may be desirable for the subsequent formulation of the ethoxylated polyamine or may be necessary for further processing steps. Therefore the process of the present invention does not require removal of all added water from the polyamine.
• Both the quantity of heat and water introducing means employed, however, may not be critical as long as the starting material in the deodorization vessel is subject to a particular amount of a water at a deodorization temperature of at least about 110° C to about 200° C, preferably from about 135° C to about 175° C, more preferably from about 140° C to about 160° C when the temperature is measure at standard atmospheric conditions.
• the initial temperature at which the deodorization process is conducted may be higher or lower than the final deodorization temperature.
• One preferable embodiment of this malodor removal technique increases the temperature of the ethoxylated polyamine to the minimum temperature sufficient to conduct deodorization and then over the course of the process increases the temperature stepwise or at a steady rate until a final deodorization temperature is obtained.
• This steady increase in temperature or "temperature ramping" is conducted at a rate of from about 0.01° C per minute to about 10° C per minute, preferably from about 0.1° C per minute to about 5° C per minute, more preferably from about 0.1° C per minute to about 1° C per minute.
• a temperature change of approximately 100° C is suitable for deodorizing the polyamines, preferably the temperature change is approximately 60° C over the course of the deodorization process.
• the residence time in which the introduced water remains in the liquid state prior to vaporization is a critical variable adjustable under the conditions of the present process.
• the liquid phase residence time can . be adjusted by the formulator to fit the type of ethoxylated polyamine present or the degree of deodorization necessary. This ability to adjust the rate of vaporization allows for a wide control in the liquid water contact time. For example, the formulator may find that a longer liquid water/impurity contact time favors the removal of a particular malodor.
• This control can accomplished by the adjusting the rate of water introduction as well as by varying the temperature profile of the deodorization vessel.
• it is not critical to limit the amount of water used in the removal of malodorous materials according to the present process. This is especially critical when high temperatures are necessary to remove unwanted malodorous compounds.
• the process of the present invention makes use of the surprisingly stable nature and water compatibility of the ethoxylated polyamines described herein above.
• the water may be introduced at any depth of the reaction vessel especially if sufficient agitation or mixing of the ethoxylated polyamine is achieved.
• the formulator may rely upon the agitation caused by the vaporization of the water and escape of the resultant steam to efficiently mix the contents of the deodorization vessel.
• the source of water may be introduced at the bottom of the deodorization vessel by a single water injection port, along a removable vertical tube having a plurality of water injection ports extending from the bottom of the vessel to a level just below the surface of the polyamine, or by a plurality of water injection ports along the surface of the vessel itself.
• the shape and means in which the water is introduced into the vessel containing the ethoxylated polyamine does not effect the efficiency of the present process.
• This method also relates to a process for removing the malodorous compounds from ethoxylated polyamines by the use of a particular amount of a non-condensable gas which can be operated in a continuous, semicontinuous or batchwise manner.
• non- condensable gases suitable for use in the present process are helium, argon, carbon dioxide, and nitrogen. However, this list is not meant to be totally inclusive of all gases suitable for the present invention.
• the non- condensable gas is introduced in a particular way and/or in a particular form, the removal of undesirable volatile impurities in the ethoxylated polyamine is also found to be improved.
• the level of impurities in the starting ethoxylated polyamine may dictate the operating conditions of the deodorization process. Severe operating conditions, for example, may be necessary as the impurities level in the starting material fed to the deodorization vessel increases.
• the stripping gas may be introduced by means such as sparging or distributing means having particular orifice sizes, preferably placed in at least one upper, middle and lower sections of the vessel. Both the quantity of heat and stripping gas introducing means employed, however, may not be critical as long as the starting material in the deodorization vessel is subject to a particular amount of a stripping gas at a deodorization temperature of at least about 110° C to about 200° C, preferably from about 135° C to about 175° C, more preferably from about 140° C to about 160° C. Typically a temperature change of approximately 100° C is suitable for deodorizing the ethoxylated polyamines, preferably the temperature change is approximately 60° C over the course of the deodorization process.
• the amount of the non-condensable gas entering the vessel should be at least the minimum necessary to produce a deodorized ethoxylated polyamine product having the desired characteristics described herein.
• the minimum amount of the non-condensable gas may vary depending on the type of deodorization vessel used, the type and extent of modifications made to the polyamine backbone, and with the reaction conditions used to make said modifications.
• the present invention does not limit the volume of gas introduced per unit time nor the amount of gas introduced per unit mass of ethoxylated polyamine nor the volume of gas introduced per unit mass of water.
• the water vaporization process may be combined with the gaseous purge process. Typically this combination is employed for reasons of deodorization vessel configuration, susceptibility of the ethoxylated polyamine to degradation by air, or to increase the efficiency of low temperature deodorization.
• the gaseous purge can commence before or after the introduction of water into the vessel and may also begin or end at any temperature point.
• vacuum may be used to assist in the deodorization process.
• the vacuum may be formed by a pump, by a steam injector, or by any other suitable means of forming a vacuum.
• the amount of vacuum may vary or be constant during the deodorization process.
• the amount of vacuum present during the deodorization process can range from a slight vacuum to full vacuum.
• the term "slight vacuum” is defined as a drop in the pressure of the deodorization vessel of 10% or less from the ambient pressure.
• full vacuum is defined as a pressure inside the deodorization vessel of less than 0.1 mm Hg. All other levels of vacuum is equally suitable for use in the present process.
• the exact amount of aldehyde present within the polymer so as to ensure that no more than the maximum amount of total aldehydes, expressed as acetaldehyde is present, i.e. less than 100ppm, preferably less than 50ppm, and more preferably less than 25ppm.
• KRUG A; KELLNER R "Spectrophotometric flow injection analysis of formaldehyde in aqueous solutions using 3-methyl-2-benzthiazolinone hydrazone";
• a typical titrating reagent is 3-methyl-2-benzothiazolinone hydrazone hydrochloride (MBTH).
• MBTH 3-methyl-2-benzothiazolinone hydrazone hydrochloride
• the ethoxylated amino-functional polymer thus obtained can then be used in a wide variety of applications where a care to the colors of fabrics is desired.
• Typical of such compositions include stand-alone products such as for use as a pre- and or post wash additive. It can also be used in fully-formulated compositions including laundry and cleaning compositions as well as rinse added fabric softener compositions and dryer added compositions (e.g. sheets) which provide softening and/or antistatic benefits.
• a typical amount of amino-functional polymer to be employed is of at least 0.01 % by weight, preferably of at least 1 % by weight, more preferably of from 1 % to 50% by weight of the composition, most preferably of from 1% to 10% by weight and even most preferred from 1% to 5% by weight of the composition.
• Typical levels of incorporation of the softening compound in the softening composition are of from 1 % to 80% by weight, preferably from 5% to 75%, more preferably from 15% to 70%, and even more preferably from 19% to 65%, by weight of the composition.
• the fabric softener compound is preferably selected from a cationic, nonionic, amphoteric or anionic fabric softening component.
• Typical of the cationic softening components are the quaternary ammonium compounds or amine precursors thereof as defined hereinafter.
• Preferred quaternary ammonium fabric softening active compound have the formula
• each R unit is independently hydrogen, C-i-C ⁇ alkyl, C ⁇ -CQ hydroxyalkyl, and mixtures thereof, preferably methyl or hydroxy alkyl; each R1 unit is independently linear or branched C-11-C22 alkyl, linear or branched C-11-C22 alkenyl, and mixtures thereof, R 2 is hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and mixtures thereof; X is an anion which is compatible with fabric softener actives and adjunct ingredients; the index m is from 1 to 4, preferably 2; the index n is from 1 to 4, preferably 2.
• An example of a preferred fabric softener active is a mixture of quaternized amines having the formula:
• the unit -O2CRI represents a fatty acyl unit which is typically derived from a triglyceride source.
• the triglyceride source is preferably derived from tallow, partially hydrogenated tallow, lard, partially hydrogenated lard, vegetable oils and/or partially hydrogenated vegetable oils, such as, canola oil, safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, tall oil, rice bran oil, etc. and mixtures of these oils.
• the preferred fabric softening actives of the present invention are the Diester and/or Diamide Quaternary Ammonium (DEQA) compounds, the diesters and diamides having the formula:
• R is preferably methyl, Z is -OH, -NH2, or mixtures thereof; followed by quaternization to the final softener active.
• Non-limiting examples of preferred amines which are used to form the DEQA fabric softening actives according to the present invention include methyl bis(2- hydroxyethyl)amine having the formula:
• the counterion, X « above, can be any softener-compatible anion, preferably the anion of a strong acid, for example, chloride, bromide, methylsulfate, ethylsulfate, sulfate, nitrate and the like, more preferably chloride or methyl sulfate.
• the anion can also, but less preferably, carry a double charge in which case ⁇ ( " ) represents half a group.
• Tallow and canola oil are convenient and inexpensive sources of fatty acyl units which are suitable for use in the present invention as Rl units.
• Rl units The following are non-limiting examples of quaternary ammonium compounds suitable for use in the compositions of the present invention.
• tallowyl indicates the R ⁇ unit is derived from a tallow triglyceride source and is a mixture of fatty acyl units.
• canolyl refers to a mixture of fatty acyl units derived from canola oil.
• N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride N,N-di(canolyl-oxy-ethyl)-N,N-dimethyl ammonium chloride; N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium chloride; N,N-di(canolyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium chloride; N,N-di(2-tallowyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride; N,N-di(2-canolyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride; N,N-di(2-canolyloxy-2-oxo-ethyl)-N,N-dimethyl am
• quaternay ammoniun softening compounds are methylbis(tallowamidoethyl)(2-hydroxyethyl)ammonium methylsulfate and methylbis(hydrogenated tallowamidoethyl)(2-hydroxyethyl)ammonium methylsulfate; these materials are available from Witco Chemical Company under the trade names Varisoft® 222 and Varisoft® 110, respectively. Particularly preferred is N,N-di(tallowoyl-oxy-ethyl)-N,N-dimethyl ammonium chloride, where the tallow chains are at least partially unsaturated.
• the level of unsaturation contained within the tallow, canola, or other fatty acyl unit chain can be measured by the Iodine Value (IV) of the corresponding fatty acid, which in the present case should preferably be in the range of from 5 to 100 with two categories of compounds being distinguished, having a IV below or above 25.
• IV Iodine Value
• R units are preferably methyl, however, suitable fabric softener actives are described by replacing the term "methyl” in the above examples in Table II with the units "ethyl, ethoxy, propyl, propoxy, isopropyl, butyl, isobutyl and t-butyl.
• the counter ion, X in the examples of Table II can be suitably replaced by bromide, methylsulfate, formate, sulfate, nitrate, and mixtures thereof.
• the anion, X is merely present as a counterion of the positively charged quaternary ammonium compounds. The scope of this invention is not considered limited to any particular anion.
• the pH of the compositions herein is an important parameter of the present invention. Indeed, it influences the stability of the quaternary ammonium or amine precursors compounds, especially in prolonged storage conditions.
• the pH is measured in the neat compositions at 20 °C. While these compositions are operable at pH of less than about 6.0, for optimum hydrolytic stability of these compositions, the neat pH, measured in the above-mentioned conditions, must preferably be in the range of from about 2.0 to about 5, preferably in the range of 2.5 to 4.5, preferably about 2.5 to about 3.5.
• the pH of these compositions herein can be regulated by the addition of a Bronsted acid.
• suitable acids include the inorganic mineral acids, carboxylic acids, in particular the low molecular weight (C1-C5) carboxylic acids, and alkylsulfonic acids. Suitable inorganic acids include HCI, H2SO4, HNO3 and H3PO4.
• Suitable organic acids include formic, acetic, citric, methylsulfonic and ethylsulfonic acid.
• Preferred acids are citric, hydrochloric, phosphoric, formic, methylsulfonic acid, and benzoic acids.
• the softening compositions are preferably used in the pH ranges above mentioned, that is acidic conditions.
• acidic conditions ethoxylated amino-functional polymers which have not been treated so as to eliminate the aldehydes present within the raw material will produce these indesirable by-product thus producing a malodour and discoloration.
• the amino-functional polymer of the invention this is not so, the polymer are stable upon acidic conditions and so is their resulting odor and color.
• the diester when specified, it will include the monoester that is normally present in manufacture. For softening, under no/low detergent carry-over laundry conditions the percentage of monoester should be as low as possible, preferably no more than about 2.5%. However, under high detergent carry-over conditions, some monoester is preferred.
• the overall ratios of diester to monoester are from about 100:1 to about 2:1 , preferably from about 50:1 to about 5:1 , more preferably from about 13:1 to about 8:1. Under high detergent carry-over conditions, the di/monoester ratio is preferably about 11 :1.
• the level of monoester present can be controlled in the manufacturing of the softener compound.
• Mixtures of actives of formula (1) and (2) may also be prepared.
• quaternary ammonium fabric softening compounds for use herein are cationic nitrogenous salts having two or more long chain acyclic aliphatic C8-C22 hydrocarbon groups or one said group and an arylalkyl group which can be used either alone or as part of a mixture are selected from the group consisting of:
• R 4 is an acyclic aliphatic C8-C22 hydrocarbon group
• R ⁇ is a C ⁇ C4 saturated alkyl or hydroxyalkyl group
• R ⁇ is selected from the group consisting of R 4 and R5 groups
• A- is an anion defined as above;
• n is equal to 1 to about 5, and R1 , R 2 , R 5 and A- are as defined above;
• Examples of the above class cationic nitrogenous salts are the well-known dialkyldi methylammonium salts such as ditailowdimethylammonium chloride, ditallowdimethylammonium methylsulfate, di(hydrogenatedtallow)dimethylammonium chloride, distearyldimethylammonium chloride, dibehenyldimethylammonium chloride. Di(hydrogenatedtallow)di methylammonium chloride and ditallowdimethylammonium chloride are preferred.
• dialkyldimethyl ammonium salts examples include di(hydrogenatedtallow)dimethylammonium chloride (trade name Adogen® 442), ditallowdimethylammonium chloride (trade name Adogen® 470, Praepagen® 3445), distearyl dimethylammonium chloride (trade name Arosurf® TA-100), all available from Witco Chemical Company.
• Dibehenyldimethylammonium chloride is sold under the trade name Kemamine Q-2802C by Humko Chemical Division of Witco Chemical Corporation.
• Dimethylstearylbenzyl ammonium chloride is sold under the trade names Varisoft ® SDC by Witco Chemical Company and Ammonyx® 490 by Onyx Chemical Company.
• Suitable amine fabric softening compounds for use herein, which may be in amine form or cationic form are selected from:
• the preferred Component (i) is a nitrogenous compound selected from the group consisting of the reaction product mixtures or some selected components of the mixtures.
• One preferred component (i) is a compound selected from the group consisting of substituted imidazoline compounds having the formula:
• R? is an acyclic aliphatic C15-C21 hydrocarbon group and R ⁇ is a divalent C1-C3 alkylene group.
• Component (i) materials are commercially available as: Mazamide® 6, sold by Mazer Chemicals, or Ceranine® HC, sold by Sandoz Colors & Chemicals; stearic hydroxyethyl imidazoline sold under the trade names of Alkazine® ST by Alkaril Chemicals, Inc., or Schercozoline® S by Scher Chemicals, Inc.; N,N"- ditallowalkoyldiethylenetriamine; 1 -tallowamidoethyl-2-tallowimidazoline (wherein in the preceding structure R1 is an aliphatic C15-C17 hydrocarbon group and R 8 is a divalent ethylene group).
• compositions (i) can also be first dispersed in a Bronsted acid dispersing aid having a pKa value of not greater than about 4; provided that the pH of the final composition is not greater than about 6.
• a Bronsted acid dispersing aid having a pKa value of not greater than about 4; provided that the pH of the final composition is not greater than about 6.
• Some preferred dispersing aids are hydrochloric acid, phosphoric acid, or methylsulfonic acid.
• N,N"-ditallowalkoyldiethylenetriamine and 1-tallow(amidoethyl)-2- tallowimidazoline are reaction products of tallow fatty acids and diethylenetriamine, and are precursors of the cationic fabric softening agent methyl-1-tallowamidoethyl-2-tallowimidazolinium methylsulfate (see "Cationic Surface Active Agents as Fabric Softeners," R. R. Egan, Journal of the American Oil Chemicals' Society, January 1978, pages 118-121).
• N,N"-ditallow alkoyldiethylenetriamine and 1-tallowamidoethyl-2-tallowimidazoline can be obtained from Witco Chemical Company as experimental chemicals.
• Methyl-1- tallowamidoethyl-2-tallowimidazolinium methylsulfate is sold by Witco Chemical Company under the tradename Varisoft® 475.
• each R 2 is a C- ⁇ alkylene group, preferably an ethylene group; and G is an oxygen atom or an -NR- group; and each R, R ⁇ , R 2 and R have the definitions given above and A" has the definitions given above for X " .
• Compound (ii) is 1-oleylamidoethyl-2-oleylimidazolinium chloride wherein Rl is an acyclic aliphatic C15-C-17 hydrocarbon group, R 2 is an ethylene group, G is a NH group, R ⁇ is a methyl group and A" is a chloride anion.
• R, R1 , R 2 , and A are defined as above.
• Compound (iii) is the compound having the formula:
• R1 is derived from oleic acid.
• DEQA diester or diamido quaternary ammonium fabric softening active compound
• An optional, but preferred, ingredient is a liquid carrier.
• the liquid carrier employed in the instant compositions is preferably at least primarily water due to its low cost, relative availability, safety, and environmental compatibility.
• the level of water in the liquid carrier is preferably at least about 50%, most preferably at least about 60%, by weight of the carrier.
• Mixtures of water and low molecular weight, e.g., ⁇ about 200, organic solvent, e.g., lower alcohols such as ethanol, propanol, isopropanol or butanol are useful as the carrier liquid.
• Low molecular weight alcohols include monohydric, dihydric (glycol, etc.) trihydric (glycerol, etc.), and higher polyhydric (polyols) alcohols.
• compositions of the present invention may comprise one or more solvents which provide increased ease of formulation.
• ease of formulation solvents are all disclosed in WO 97/03169. This is particularly the case when formulating liquid, clear fabric softening compositions.
• the ease of formulation solvent system preferably comprises less than about 40%, preferably from about 10% to about 35%, more preferably from about 12% to about 25%, and even more preferably from about 14% to about 20%, by weight of the composition.
• the ease of formulation solvent is selected to minimize solvent odor impact in the composition and to provide a low viscosity to the final composition.
• isopropyl alcohol is not very effective and has a strong odor.
• n-Propyl alcohol is more effective, but also has a distinct odor.
• butyl alcohols also have odors but can be used for effective clarity/stability, especially when used as part of a ease of formulation solvent system to minimize their odor.
• the alcohols are also selected for optimum low temperature stability, that is they are able to form compositions that are liquid with acceptable low viscosities and translucent, preferably clear, down to about 40°F (about 4.4°C) and are able to recover after storage down to about 20°F (about 6.7°C).
• Suitable solvents can be selected based upon their octanol/water partition coefficient (P) as defined in WO 97/03169.
• the ease of formulation solvents herein are selected from those having a ClogP of from about 0.15 to about 0.64, preferably from about 0.25 to about 0.62, and more preferably from about 0.40 to about 0.60, said ease of formulation solvent preferably being at least somewhat asymmetric, and preferably having a melting, or solidification, point that allows it to be liquid at, or near room temperature. Solvents that have a low molecular weight and are biodegradable are also desirable for some purposes.
• compositions that have been diluted to the concentration used in the rinse.
• dilute compositions appear to have dispersions of fabric softener that exhibit a more unilamellar appearance than conventional fabric softener compositions. The closer to uni-lamellar the appearance, the better the compositions seem to perform.
• These compositions provide surprisingly good fabric softening as compared to similar compositions prepared in the conventional way with the same fabric softener active.
• Particularly preferred ease of formulation solvents include hexanediols such as 1 ,2-Hexanediol and 2-Ethyl-1 ,3-hexanediol and pentanediols such as 2,2,4-Trimethyl-1 ,3-pentanediol.
• compositions containing both saturated and unsaturated diester quaternary ammonium compounds can be prepared that are stable without the addition of concentration aids.
• the compositions of the present invention may require organic and/or inorganic concentration aids to go to even higher concentrations and/or to meet higher stability standards depending on the other ingredients.
• concentration aids which typically can be viscosity modifiers may be needed, or preferred, for ensuring stability under extreme conditions when particular softener active levels are used.
• the surfactant concentration aids are typically selected from the group consisting of (1) single long chain alkyl cationic surfactants; (2) nonionic surfactants; (3) amine oxides; (4) fatty acids; and (5) mixtures thereof.
• the total level is from 2% to 25%, preferably from 3% to 17%, more preferably from 4% to 15%, and even more preferably from 5% to 13% by weight of the composition.
• These materials can either be added as part of the active softener raw material, (I), e.g., the mono- long chain alkyl cationic surfactant and/or the fatty acid which are reactants used to form the biodegradable fabric softener active as discussed hereinbefore, or added as a separate component.
• the total level of dispersibility aid includes any amount that may be present as part of component (I).
• Inorganic viscosity/dispersibility control agents which can also act like or augment the effect of the surfactant concentration aids, include water-soluble, ionizable salts which can also optionally be incorporated into the compositions of the present invention.
• ionizable salts can be used. Examples of suitable salts are the halides of the Group IA and HA metals of the Periodic Table of the Elements, e.g., calcium chloride, magnesium chloride, sodium chloride, potassium bromide, and lithium chloride.
• the ionizable salts are particularly useful during the process of mixing the ingredients to make the compositions herein, and later to obtain the desired viscosity.
• the amount of ionizable salts used depends on the amount of active ingredients used in the compositions and can be adjusted according to the desires of the formulator. Typical levels of salts used to control the composition viscosity are from about 20 to about 20,000 parts per million (ppm), preferably from about 20 to about 11 ,000 ppm, by weight of the composition.
• Alkylene polyammonium salts can be incorporated into the composition to give viscosity control in addition to or in place of the water-soluble, ionizable salts above.
• these agents can act as scavengers, forming ion pairs with anionic detergent carried over from the main wash, in the rinse, and on the fabrics, and may improve softness performance. These agents may stabilize the viscosity over a broader range of temperature, especially at low temperatures, compared to the inorganic electrolytes.
• alkylene polyammonium salts include l-lysine monohydrochloride and 1 ,5-diammonium 2-methyl pentane dihydrochloride.
• composition of the invention may optionally comprise a dye fixing agent.
• Dye fixing agents or "fixatives”, are well-known, commercially available materials which are designed to improve the appearance of dyed fabrics by minimizing the loss of dye from fabrics due to washing. Not included within this definition are components which are fabric softeners or those described hereinbefore as amino-functional polymers.
• Cationic fixatives are available under various trade names from several suppliers. Representative examples include: CROSCOLOR PMF (July 1981 , Code No. 7894) and CROSCOLOR NOFF (January 1988, Code No. 8544) from Crosfield; INDOSOL E-50 (February 27, 1984, Ref. No.
• Dye fixing agents suitable for use in the present invention are ammonium compounds such as fatty acid - diamine condensates e.g.
• a typical amount of the dye fixing agent to be employed in the composition of the invention is preferably up 90% by weight, preferably up to 50% by weight, more preferably from 0.001 % to 10% by weight, most preferably from 0.5% to 5% active by weight of the composition.
• Stabilizers can be present in the compositions of the present invention.
• the term "stabilizer,” as used herein, includes antioxidants and reductive agents. These agents are present at a level of from 0% to about 2%, preferably from about 0.01 % to about 0.2%, more preferably from about 0.035% to about 0.1% for antioxidants, and more preferably from about 0.01 % to about 0.2% for reductive agents. These assure good odor stability under long term storage conditions for the compositions and compounds stored in molten form.
• the use of antioxidants and reductive agent stabilizers is especially critical for low scent products (low perfume).
• antioxidants examples include a mixture of ascorbic acid, ascorbic palmitate, propyl gallate, available from Eastman Chemical Products, Inc., under the trade names Tenox® PG and Tenox S-1 ; a mixture of BHT (butylated hydroxytoluene), BHA (butylated hydroxyanisole), propyl gallate, and citric acid, available from Eastman Chemical Products, Inc., under the trade name Tenox-6; butylated hydroxytoluene, available from UOP Process Division under the trade name Sustane® BHT; tertiary butylhydroquinone, Eastman Chemical Products, Inc., as Tenox TBHQ; natural tocopherols, Eastman Chemical Products, Inc., as Tenox GT-1/GT-2; and butylated hydroxyanisole, Eastman Chemical Products, Inc., as BHA; long chain esters (C8-C22) of gallic acid, e.g., dodecyl gallate, available from Eastman Chemical Products, Inc.
• reductive agents include sodium borohydride, hypophosphorous acid, Irgafos® 168, and mixtures thereof.
• Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
• soil release agents will generally comprise from about 0.01% to about 10.0%, by weight, of the detergent compositions herein, typically from about 0.1 % to about 5%, preferably from about 0.2% to about 3.0%.
• soil release agents include the METOLOSE SM100, METOLOSE SM200 manufactured by Shin-etsu Kagaku Kogyo K.K., SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (Germany), ZELCON 5126 (from Dupont) and MILEASE T (from ICI).
• bactericides used in the compositions of this invention include glutaraldehyde, formaldehyde, 2-bromo-2-nitro-propane-1 ,3-diol sold by Inolex Chemicals, located in Philadelphia, Pennsylvania, under the trade name Bronopol®, and a mixture of 5-chloro-2-methyl-4-isothiazoline-3-one and 2- methyl-4-isothiazoline-3-one sold by Rohm and Haas Company under the trade name Kathon 1 to 1 ,000 ppm by weight of the agent.
• the present invention can contain a perfume. Suitable perfumes are disclosed in
• perfume includes fragrant substance or mixture of substances including natural (i.e., obtained by extraction of flowers, herbs, leaves, roots, barks, wood, blossoms or plants), artificial (i.e., a mixture of different nature oils or oil constituents) and synthetic (i.e., synthetically produced) odoriferous substances.
• natural i.e., obtained by extraction of flowers, herbs, leaves, roots, barks, wood, blossoms or plants
• artificial i.e., a mixture of different nature oils or oil constituents
• synthetic i.e., synthetically produced
• Such materials are often accompanied by auxiliary materials, such as fixatives, extenders, stabilizers and solvents. These auxiliaries are also included within the meaning of "perfume", as used herein.
• perfumes are complex mixtures of a plurality of organic compounds.
• the range of the natural raw substances can embrace not only readily-volatile, but also moderately-volatile and slightly-volatile components and that of the synthetics can include representatives from practically all classes of fragrant substances, as will be evident from the following illustrative compilation: natural products, such as tree moss absolute, basil oil, citrus fruit oils (such as bergamot oil, mandarin oil, etc.), mastix absolute, myrtle oil, palmarosa oil, patchouli oil, petitgrain oil Paraguay, wormwood oil, alcohols, such as farnesol, geraniol, linalool, nerol, phenylethyl alcohol, rhodinol, cinnamic alcohol, aldehydes, such as citral, HelionalTM, alpha-hexyl-cinnamaldehyde, hydroxycitronellal, LilialTM (p-tert-butyl-alpha -methyldihydrocinnamaldehyde
• any conventional fragrant acetal or ketal known in the art can be added to the present composition as an optional component of the conventionally formulated perfume (c).
• Such conventional fragrant acetals and ketals include the well-known methyl and ethyl acetals and ketals, as well as acetals or ketals based on benzaldehyde, those comprising phenylethyl moieties, or more recently developed specialties such as those described in a United States Patent entitled "Acetals and Ketals of Oxo-Tetralins and Oxo-lndanes, see U.S. Pat. No. 5 ,084,440, issued January 28, 1992, assigned to Givaudan Corp.
• perfume compositions for fully-formulated fabric softening compositions include the enol ethers of alkyl-substituted oxo-tetralins and oxo-indanes as described in U.S. Pat. 5,332,725; or Schiff Bases as described in U.S. Pat. 5,264,615.
• the perfumes useful in the present invention compositions are substantially free of halogenated materials and nitromusks.
• Perfume can be present at a level of from 0% to 10%, preferably from 0.1% to 5%, and more preferably from 0.2% to 3%, by weight of the finished composition.
• Fabric softener compositions of the present invention provide improved fabric perfume deposition.
• compositions and processes herein can optionally employ one or more copper and/or nickel chelating agents ("chelators").
• chelators can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof, all as hereinafter defined.
• the whiteness and/or brightness of fabrics are substantially improved or restored by such chelating agents and the stability of the materials in the compositions are improved.
• Amino carboxylates useful as chelating agents herein include ethylenedi- aminetetraacetates (EDTA), N-hydroxyethylethylenediaminetriacetates, nitrilotri- acetates (NTA), ethylenediamine tetraproprionates, ethylenediamine-N,N'- diglutamates, 2-hyroxypropylenediamine-N,N'-disuccinates, triethylenetetraaminehexacetates, diethylenetriaminepentaacetates (DETPA), and ethanoldiglycines, including their water-soluble salts such as the alkali metal, ammonium, and substituted ammonium salts thereof and mixtures thereof.
• EDTA ethylenedi- aminetetraacetates
• NDA nitrilotri- acetates
• ethylenediamine tetraproprionates ethylenediamine-N,N'- diglutamates
• Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates), and diethylenetriamine-N,N,N',N",N"- pentakis(methane phosphonate) (DETMP).
• these amino phosphonates do not contain alkyl or alkenyl groups with more than 6 carbon atoms.
• the chelating agents are typically used in the present rinse process at levels from 2 ppm to 25 ppm, for periods from 1 minute up to several hours' soaking.
• the preferred EDDS chelator used herein also known as ethylenediamine-N,N'- disuccinate
• U.S. Patent 4,704,233 cited hereinabove.
• EDDS can be prepared using maleic anhydride and ethylenediamine.
• the preferred biodegradable [S,S] isomer of EDDS can be prepared by reacting L-aspartic acid with 1 ,2-dibromoethane.
• the EDDS has advantages over other chelators in that it is effective for chelating both copper and nickel cations, is available in a biodegradable form, and does not contain phosphorus.
• the EDDS employed herein as a chelator is typically in its salt form, i.e., wherein one or more of the four acidic hydrogens are replaced by a water-soluble cation M, such as sodium, potassium, ammonium, triethanolammonium, and the like. At certain pH's the EDDS is preferably used in combination with zinc cations.
• chelators can be used herein. Indeed, simple polycarboxylates such as citrate, oxydisuccinate, and the like, can also be used, although such chelators are not as effective as the amino carboxylates and phosphonates, on a weight basis. Accordingly, usage levels may be adjusted to take into account differing degrees of chelating effectiveness.
• the chelators herein will preferably have a stability constant (of the fully ionized chelator) for copper ions of at least 5, preferably at least 7. Typically, the chelators will comprise from 0.5% to 10%, more preferably from 0.75% to 5%, by weight of the compositions herein.
• Preferred chelators include DETMP, DETPA, NTA, EDDS and mixtures thereof.
• compositions herein can optionally employ one or more enzymes such as lipases, proteases, cellulase, amylases and peroxidases.
• a preferred enzyme for use herein is a cellulase enzyme. Indeed, this type of enzyme will further provide a color care benefit to the treated fabric.
• Cellulases usable herein include both bacterial and fungal types, preferably having a pH optimum between 5 and 9.5. U.S.
• 4,435,307 discloses suitable fungal cellulases from Humicola insolens or Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk, Dolabella Auricula Solander. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME® and CELLUZYME® (Novo) are especially useful.
• compositions herein will typically comprise from 0.001 % to 5%, preferably 0.01%- 1% by weight of a commercial enzyme preparation.
• activity units are preferred (e.g. CEVU or cellulase Equivalent Viscosity Units).
• compositions of the present invention can contain cellulase enzymes at a level equivalent to an activity from 0.5 to 1000 CEVU/gram of composition.
• Cellulase enzyme preparations used for the purpose of formulating the compositions of this invention typically have an activity comprised between 1 ,000 and 10,000 CEVU/gram in liquid form, around 1 ,000 CEVU/gram in solid form.
• the present invention composition can include optional components conventionally used in fully formulated laundry detergent compositions such as described in WO 97/05226, for example builders, bleaches, brighteners, colorants; surfactants; anti-shrinkage agents; fabric crisping agents; spotting agents; germicides; fungicides; anti-oxidants such as butylated hydroxy toluene, anti-corrosion agents, antifoam agents, and the like.
• the present invention can also include other compatible ingredients, including those as disclosed in WO96/02625, W096/21714, and W096/21715.
• the acidic medium is provided by a fabric softening composition as defined hereinbefore in which the polymer is used.
• the aldehyde malodour reduction benefit is assessed by comparison with a nil polymer containing composition whereby an acceptable product is when trained perfumers are unable to distinguish a difference in odour between the two compositions.
• the color benefit is assessed visually by comparison with a polymer containing composition submitted to acidic conditions versus a reference (same polymer containing composition but not submitted to acidic conditions).
• the composition containing the polymer according to the invention exhibits less color deviation versus its reference compared to a polymer having more than 100ppm after acidic conditions treatments versus its respective reference.
• compositions of the invention are suitable for use in any steps of the domestic treatment, that is as a pre-or post treatment composition, as a wash additive, as a laundry composition, as a composition suitable for use in the rinse- cycle of the laundry cycle or applied on a dryer-sheet.
• a pre-treatment composition of the invention and also thereafter with a composition of the invention suitable for use in the rinse cycle and/or suitable for use as a dryer-sheet.
• the compositions of the invention may also be in a spray, foam, or aerosol form which for example can be suitable for use while ironing, or applied on the surfaces of the tumble dryer.
• the invention is illustrated in the following non limiting examples, in which all percentages are on an active weight basis unless otherwise stated.
• DEQA Di-(tallowyl-oxy-ethyl) dimethyl ammonium chloride DOEQA Di-(oleyloxyethyl) dimethyl ammonium methylsulfate
• DTDMAC Ditallow dimethylammonium chloride
• DHEQA Di-(soft-tallowyl-oxy-ethyl) hydroxyethyl methyl ammonium methylsulfate
• Glycosperse S-20 Polyethoxylated sorbitan monostearate available from Lonza
• PEI 1800 E4 Ethoxylated polyethylene imine (MW 1800, at 50% active) as synthesised and treated in Synthesis example 1
• PEI 1800 E7 Ethoxylated polyethylene imine (MW 1800, at 50% active) as synthesised and treated as per Synthesis example 1
• PEI 1200 E1 Ethoxylated polyethylene imine (MW 1200, at 50% active in water) as synthesised and treated in Synthesis example 2
• Dye Fix 1 Cationic dye fixing agent (50% active) available under the tradename Tinofix Eco from Ciba-Geigy
• Dye Fix 2 Emulsified cationic dye fixative (30% active) available under the tradename Rewin SRF-0 from CHT-Beitlich
• Citric acid Anhydrous citric acid Carbonate Anhydrous sodium carbonate with a particle size between 200 ⁇ m and 900 ⁇ m
• Silicate Amorphous Sodium Silicate Si ⁇ 2:Na2 ⁇ ; 2.0 ratio
• MA/AA Copolymer of 1 :4 maleic/acrylic acid average molecular weight about 70,000.
• Lipolase Lipolytic enzyme of activity 100kLU/g all sold by NOVO Industries A/S and of activity mentioned above unless otherwise specified PB4 Sodium perborate tetrahydrate of nominal formula NaB ⁇ 2.3H 2 O.H 2 ⁇ 2
• Step A)-The ethoxylation is conducted in a 2 gallon stirred stainless steel autoclave equipped for temperature measurement and control, pressure measurement, vacuum and inert gas purging, sampling, and for introduction of ethylene oxide as a liquid.
• a ⁇ 20 lb. net cylinder of ethylene oxide (ARC) is set up to deliver ethylene oxide as a liquid by a pump to the autoclave with the cylinder placed on a scale so that the weight change of the cylinder could be monitored.
• PEI polyethyleneimine
• the autoclave is then sealed and purged of air (by applying vacuum to minus 28" Hg followed by pressurization with nitrogen to 250 psia, then venting to atmospheric pressure).
• the autoclave contents are heated to 130 °C while applying vacuum.
• the autoclave is charged with nitrogen to about 250 psia while cooling the autoclave to about 105 °C.
• Ethylene oxide is then added to the autoclave incrementally over time while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate.
• the ethylene oxide pump is turned off and cooling is applied to limit any temperature increase resulting from any reaction exotherm.
• the temperature is maintained between 100 and 110 °C while the total pressure is allowed to gradually increase during the course of the reaction.
• the temperature is increased to 110 °C and the autoclave is allowed to stir for an additional hour. At this point, vacuum is applied to remove any residual unreacted ethylene oxide.
• Step B)- The reaction mixture is then deodorized by passing about 100 cu. ft. of inert gas (argon or nitrogen) through a gas dispersion frit and through the reaction mixture while agitating and heating the mixture to 130 °C.
• inert gas argon or nitrogen
• the final reaction product is cooled slightly and collected in glass containers purged with nitrogen.
• the obtained polymer contains 476ppm on 100% basis of acetaldehyde. After treatment with 1 % Na2S03, the polymer contained 6.8ppm on 100% basis of acetaldehydes.
• Step A and B If a PEI 1800 E7 is desired, the following step of catalyst addition will be included between Step A and B.
• Vacuum is continuously applied while the autoclave is cooled to about 50 °C while introducing 376 g of a 25% sodium methoxide in methanol solution (1.74 moles, to achieve a 10% catalyst loading based upon PEI nitrogen functions).
• the methoxide solution is sucked into the autoclave under vacuum and then the autoclave temperature controller setpoint is increased to 130 °C.
• a device is used to monitor the power consumed by the agitator.
• the agitator power is monitored along with the temperature and pressure. Agitator power and temperature values gradually increase as methanol is removed from the autoclave and the viscosity of the mixture increases and stabilizes in about 1 hour indicating that most of the methanol has been removed.
• the mixture is further heated and agitated under vacuum for an additional 30 minutes. Vacuum is removed and the autoclave is cooled to 105 °C while it is being charged with nitrogen to 250 psia and then vented to ambient pressure. The autoclave is charged to 200 psia with nitrogen. Ethylene oxide is again added to the autoclave incrementally as before while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate while maintaining the temperature between 100 and 110 °C and limiting any temperature increases due to reaction exotherm. After the addition of 4500 g of ethylene oxide (resulting in a total of 7 moles of ethylene oxide per mole of PEI nitrogen function) is achieved over several hours, the temperature is increased to 110 °C and the mixture stirred for an additional hour.
• reaction mixture is then collected in nitrogen purged containers and eventually transferred into a 22 L three neck round bottomed flask equipped with heating and agitation.
• the strong alkali catalyst is neutralized by adding 167 g methanesulfonic acid (1.74 moles).
• the obtained polymer contains 980ppm on 100% basis of acetaldehyde. After treatment with 1 % Na2S03, the polymer contained 5.6ppm on 100% basis of acetaldehyde.
• PEI 1800 E2 PEI 1800 E4, PEI 1800 E15 and PEI 1800 E20 can be prepared by the above method by adjusting the reaction time and the relative amount of ethylene oxide used in the reaction.
• Step A)-The ethoxylation is conducted in a 2 gallon stirred stainless steel autoclave equipped for temperature measurement and control, pressure measurement, vacuum and inert gas purging, sampling, and for introduction of ethylene oxide as a liquid.
• a ⁇ 20 lb. net cylinder of ethylene oxide (ARC) is set up to deliver ethylene oxide as a liquid by a pump to the autoclave with the cylinder placed on a scale so that the weight change of the cylinder could be monitored.
• a 750 g portion of polyethyleneimine (PEI) (having a listed average molecular weight of 1200 equating to about 0.625 moles of polymer and 17.4 moles of nitrogen functions) is added to the autoclave.
• the autoclave is then sealed and purged of air (by applying vacuum to minus 28" Hg followed by pressurization with nitrogen to 250 psia, then venting to atmospheric pressure).
• the autoclave contents are heated to 130 °C while applying vacuum.
• the autoclave is charged with nitrogen to about 250 psia while cooling the autoclave to about 105 °C.
• Ethylene oxide is then added to the autoclave incrementally over time while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate.
• the ethylene oxide pump is turned off and cooling is applied to limit any temperature increase resulting from any reaction exotherm.
• the temperature is maintained between 100 and 110 °C while the total pressure is allowed to gradually increase during the course of the reaction.
• Step B)- The reaction mixture is then deodorized by passing about 100 cu. ft. of inert gas (argon or nitrogen) through a gas dispersion frit and through the reaction mixture while agitating and heating the mixture to 130 °C.
• inert gas argon or nitrogen
• the final reaction product is cooled slightly and collected in glass containers purged with nitrogen.
• the obtained polymer contains 4894ppm on 100% basis of acetaldehyde. After treatment with 1% Na2S03, the polymer contained 28.5ppm on 100% basis of acetaldehyde.
• Step A If a PEI 1200 E7 is desired, the following step of catalyst addition will be included between Step A and B.
• Vacuum is continuously applied while the autoclave is cooled to about 50 °C while introducing 376 g of a 25% sodium methoxide in methanol solution (1.74 moles, to achieve a 10% catalyst loading based upon PEI nitrogen functions).
• the methoxide solution is sucked into the autoclave under vacuum and then the autoclave temperature controller setpoint is increased to 130 °C.
• a device is used to monitor the power consumed by the agitator.
• the agitator power is monitored along with the temperature and pressure. Agitator power and temperature values gradually increase as methanol is removed from the autoclave and the viscosity of the mixture increases and stabilizes in about 1 hour indicating that most of the methanol has been removed.
• the mixture is further heated and agitated under vacuum for an additional 30 minutes. Vacuum is removed and the autoclave is cooled to 105 °C while it is being charged with nitrogen to 250 psia and then vented to ambient pressure. The autoclave is charged to 200 psia with nitrogen. Ethylene oxide is again added to the autoclave incrementally as before while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate while maintaining the temperature between 100 and 110 °C and limiting any temperature increases due to reaction exotherm. After the addition of 4500 g of ethylene oxide (resulting in a total of 7 moles of ethylene oxide per mole of PEI nitrogen function) is achieved over several hours, the temperature is increased to 110 °C and the mixture stirred for an additional hour.
• reaction mixture is then collected in nitrogen purged containers and eventually transferred into a 22 L three neck round bottomed flask equipped with heating and agitation.
• the strong alkali catalyst is neutralized by adding 167 g methanesulfonic acid (1.74 moles).
• the obtained polymer contains 388ppm on 100% basis of acetaldehyde. After treatment with 1% Na2S03, the polymer contained 5.8ppm on 100% basis of acetaldehyde.
• PEI 1200 E2, PEI 1200 E3, PEI 1200 E15 and PEI 1200 E20 can be prepared by the above method by adjusting the reaction time and the relative amount of ethylene oxide used in the reaction.
• Synthesis Example 3-Preparation of PEI 1800 E7 The ethoxylation is conducted in a 2 gallon stirred stainless steel autoclave equipped for temperature measurement and control, pressure measurement, vacuum and inert gas purging, sampling, and for introduction of ethylene oxide as a liquid.
• a ⁇ 20 lb. net cylinder of ethylene oxide (ARC) is set up to deliver ethylene oxide as a liquid by a pump to the autoclave with the cylinder placed on a scale so that the weight change of the cylinder could be monitored.
• PEI polyethyleneimine
• the autoclave is then sealed and purged of air (by applying vacuum to minus 28" Hg followed by pressurization with nitrogen to 250 psia, then venting to atmospheric pressure).
• the autoclave contents are heated to 130 °C while applying vacuum.
• the autoclave is charged with nitrogen to about 250 psia while cooling the autoclave to about 105 °C.
• Ethylene oxide is then added to the autoclave incrementally over time while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate.
• the ethylene oxide pump is turned off and cooling is applied to limit any temperature increase resulting from any reaction exotherm.
• the temperature is maintained between 100 and 110 °C while the total pressure is allowed to gradually increase during the course of the reaction.
• the temperature is increased to 110 °C and the autoclave is allowed to stir for an additional hour. At this point, vacuum is applied to remove any residual unreacted ethylene oxide.
• the mixture is further heated and agitated under vacuum for an additional 30 minutes. Vacuum is removed and the autoclave is cooled to 105 °C while it is being charged with nitrogen to 250 psia and then vented to ambient pressure. The autoclave is charged to 200 psia with nitrogen. Ethylene oxide is again added to the autoclave incrementally as before while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate while maintaining the temperature between 100 and 110 °C and limiting any temperature increases due to reaction exotherm. After the addition of 4500 g of ethylene oxide (resulting in a total of 7 moles of ethylene oxide per mole of PEI nitrogen function) is achieved over several hours, the temperature is increased to 110 °C and the mixture stirred for an additional hour.
• reaction mixture is then collected in nitrogen purged containers and eventually transferred into a 22 L three neck round bottomed flask equipped with heating and agitation.
• the strong alkali catalyst is neutralized by adding 167 g methanesulfonic acid (1.74 moles).
• the reaction mixture is then deodorized by passing about 100 cu. ft. of inert gas (argon or nitrogen) through a gas dispersion frit and through the reaction mixture while agitating and heating the mixture to 130 °C.
• inert gas argon or nitrogen
• the final reaction product is cooled slightly and collected in glass containers purged with nitrogen.
• the ethoxylation is conducted in a 2 gallon stirred stainless steel autoclave equipped for temperature measurement and control, pressure measurement, vacuum and inert gas purging, sampling, and for introduction of ethylene oxide as a liquid.
• a ⁇ 20 lb. net cylinder of ethylene oxide (ARC) is set up to deliver ethylene oxide as a liquid by a pump to the autoclave with the cylinder placed on a scale so that the weight change of the cylinder could be monitored.
• PEI polyethyleneimine
• 018 having a listed average molecular weight of 1800 equating to about 0.216 moles of polymer and 9.16 moles of nitrogen functions is added to the autoclave.
• the autoclave is then sealed and purged of air (by applying vacuum to minus 28" Hg followed by pressurization with nitrogen to 250 psia, then venting to atmospheric pressure).
• the autoclave contents are heated to 130 °C while applying vacuum.
• the autoclave is charged with nitrogen to about 250 psia while cooling the autoclave to about 105 °C.
• Ethylene oxide is then added to the autoclave incrementally over time while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate.
• the ethylene oxide pump is turned off and cooling is applied to limit any temperature increase resulting from any reaction exotherm.
• the temperature is maintained between 100 and 110 °C while the total pressure is allowed to gradually increase during the course of the reaction.
• the temperature is increased to 110 °C and the autoclave is allowed to stir for an additional hour. At this point, vacuum is applied to remove any residual unreacted ethylene oxide.
• the mixture is further heated and agitated under vacuum for an additional 30 minutes. Vacuum is removed and the autoclave is cooled to 105 °C while it is being charged with nitrogen to 250 psia and then vented to ambient pressure. The autoclave is charged to 200 psia with nitrogen. Ethylene oxide is again added to the autoclave incrementally as before while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate while maintaining the temperature between 100 and 110 °C and limiting any temperature increases due to reaction exotherm. After the addition of 2178 g of ethylene oxide (resulting in a total of 7 moles of ethylene oxide per mole of PEI nitrogen function) is achieved over several hours, the temperature is increased to 110 °C and the mixture stirred for an additional hour.
• reaction mixture is then collected in nitrogen purged containers and eventually transferred into a 22 L three neck round bottomed flask equipped with heating and agitation.
• the strong alkali catalyst is neutralized by adding 86.5 g methanesulfonic acid (0.9 moles).
• the reaction mixture is then deodorized by passing about 100 cu. ft. of inert gas (argon or nitrogen) through a gas dispersion frit and through the reaction mixture while agitating and heating the mixture to 130 °C.
• inert gas argon or nitrogen
• the final reaction product is cooled slightly and collected in glass containers purged with nitrogen.
• the synthesis is repeated except that the catalyst is added after hydroxyethylation to the E1 level.
• Sample color is lighter in the preparation in which the catalyst is added after hydroxyethylation to the E0.9 level.
• the synthesis is repeated with base catalyst added after hydroxyethylation to the E 0.1 level. Again the color of the final ethoxyated sample is lighter than for the control in which catalyst is added after hydroxyethylation to the E1 level.
• a -20 lb. net cylinder of ethylene oxide (ARC) is set up to deliver ethylene oxide as a liquid by a pump to the autoclave with the cylinder placed on a scale so that the weight change of the cylinder could be monitored.
• PEI polyethyleneimine
• Epomin SP- 018 having a listed average molecular weight of 1800 equating to about 0.35 moles of polymer and 14.95 moles of nitrogen functions
• 600 mg of sodium borohydride is added to the autoclave.
• the autoclave is then sealed and purged of air (by applying vacuum to minus 28" Hg followed by pressurization with nitrogen to 250 psia, then venting to atmospheric pressure).
• the autoclave contents are heated to 130 °C while applying vacuum.
• the autoclave is charged with nitrogen to about 250 psia while cooling the autoclave to about 105 °C.
• Ethylene oxide is then added to the autoclave incrementally over time while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate.
• the ethylene oxide pump is turned off and cooling is applied to limit any temperature increase resulting from any reaction exotherm.
• the temperature is maintained between 100 and 110 °C while the total pressure is allowed to gradually increase during the course of the reaction.
• the temperature is increased to 110 °C and the autoclave is allowed to stir for an additional hour. At this point, vacuum is applied to remove any residual unreacted ethylene oxide.
• reaction mixture is then collected in nitrogen purged containers and eventually transferred into a 2 L three neck round bottomed flask equipped with heating and agitation.
• the reaction mixture is then deodorized by passing about 100 cu. ft. of inert gas (argon or nitrogen) through a gas dispersion frit and through the reaction mixture while agitating and heating the mixture to 130 °C.
• inert gas argon or nitrogen
• the final reaction product is cooled slightly and collected in glass containers purged with nitrogen.
• the synthesis is repeated except that no sodium borohydride is added.
• the color or the preparation made in the presence of sodium borohydride is much lighter.
• sodium borohydride is added to the sample prepared without borohydride and odor is improved.
• the synthesis is repeated with sodium borohydride added at the beginning except that after hydroxyethylating to the E1 level, strong base catalyst is added and ethoxylation is resumed until the E7 level is achieved. Color is lighter than in a control experiment run the same way except for omitting the borohydride.
• the synthesis is repeated except that the sodium borohydride is added after hydroxyethylation to the E1 level and addition of strong base catalyst. Further ethoxylation to the E7 level gives a lighter color than the control in which no borohydride was added.
• compositions for use as dryer-added sheets are in accordance with the invention.
• liquid detergent formulation according to the present invention was prepared:

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• 1997
  • 1997-09-29 EP EP97911602A patent/EP1019447A1/de not_active Ceased
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