Deprecated: The each() function is deprecated. This message will be suppressed on further calls in /home/zhenxiangba/zhenxiangba.com/public_html/phproxy-improved-master/index.php on line 456
GB2321900A - Cationic surfactants - Google Patents
[go: Go Back, main page]

GB2321900A - Cationic surfactants - Google Patents

Cationic surfactants Download PDF

Info

Publication number
GB2321900A
GB2321900A GB9702731A GB9702731A GB2321900A GB 2321900 A GB2321900 A GB 2321900A GB 9702731 A GB9702731 A GB 9702731A GB 9702731 A GB9702731 A GB 9702731A GB 2321900 A GB2321900 A GB 2321900A
Authority
GB
United Kingdom
Prior art keywords
cationic surfactant
group
surfactant according
polyamine cationic
diamine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
GB9702731A
Other versions
GB9702731D0 (en
Inventor
Stephen Wayne Heinzman
Barry Thomas Ingram
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to GB9702731A priority Critical patent/GB2321900A/en
Publication of GB9702731D0 publication Critical patent/GB9702731D0/en
Priority to PCT/US1998/002365 priority patent/WO1998035002A1/en
Priority to AU63220/98A priority patent/AU6322098A/en
Priority to JP53493598A priority patent/JP2001511209A/en
Priority to AU63210/98A priority patent/AU6321098A/en
Priority to EP98906216A priority patent/EP0975720A4/en
Priority to ARP980100607A priority patent/AR012033A1/en
Priority to ARP980100605 priority patent/AR011665A1/en
Priority to AU62722/98A priority patent/AU6272298A/en
Priority to PCT/US1998/002367 priority patent/WO1998035004A1/en
Priority to AU61496/98A priority patent/AU6149698A/en
Priority to PCT/US1998/002461 priority patent/WO1998035005A1/en
Priority to CA002279882A priority patent/CA2279882A1/en
Priority to ARP980100606 priority patent/AR011666A1/en
Priority to AU61520/98A priority patent/AU6152098A/en
Priority to PCT/US1998/002462 priority patent/WO1998035006A1/en
Priority to CN 98804060 priority patent/CN1252091A/en
Priority to ARP980100604 priority patent/AR011664A1/en
Priority to PCT/US1998/002366 priority patent/WO1998035003A1/en
Priority to BR9807832-1A priority patent/BR9807832A/en
Publication of GB2321900A publication Critical patent/GB2321900A/en
Withdrawn legal-status Critical Current

Links

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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/62—Quaternary ammonium compounds
    • C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/65—Mixtures of anionic with cationic compounds

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Cationic surfactants containing at least one quaternary amine group and at least one primary, secondary or tertiary amine group may be used in cleaning or detergent compositions.

Description

Detereent compound Technical field The present invention relates to a polyamine cationic surfactant, containing at least one quaternary amine group and at least one primary, secondary or tertiary amine group and methods for making them. The surfactants may be used in any application where surfactancy is required. In particular they may be used in cleaning or detergent compositions or components thereof.
Background to the invention The satisfactory removal of greasy soils/stains, that is soils/stains having a high proportion of triglycerides or fatty acids, is a challenge faced by the formulator of detergent compositions for use in laundry and dish washing methods. Surfactant components have traditionally been employed in detergent products to facilitate the removal of such greasy soils/stains. In particular, surfactant systems comprising cationic surfactants have been described for use in greasy soil/stain removal.
A wide selection of surfactants for use in detergents can be found in the literature, but the reality is that many such surfactants are chemicals which are not always suitable in detergents, because of certain properties they have (such as instability in acidic or basic environment, incompatibility with bleach, malodour problems, biodegradability problems). Thus, the challenge to the detergent manufacturer seeking improved performance has been increased by these various factors. For example, some nonbiodegradable ingredients have fallen into disfavour. As a result, the manufacturer is somewhat more limited than the literature would suggest in the selection of effective, yet affordable, ingredients.
A variety of cationic surfactants are suggested to be usable in detergents. One group of cationic surfactants which is widely studied is the group consisting of quaternary ammonium or imidazolinium compounds, which are often designed for speciality use.
For example, various quaternary ammonium surfactants have been suggested for use in shampoo compositions and are said to provide cosmetic benefits to hair.
US-A-4,228,042 discloses biodegradable cationic surfactants, including cationic ester surfactants for use in detergent compositions to provide greasy/oily soil removal. For example, US 3,567,729 discloses diquatemary ammonium compounds for use in detergents. For example, US 5,068,431 describes quaternary ammonium compounds, containing amphoteric amine oxide groups.
The Applicants have now found that certain polyamine cationic compounds, containing at least one cationically charged quaternary amine group and at least one primary, secondary or tertiary amine group are very good surfactants, suitable for use in cleaning or detergent compositions. These compounds are found to be very surface active under alkaline washing conditions, and they are found to give excellent cleaning performance benefits. This is believed to be due to the compounds containing both a positively charged group and a neutral, more hydrophobic group.
Furthermore, several examples of these surfactants are found to be more biodegradable and to have a very low aquatic toxicity, relative to most quaternary amine compounds.
It has been found that the stability of the polyamine cationic surfactants is not affected by changes of the pH. Furthermore, it has been found that, depending on their structure, most of the polyamine cationic compounds of the present invention and detergent compositions containing these polyamine cationic surfactants, are stable under standard storage and washing conditions.
Furthermore, it has been found that the polyamine cationic surfactants can be compatible with bleach, especially oxygen-based bleaches, and with certain bleach activators.
The polyamine cationic surfactants can be obtained via various efficient synthesis routes, and the production of these compounds can be very cost-effective.
All documents cited in the present description are, in relevant part, incorporated herein by reference.
Summary of the Invention The present invention relates to polyamine cationic surfactants, containing at least one quaternary amine group and at least one primary, secondary or tertiary amine group.
The invention also relates to methods of making the polyamine cationic surfactants.
The polyamine cationic compounds of the invention can be used as a surfactant in any composition where surfactancy is required, for example in cleaning or detergent compositions or components thereof.
Detailed description of the invention Cationic surfactant A cationic surfactant according to the present invention comprises at least one quaternized ammonium group and at least one primary, secondary or tertiary amine group, whereby not more than one linear or branched polyoxyalkylene group is present as substituent group.
Preferred cationic surfactant of the present invention are polyamine cationic surfactants of the general formula (I):
wherein L is a linking unit, and each L is independently selected from the group consisting of C2-C30 linear or branched alkylene, alkenylene, alkarylene, aralkylene, arylene, (poly) hydroxyalkylene, (poly) alkylenoxy, (poly) hydroxy alkenylene; L can be substituted by one or more A, B, C or D units; x is a number from 0 to 10, y is a number from 0 to 10; and wherein the units A- and D- are each independently selected from
wherein R1, R2, R3, R4, Rg, R6, R7 and R8 are independently selected from the group consisting of C1-C30 linear or branched alkyl, alkenyl, alkaryl, aralkyl, aryl, (poly) hydroxyalkyl, (poly) hydroxy alkenyl, alkoxy group and hydrogen, one of R1, R2, R3, R4, Rg, R6, R7 or R8 can be a linear or branched polyoxyalkylene group with from 2 to 26 oxyalkylene units or R1 and R2, R1and R2 and R3, R4 and R5 or R6 and R7 form together with the nitrogen atom part of a ring structure; or R3 is not present and R1 or R2 is double bonded to the nitrogen; or R7 is not present and R6 is double bonded to the nitrogen; or R5 is not present and R4 is double bonded to the nitrogen; M- is one or more counterions, and at least one A or D comprises a quaternized ammonium group in which none ofR1, R2 or R3 is hydrogen, or at least one B is present in which neither R6 nor R7 is hydrogen, and at least one A or D comprises a primary, secondary or tertiary amine group, or at least one C is present.
The units B-L and C-L are linked when both are present (i.e. when x and y do not equal 0), and they can be randomly present along the chain between the end units A-L and D.
Preferably, the value of x+y is from 1 to 4. More preferably, x=0 and y is a number from 1 to 4 Even more preferably, both x and y are 0.
Preferably R6, R7 and/or R8 are each independently selected from a C1-C6, more preferably C1-C3 alkyl, alkoxyalkyl or (poly) hydroxyalkyl group or, most preferably hydrogen.
Preferably, R1 is a C6-C14 alkyl, (poly) hydroxyalkyl or alkoxy group or an aralkyl group, most preferably a 2-ethylhexyl group, R2 and R3 are each independently C1 - C6, more preferably C1-C3 alkyl or hydroxyalkyl groups and preferably R4 and R5 (and R6, R7 and R8 when present) are each independently C1 -C6, more preferably C1-C3 alkyl, alkoxyalkyl or (poly) hydroxyalkyl groups or, most preferably, hydrogen atoms In a further preferred alternative, R4 is preferably a C6-C14 alkyl, (poly) hydroxyalkyl, alkoxy group or an aralkyl group, most preferably a 2-ethylhexyl group R5 is preferably a C1-C6, more preferably a C I -C3 alkyl, (poly) hydroxyalkyl group or hydrogen and R1, R2 and R3 (and R6, R7 and R8 when present) are each independently preferably C1-C6, more preferably C1-C3 alkyl, alkoxyalkyl or (poly) hydroxyalkyl groups or aralkyl groups.
When R1 and R2, R1 and R2 and R3, R and R5 or R6 and R7 form together with the nitrogen atom part of a ring structure, the ring structure is preferably a benzene ring structure, morpholino ring structure or a piperazino ring structure, or a subtituted benzene or substituted morpholino or substituted piperazino ring structure.
L groups are independently preferably a C2-Cg, more preferably a C2-C4 linear or branched alkyl, hydroxy alkyl, alkoxy or hydroxy alkoxy group Examples of preferred polyamine cationic surfactants of the present invention are:
wherein R1, R4, R6 and R8 are as described above; R2, R3 and R5 are independently selected from the group consisting of methyl, ethyl, hydroxyethyl, hydroxypropyl, polyhydroxy propyl, ethoxy, propoxy or 2,3,4,5,6-penta hydroxy hexyl, and are most preferably methyl or hydroxyethyl groups; R10 is a methyl or hydroxyethyl group; L is as described above; R1 and/or R2 and/or R4 are most preferably a 2-ethylhexyl group.
A highly preferred cationic polyamine surfactant is of formula VI, as defined above, wherein R2 is a hydroxypropyl or hydroxyethyl group, R3 and R10 are methyl groups, L is C2-C3 alkyl group.
Highly preferred polyamine cationic surfactant are those ofthe formulas:
or
wherein R1 is as described above, preferably a C2-C14, preferably C6-C14 linear or branched alkyl, (poly) hydroxy alkyl, alkoxy or aralkyl group; particularly preferred R1 groups are hydroxyalkyl groups, where the alkyl groups have 2 to 5 carbon atoms, especially hydroxyethyl and hydroxypropyl are preferred; particularly preferred alkyl R1 groups have up to 9 carbon atoms, most preferably R1 is a 2-ethylhexyl group; and R1 1 is a C2-C14 alkyl, (poly) hydroxy alkyl, alkoxy or aralkyl group or a A or D unit as described above.
The anion M- is a counterion for the cationically charged polyamine surfactant.
Therefore, the number of M anions present will depend on the cationic charge of the polyamine surfactant, which depends on the groups A, B, C and D. The number of M- anions will be at least 1. A preferred counterion is a halide anion, more preferably a sulphate anion.
Svnthesis of the polyamine cationic surfactant A variety of synthesis routes may be used for making the polyamine cationic surfactant of the present invention. Depending on which polyamine cationic surfactant reaction product is to be prepared and which starting material is available therefor, one synthesis route will be preferred over other possible routes and this choice will be well within the ambit of the skilled person given the examples below. The starting materials can be selected from a variety of (readily), commercially available compounds, depending on which polyamine cationic surfactant needs to be prepared, and again, this selection is well within the ambit of the skilled person. Preferably, the starting material is an amine or diamine compound.
Preferred synthesis routes (A-D) A. Reaction of two amine containing compounds A preferred synthesis route is as follows. In a preferably organic solvent one or more primary or secondary amine compound and a quaternary halide or sulphate containing amine compound are mixed, preferably in a mole ratio of 1.5:1 to 3:1, to make them react together. When the reaction is complete, a basic compound is added, preferably sodium hydroxide, and the polyamine cationic surfactant reaction product can be removed from the reaction mixture by conventional methods.
Examples of this synthesis route are the reactions of any of hexylamine, octylamine, decylamine, dodecylamine or 2-ethylhexylamine with (3-bromo, chloro or sulphate propyl) trimethyl ammonium bromide, chloride or sulphate, in a ratio of about 2:1, in an organic solvent (ethanol), whereafter sodium hydroxide is added. Once the reaction is substantially completed (after reacting for up to 24 hours), the organic solvent and the possibly unreacted amine compound are removed from the reaction mixture via evaporation, and washed with (for example) diethyl ether, to yield a white solid diamine cationic surfactant, i.e. a (1 -hexyl, octyl, decyl, dodecyl or 2-ethylhexyl amine) (3-trimethylamine) propane.
B. Alkylation of a diamine Another preferred synthesis route is as follows.
A diamine compound and an alkylating agent are mixed in an organic solvent, preferably the diamine to alkylating agent are in a mole ratio of from 3.5:1 to 1.1:1.
When the reaction is completed the polyamine cationic surfactant reaction product can be removed from the reaction mixture by conventional methods.
Examples of this synthesis are the reactions of any of l-bromo or chloro hexane, octane, decane, dodecane or tetradecane or 2- ethylhexylbromide with tetramethylpropanediamine in an organic solvent (ethanol). The mole ratio of the reactants is preferably about 1:1. Once the reaction is substantially completed, the organic solvent and any unreacted amine compound are removed from the reaction mixture via evaporation. The remaining product is then washed with (for example) diethyl ether, to yield the diamine cationic surfactant, i.e. hexyl, octyl, decyl dodecyl, tetradecyl 2-ethylhexyl, tetramethyl propanediamine.
C. Preparation of an imine. reduction and alkvlation A further preferred synthesis route is as follows.
In an organic solvent an aldehyde compound and a diamine compound are mixed in a mole ratio of from 2:1 to 1:2, whereby an imine is formed. The imine reaction product is reduced to a secondary diamine with a reducing agent. The secondary diamine product is then selectively alkylated on the secondary amine with an alkylating agent such as formaldehyde/ formic acid. The diamine is then quaternised/ alkylated using an alkylating agent to form a diamine cationic surfactant.
Examples of this synthesis route are the reactions of any of 2-ethylhexanal, hexanal, octanal, decanal or dodecanal with N,N, dimethylene diamine in an organic solvent (toluene), in a mole ratio of about 1:1. Once the reaction is substantially completed, the solvent is removed and borohydride is added to effect the reduction step. The reduced reaction product is then neutralised with formic acid and formaldehyde. Then, methyl bromide/ chloride is added to the reaction product to yield a white solid diamine cationic surfactant, i.e. N'-hexyl, octyl, decyl, dodecyl or ethylhexyl N,N, dimethylethylene diamine.
D. Selective alkylation of diamine Yet another preferred synthesis route is as follows: In an organic solvent a tertiary/primary alkyl diamine and an anhydride, acid, methyl ester or acid chloride are reacted, whereby the primary amine group is acylated to produce an amide compound. The reaction product is then selectively alkylated with an alkylating agent, and the amide product is hydrolysed using a mineral acid, to produce a diamine cationic surfactant.
An example of this synthesis route is the reaction of the N,N dimethylethylene diamine with acetic anhydride in an organic solvent (toluene), followed by alkylation in an organic solvent (ethanol) with bromo- or chloro- hexane, octane, decane or dodecane to yield a quaternary amine amide. This reaction product is hydrolysed using hydrobromic acid in water, to produce a diamine cationic surfactant, i.e. a N,N,N, hexyl, octyl, decyl or dodecyl-dimethyl ethylene diamine.
Examples of small scale synthesis of preferred polyamine cationic surfactants Example 1 1.1 Into a 250ml round bottom flask fitted with reflux condenser and drying tube was placed l-bromohexane (10.0g, 0.061 mol) and tetramethylpropanediamine (8.68g, 0.067 mol) in 100ml ethanol. The mixture was refluxed for 72 hours. Ethanol was removed by rotary evaporation, adding additional ethanol to remove unreacted amine.
The resultant sticky solid was triturated with diethyl ether, but remained a syrup.
Analysis by 270 M Hzl H NMR in CDC13 gave the following peaks: 6 0.9 (t, 4H), 1.3-1.5 (bs), 1.7(m, 2H), 1.95 (m, 2H), 2.25 (s, 6H), 2.4 (t, 2H), 3.4-3.7 (2s, m, 14H inc. ethanol).
This synthesis was also carried out using the following materials: 1.2 replacing bromohexane with other alkyl bromides: Bromooctane Yield 24% Bromodecane Yield 14% 1.3 replacing tetramethylpropanediamine with tetramethylethanediamine and using the following alkyl bromides: Alkvl Bromide Yield Bromohexane 85% Bromoctane 91 % Bromodecane 85% Bromotetradecane 75% 2-Ethylexylbromide 88% Example 2 2.1 Into a 250 ml round bottom flask fitted with reflux condenser and drying tube was placed octylamine (7.50g, 0.58 mol) and (3.bromopropyl)trimethylammoniumbromide (10. 15g, 0.0387 mol) in 100 ml ethanol. The mixture was refluxed for 1 day. Further octylamine (2.50g, 0.0193 mol) was added and the mixture refluxed for 1 day.
Sodium hydroxide (1.56g) was added and the mixture filtered to remove the resultant precipitate. Ethanol was removed by rotary evaporation, adding additional ethanol to remove unreacted amine. The resultant sticky solid was triturated with diethyl ether, to yield a white solid, (lOg, 87.60% yield). Analysis by 270 M Hzl H NMR in CD30D gave the following peaks: 50.9(t), 1.2-1.4(bs), 1.6(m), 2.0(m), 2.52.7(2m), 3.2(2s), 3.4(m).
This synthesis was also carried out with the following materials: 2.2 replacing octylamine with the following alkylamines.
Butylamine Hexylamine Decylamine Dodecylamine 2-Ethylhexylamine Detergent compositions and components thereof The polyamine cationic surfactant of the present invention may be used in any application where surfactancy is required. For example, the polyamine cationic surfactant of the present invention can be used in detergent compositions or components thereof.
Depending on the type of detergent composition or component the polyamine cationic surfactant of the present invention can be present at a level of from 0.05% to 95% by weight of the composition or component.
The detergent compositions or components thereof can contain any of the traditionally known and used detergent ingredients or components. The precise nature of these components, and levels of incorporation thereof will depend on the physical form of the composition, and the precise nature of the washing operation for which it is to be used.
The detergent compositions or components thereof preferably contain one or more detergent components selected from additional surfactants, bleaches, bleach catalysts, bleach precursors, water-soluble and insoluble builders, chelants, organic polymeric compounds, enzymes, suds suppressors, lime soap dispersants, soil suspension and anti-redeposition agents, perfumes, brighteners and corrosion inhibitors.
The additional surfactant can be selected from anionic, nonionic, additional cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.
Where present, ampholytic, amphoteric and zwitterionic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants.
pH of the detergent compositions The detergent compositions preferably have a pH measured as a 1% solution in distilled water of at least 8.5, preferably from 9.0 to 12.5, most preferably from 9.5 to 11.0.
Form of the compositions The detergent or cleaning compositions, comprising the polyamine cationic surfactant of the present invention, can take a variety of physical forms including granular, tablet, bar and liquid forms. The compositions are particularly the so-called concentrated granular detergent compositions adapted to be added to a washing machine by means of a dispensing device placed in the machine drum with the soiled fabric load.
In general, granular detergent compositions in accordance with the present invention can be made via a variety of methods including dry mixing, spray drying, agglomeration and granulation.

Claims (18)

1. A cationic surfactant comprising at least one quaternized ammonium group and at least one primary, secondary or tertiary amine group, wherein not more than one linear or branched polyoxyalkylene group is present as substituent group.
2. A cationic surfactant according to Claim 1 of the general formula:
wherein L is a linking unit, and each L is independently selected from the group consisting of C2-C30 linear or branched alkylene, alkenylene, alkarylene, aralkylene, arylene, (poly) hydroxyalkylene, (poly) alkylenoxy, (poly) hydroxy alkenylene; L can be substituted by one or more A, B, C or D units; x is a number from 0 to 10, y is a number from 0 to 10; and wherein the units A- and D- are each independently selected from:
wherein R1, R2, R3, R4, Rg, R6, R7 and R8 are independently selected from the group consisting ofC1-C30 linear or branched alkyl, alkenyl, alkaryl, aralkyl, aryl, (poly) hydroxyalkyl, (poly) hydroxy alkenyl, alkoxy group and hydrogen, one of R1, R2, R3,R4,R5,R6,R7 or R8 can be a linear or branched polyoxyalkylene group with from 2 to 26 oxyalkylene units or R1 and R2, Rland R2 and R3, R4 and R5 or R6 and R7 form together with the nitrogen atom part of a ring structure; or R3 is not present and R1 or R2 is double bonded to the nitrogen; or R7 is not present and R6 is double bonded to the nitrogen; or R5 is not present and R4 is double bonded to the nitrogen; M- is one or more counterions, and at least one A or D comprises a quaternized ammonium group in which none of R1, R2 or R3 is hydrogen, or at least one B is present in which neither R6 or R7 is hydrogen, and at least one A or D comprises a primary, secondary or tertiary amine group, or at least one C is present
3. A polyamine cationic surfactant according to Claim 2 wherein x=0.
4. A polyamine cationic surfactant according to Claim 2 wherein x=0 and y=0.
5. A polyamine cationic surfactant according to any of Claims 2 to 4 wherein R1 is a C6-C14 alkyl group.
6. A polyamine cationic surfactant according to any of Claims 2 to 5 wherein R1 or R4 is a 2-ethylhexyl group.
7. A polyamine cationic surfactant according to Claim 5 wherein R4 and R5 are, independently from each other, C1 -C6 alkyl or (poly) hydroxyalkyl group or hydrogen atom.
8. A polyamine cationic surfactant according to any of Claims 5 or 7 wherein R4 and R5 are hydrogen.
9. A polyamine cationic surfactant according to any of Claims 2 to 8 wherein L is a C2-C4 linear or branched alkyl or hydroxyalkyl group.
10. A polyamine cationic surfactant according to any of Claims 2 to 8 wherein L iN a C2-C4 linear or branched alkoxy or hydroxy alkoxy group.
11. A process for preparing a polyamine cationic surfactant according to any of Claims 2 to 10 comprising the reaction of one or more primary, secondary or tertiary amine compounds with a quaternary amine compound.
12. A process for preparing a polyamine cationic surfactant according to any of Claims 4 to 10 comprising the reaction of a diamine with an alkylating agent.
13. A process for preparing a polyamine cationic surfactant according to any of Claims 4 to 10 comprising the steps of (1) reaction of an aldehyde compound and a diamine compound to form an imide; (2) reduction of the imine of step (1) to an secondary diamine with a reducing agent; (3) selective alkylation of the secondary amine of step (2) to an alkylated diamine with an alkylating agent; and (4) alkylation of the alkylated diamine of step (3) with an alkylating agent to form a polyamine cationic surfactant according to any of Claims 4 to 10.
14. A process for preparing a polyamine cationic surfactant according to any of Claims 4 to 10 comprising the steps of (1) reaction of a diamine with an anhydride to form an acylated diamine; (2) selective alkylation of the acylated diamine to form an acylated and alkylated diamine; and (3) hydrolysis of the acylated alkylated diamine to form a polyamine cationic surfactant according to any of Claims 4 to 10.
15. A detergent composition or component thereof, comprising the polyamine cationic surfactant according to any of Claims 1 to 10 and comprising one of more other detergent components.
16. A detergent composition according to Claim 15 in which the detergent composition is selected from the group of anionic, nonionic surfactants, water soluble and non-soluble builders and bleaching agents.
17. A method for preparing a detergent composition according to Claim 15 or Claim 16 comprising mixing the polyamine cationic surfactant according to any of Claims 1 to 10 with one or more other detergent components.
18. Detergent compositions produced according to Claim 17.
GB9702731A 1997-02-11 1997-02-11 Cationic surfactants Withdrawn GB2321900A (en)

Priority Applications (20)

Application Number Priority Date Filing Date Title
GB9702731A GB2321900A (en) 1997-02-11 1997-02-11 Cationic surfactants
BR9807832-1A BR9807832A (en) 1997-02-11 1998-02-11 Detergent compound
AU61496/98A AU6149698A (en) 1997-02-11 1998-02-11 Detergent compound
CA002279882A CA2279882A1 (en) 1997-02-11 1998-02-11 Detergent compound
JP53493598A JP2001511209A (en) 1997-02-11 1998-02-11 Detergent compound
AU63210/98A AU6321098A (en) 1997-02-11 1998-02-11 Cleaning compositions
EP98906216A EP0975720A4 (en) 1997-02-11 1998-02-11 DETERGENT COMPOUND
ARP980100607A AR012033A1 (en) 1997-02-11 1998-02-11 DETERGENT COMPOSITION OR COMPONENT CONTAINING A CATIONIC SURFACTANT
ARP980100605 AR011665A1 (en) 1997-02-11 1998-02-11 DETERGENT OR CLEANING COMPOSITION OR A COMPONENT THEREOF INCLUDING SURFACE AGENTS AND AN OXYGEN RELEASING BLEACH
AU62722/98A AU6272298A (en) 1997-02-11 1998-02-11 Solid detergent compositions
PCT/US1998/002367 WO1998035004A1 (en) 1997-02-11 1998-02-11 Solid detergent compositions
PCT/US1998/002365 WO1998035002A1 (en) 1997-02-11 1998-02-11 Cleaning compositions
PCT/US1998/002461 WO1998035005A1 (en) 1997-02-11 1998-02-11 A cleaning composition
AU63220/98A AU6322098A (en) 1997-02-11 1998-02-11 A cleaning composition
ARP980100606 AR011666A1 (en) 1997-02-11 1998-02-11 SOLID COMPOSITION OR COMPONENT, DETERGENT THAT INCLUDES CATIONIC SURFACTANT / S AND ITS USE TO IMPROVE DISTRIBUTION AND / OR DISPERSION IN WATER.
AU61520/98A AU6152098A (en) 1997-02-11 1998-02-11 Liquid cleaning composition
PCT/US1998/002462 WO1998035006A1 (en) 1997-02-11 1998-02-11 Liquid cleaning composition
CN 98804060 CN1252091A (en) 1997-02-11 1998-02-11 Detergent compound
ARP980100604 AR011664A1 (en) 1997-02-11 1998-02-11 CLEANING LIQUID COMPOSITION INCLUDING A CATIONIC SURFACE AGENT OF POLYAMINE, A SOLVENT AND ADDITIONAL INGREDIENTS
PCT/US1998/002366 WO1998035003A1 (en) 1997-02-11 1998-02-11 Detergent compound

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB9702731A GB2321900A (en) 1997-02-11 1997-02-11 Cationic surfactants

Publications (2)

Publication Number Publication Date
GB9702731D0 GB9702731D0 (en) 1997-04-02
GB2321900A true GB2321900A (en) 1998-08-12

Family

ID=10807396

Family Applications (1)

Application Number Title Priority Date Filing Date
GB9702731A Withdrawn GB2321900A (en) 1997-02-11 1997-02-11 Cationic surfactants

Country Status (8)

Country Link
EP (1) EP0975720A4 (en)
JP (1) JP2001511209A (en)
CN (1) CN1252091A (en)
AU (1) AU6149698A (en)
BR (1) BR9807832A (en)
CA (1) CA2279882A1 (en)
GB (1) GB2321900A (en)
WO (1) WO1998035003A1 (en)

Families Citing this family (259)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2358116T3 (en) * 2003-11-20 2011-05-05 Basf Se SOLUBLE COPOLYMERS IN WATER FROM MONOMETERS OF MONOETHYLENEUALLY UNATURATED POLYCHYLENE OXIDE AND BIPOLAR MONOMERS CONTAINING AT LEAST ONE NITROGEN ATOM.
EP1851298B1 (en) 2005-02-17 2010-03-24 The Procter and Gamble Company Fabric care composition
WO2011017223A1 (en) 2009-07-31 2011-02-10 Akzo Nobel N.V. Hybrid copolymer compositions for personal care applications
CA2636869C (en) 2006-01-23 2013-05-28 Milliken & Company Laundry care compositions with thiazolium dye
US8093199B2 (en) 2006-11-17 2012-01-10 Basf Se Premoistened cleaning disposable substrate and method of incorporation of a cleaning composition into said substrate
US20080177089A1 (en) 2007-01-19 2008-07-24 Eugene Steven Sadlowski Novel whitening agents for cellulosic substrates
US7487720B2 (en) 2007-03-05 2009-02-10 Celanese Acetate Llc Method of making a bale of cellulose acetate tow
WO2008142606A1 (en) 2007-05-17 2008-11-27 The Procter & Gamble Company Detergent additive extrudates containing alkyl benzene sulphonate
US20090023625A1 (en) 2007-07-19 2009-01-22 Ming Tang Detergent composition containing suds boosting co-surfactant and suds stabilizing surface active polymer
EP2071017A1 (en) 2007-12-04 2009-06-17 The Procter and Gamble Company Detergent composition
EP2083065A1 (en) 2008-01-22 2009-07-29 The Procter and Gamble Company Colour-Care Composition
EP2103675A1 (en) 2008-03-18 2009-09-23 The Procter and Gamble Company Detergent composition comprising cellulosic polymer
EP2103676A1 (en) 2008-03-18 2009-09-23 The Procter and Gamble Company A laundry detergent composition comprising the magnesium salt of ethylene diamine-n'n' -disuccinic acid
EP2103678A1 (en) 2008-03-18 2009-09-23 The Procter and Gamble Company Detergent composition comprising a co-polyester of dicarboxylic acids and diols
US9376648B2 (en) 2008-04-07 2016-06-28 The Procter & Gamble Company Foam manipulation compositions containing fine particles
US7923426B2 (en) 2008-06-04 2011-04-12 The Procter & Gamble Company Detergent composition
EP2135931B1 (en) 2008-06-16 2012-12-05 The Procter & Gamble Company Use of soil release polymer in fabric treatment compositions
PL2272941T3 (en) 2008-06-20 2014-01-31 Procter & Gamble Laundry composition
EP2135933B1 (en) 2008-06-20 2013-04-03 The Procter and Gamble Company Laundry composition
EP2154235A1 (en) 2008-07-28 2010-02-17 The Procter and Gamble Company Process for preparing a detergent composition
EP2166077A1 (en) 2008-09-12 2010-03-24 The Procter and Gamble Company Particles comprising a hueing dye
EP2163608A1 (en) 2008-09-12 2010-03-17 The Procter & Gamble Company Laundry particle made by extrusion comprising a hueing dye and fatty acid soap
EP2166078B1 (en) 2008-09-12 2018-11-21 The Procter & Gamble Company Laundry particle made by extrusion comprising a hueing dye
RU2532165C2 (en) 2008-09-22 2014-10-27 Дзе Проктер Энд Гэмбл Компани Specific branched aldehydes, alcohols, surfactants and consumer products based thereon
US8232431B2 (en) 2008-09-22 2012-07-31 The Procter & Gamble Company Specific branched surfactants and consumer products
EP2210520A1 (en) 2009-01-22 2010-07-28 The Procter & Gamble Company Package comprising an adhesive perfume delivery material
WO2011005623A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company Laundry detergent composition comprising low level of bleach
WO2011005813A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company Method of laundering fabric using a compacted laundry detergent composition
US20110005001A1 (en) 2009-07-09 2011-01-13 Eric San Jose Robles Detergent Composition
EP2451932A1 (en) 2009-07-09 2012-05-16 The Procter & Gamble Company Method of laundering fabric using a compacted laundry detergent composition
EP2451918A1 (en) 2009-07-09 2012-05-16 The Procter & Gamble Company Method of laundering fabric using a compacted laundry detergent composition
WO2011005911A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company Method of laundering fabric using a compacted liquid laundry detergent composition
BR112012000531A2 (en) 2009-07-09 2019-09-24 Procter & Gamble catalytic laundry detergent composition comprising relatively low levels of water-soluble electrolyte
WO2011005804A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company Method of laundering fabric using a liquid laundry detergent composition
EP2451925A1 (en) 2009-07-09 2012-05-16 The Procter & Gamble Company Method of laundering fabric using a compacted laundry detergent composition
WO2011005730A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company A catalytic laundry detergent composition comprising relatively low levels of water-soluble electrolyte
US20110009307A1 (en) 2009-07-09 2011-01-13 Alan Thomas Brooker Laundry Detergent Composition Comprising Low Level of Sulphate
WO2011005917A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company Method of laundering fabric using a liquid laundry detergent composition
US20110005002A1 (en) 2009-07-09 2011-01-13 Hiroshi Oh Method of Laundering Fabric
WO2011016958A2 (en) 2009-07-27 2011-02-10 The Procter & Gamble Company Detergent composition
PL2292725T5 (en) 2009-08-13 2022-11-07 The Procter And Gamble Company Method of laundering fabrics at low temperature
EP2302025B1 (en) 2009-09-08 2016-04-13 The Procter & Gamble Company A laundry detergent composition comprising a highly water-soluble carboxmethyl cellulose particle
WO2011038078A1 (en) 2009-09-23 2011-03-31 The Procter & Gamble Company Process for preparing spray-dried particles
US20110081388A1 (en) 2009-10-07 2011-04-07 Hiroshi Oh Detergent Composition
EP2336283B1 (en) 2009-12-18 2013-01-16 The Procter & Gamble Company Cleaning composition containing hemicellulose
DE102010001350A1 (en) 2010-01-29 2011-08-04 Evonik Goldschmidt GmbH, 45127 Novel linear polydimethylsiloxane-polyether copolymers having amino and / or quaternary ammonium groups and their use
EP2529001B1 (en) 2010-01-29 2018-09-19 The Procter and Gamble Company Novel linear polydimethylsiloxane-polyether copolymers with amino and/or quaternary ammonium groups and use thereof
WO2011100411A1 (en) 2010-02-12 2011-08-18 The Procter & Gamble Company Benefit compositions comprising polyglycerol esters
US20110201537A1 (en) 2010-02-12 2011-08-18 Jennifer Beth Ponder Benefit compositions comprising crosslinked polyglycerol esters
WO2011100420A1 (en) 2010-02-12 2011-08-18 The Procter & Gamble Company Benefit compositions comprising crosslinked polyglycerol esters
US20110201534A1 (en) 2010-02-12 2011-08-18 Jennifer Beth Ponder Benefit compositions comprising polyglycerol esters
WO2011100667A1 (en) 2010-02-14 2011-08-18 Ls9, Inc. Surfactant and cleaning compositions comprising microbially produced branched fatty alcohols
WO2011109322A1 (en) 2010-03-04 2011-09-09 The Procter & Gamble Company Detergent composition
US8889612B2 (en) 2010-04-19 2014-11-18 The Procter & Gamble Company Method of laundering fabric using a compacted liquid laundry detergent composition
EP2380960A1 (en) 2010-04-19 2011-10-26 The Procter & Gamble Company Detergent composition
US20110257062A1 (en) 2010-04-19 2011-10-20 Robert Richard Dykstra Liquid laundry detergent composition comprising a source of peracid and having a ph profile that is controlled with respect to the pka of the source of peracid
US20110257060A1 (en) 2010-04-19 2011-10-20 Robert Richard Dykstra Laundry detergent composition comprising bleach particles that are suspended within a continuous liquid phase
US20110257069A1 (en) 2010-04-19 2011-10-20 Stephen Joseph Hodson Detergent composition
CN102906239B (en) 2010-05-18 2015-09-09 美利肯公司 White dyes and containing its composition
EP3020768B1 (en) 2010-05-18 2018-04-25 Milliken & Company Optical brighteners and compositions comprising the same
US20110287067A1 (en) 2010-05-24 2011-11-24 University Of Utah Research Foundation Reinforced adhesive complex coacervates and methods of making and using thereof
US8476216B2 (en) 2010-05-28 2013-07-02 Milliken & Company Colored speckles having delayed release properties
US8470760B2 (en) 2010-05-28 2013-06-25 Milliken 7 Company Colored speckles for use in granular detergents
EP2395070A1 (en) 2010-06-10 2011-12-14 The Procter & Gamble Company Liquid laundry detergent composition comprising lipase of bacterial origin
EP2585573A1 (en) 2010-06-23 2013-05-01 The Procter and Gamble Company Product for pre-treatment and laundering of stained fabric
EP2588652B1 (en) 2010-07-02 2019-06-12 The Procter and Gamble Company Method for treating a fabric
PL2588288T3 (en) 2010-07-02 2016-04-29 Procter & Gamble Process for making films from nonwoven webs
BR112013000101A2 (en) 2010-07-02 2016-05-17 Procter & Gamble filaments comprising active agent nonwoven webs and methods of manufacture thereof
BR112013000104A2 (en) 2010-07-02 2016-05-17 Procter & Gamble detergent product
RU2012154298A (en) 2010-07-02 2014-08-10 Дзе Проктер Энд Гэмбл Компани FILAMENTS CONTAINING SUITABLE FOR RECEPTION INSIDE ACTIVE AGENTS, NONWOVEN CLOTHES AND METHODS FOR THEIR MANUFACTURE
EP2588655B1 (en) 2010-07-02 2017-11-15 The Procter and Gamble Company Method for delivering an active agent
US20120172281A1 (en) 2010-07-15 2012-07-05 Jeffrey John Scheibel Detergent compositions comprising microbially produced fatty alcohols and derivatives thereof
BR112013004889A8 (en) 2010-09-20 2016-10-11 Procter & Gamble fluoropolymer-free surface protection composition
WO2012040171A1 (en) 2010-09-20 2012-03-29 The Procter & Gamble Company Non-fluoropolymer surface protection composition
MX363547B (en) 2010-09-20 2019-03-26 The Procter & Gamble Company Star Fabric care formulations and methods.
WO2012054058A1 (en) 2010-10-22 2012-04-26 The Procter & Gamble Company Bis-azo colorants for use as bluing agents
US20120101018A1 (en) 2010-10-22 2012-04-26 Gregory Scot Miracle Bis-azo colorants for use as bluing agents
WO2010151906A2 (en) 2010-10-22 2010-12-29 Milliken & Company Bis-azo colorants for use as bluing agents
WO2011017719A2 (en) 2010-11-12 2011-02-10 Milliken & Company Thiophene azo dyes and laundry care compositions containing the same
WO2011011799A2 (en) 2010-11-12 2011-01-27 The Procter & Gamble Company Thiophene azo dyes and laundry care compositions containing the same
US8715368B2 (en) 2010-11-12 2014-05-06 The Procter & Gamble Company Thiophene azo dyes and laundry care compositions containing the same
US8846596B2 (en) 2011-02-16 2014-09-30 The Procter & Gamble Company Liquid cleaning compositions
WO2012112741A1 (en) 2011-02-16 2012-08-23 The Procter & Gamble Company Compositions and methods of bleaching
CN103492062A (en) 2011-02-25 2014-01-01 美利肯公司 Capsules and compositions containing them
US9163146B2 (en) 2011-06-03 2015-10-20 Milliken & Company Thiophene azo carboxylate dyes and laundry care compositions containing the same
US20120324655A1 (en) 2011-06-23 2012-12-27 Nalini Chawla Product for pre-treatment and laundering of stained fabric
US20140141126A1 (en) 2011-06-29 2014-05-22 Solae Llc Baked food compositions comprising soy whey proteins that have been isolated from processing streams
EP2737043B1 (en) 2011-07-25 2017-01-04 The Procter and Gamble Company Detergents having acceptable color
US8841246B2 (en) 2011-08-05 2014-09-23 Ecolab Usa Inc. Cleaning composition containing a polysaccharide hybrid polymer composition and methods of improving drainage
US8636918B2 (en) 2011-08-05 2014-01-28 Ecolab Usa Inc. Cleaning composition containing a polysaccharide hybrid polymer composition and methods of controlling hard water scale
US8853144B2 (en) 2011-08-05 2014-10-07 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer composition and methods of improving drainage
US8679366B2 (en) 2011-08-05 2014-03-25 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer composition and methods of controlling hard water scale
AR089647A1 (en) 2011-08-15 2014-09-10 Procter & Gamble DETERGENT COMPOSITIONS CONTAINING PYRIDINOL N-OXIDE COMPOUNDS
JP2014534279A (en) 2011-09-20 2014-12-18 ザ プロクター アンド ギャンブルカンパニー Detergent composition comprising an isoprenoid surfactant in a specific blend ratio
MX2014003278A (en) 2011-09-20 2014-05-21 Procter & Gamble Detergent compositions comprising primary surfactant systems comprising highly branched surfactants especially isoprenoid - based surfactants.
WO2013043852A2 (en) 2011-09-20 2013-03-28 The Procter & Gamble Company Easy-rinse detergent compositions comprising isoprenoid-based surfactants
JP2014526604A (en) 2011-09-20 2014-10-06 ザ プロクター アンド ギャンブル カンパニー Detergent composition comprising a sustainable surfactant system comprising an isoprenoid-derived surfactant
WO2013043855A2 (en) 2011-09-20 2013-03-28 The Procter & Gamble Company High suds detergent compositions comprising isoprenoid-based surfactants
EP2581438A1 (en) 2011-10-12 2013-04-17 The Procter and Gamble Company Detergent composition
US9051406B2 (en) 2011-11-04 2015-06-09 Akzo Nobel Chemicals International B.V. Graft dendrite copolymers, and methods for producing the same
JP2014532791A (en) 2011-11-04 2014-12-08 アクゾ ノーベル ケミカルズ インターナショナル ベスローテン フエンノートシャップＡｋｚｏ Ｎｏｂｅｌ Ｃｈｅｍｉｃａｌｓ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｂ．Ｖ． Hybrid dendritic copolymer, composition thereof and method for producing the same
CA2853487C (en) 2011-11-11 2016-08-02 Sherri Lynn Randall Surface treatment compositions including shielding salts
CN106906573B (en) 2012-01-04 2019-08-27 宝洁公司 Active substance-containing fibrous structures with multiple regions of different densities
WO2013103629A1 (en) 2012-01-04 2013-07-11 The Procter & Gamble Company Active containing fibrous structures with multiple regions
GB2498265B (en) 2012-01-04 2015-04-08 Procter & Gamble Fibrous structures comprising particles and methods for making same
WO2013109671A1 (en) 2012-01-18 2013-07-25 The Procter & Gamble Company Acidic laundry detergent compositions
WO2013126550A2 (en) 2012-02-22 2013-08-29 Kci Licensing, Inc. New compositions, the preparation and use thereof
US8853142B2 (en) 2012-02-27 2014-10-07 The Procter & Gamble Company Methods for producing liquid detergent products
WO2013134269A2 (en) 2012-03-06 2013-09-12 Kci Licensing, Inc. New compositions, the preparation and use thereof
CA2867296C (en) * 2012-03-26 2016-09-27 The Procter & Gamble Company Cleaning compositions comprising ph-switchable amine surfactants
WO2014018309A1 (en) 2012-07-26 2014-01-30 The Procter & Gamble Company Low ph liquid cleaning compositions with enzymes
US8945314B2 (en) 2012-07-30 2015-02-03 Ecolab Usa Inc. Biodegradable stability binding agent for a solid detergent
US9796952B2 (en) 2012-09-25 2017-10-24 The Procter & Gamble Company Laundry care compositions with thiazolium dye
EP2953992B1 (en) 2013-02-06 2021-11-24 3M Innovative Properties Company Polymers, preparation and use thereof
WO2014150171A1 (en) 2013-03-15 2014-09-25 The Procter & Gamble Company Specific unsaturated and branched functional materials for use in consumer products
EP2978831B1 (en) 2013-03-28 2020-12-02 The Procter and Gamble Company Cleaning compositions containing a polyetheramine, a soil release polymer, and a carboxymethylcellulose
US20150150768A1 (en) 2013-12-04 2015-06-04 Los Alamos National Security Llc Furan Based Composition
MX381740B (en) 2013-12-09 2025-03-12 Procter & Gamble FIBROUS STRUCTURES THAT INCLUDE AN ACTIVE AGENT AND HAVE A GRAPHIC PRINTED ON THEM.
US20150210964A1 (en) 2014-01-24 2015-07-30 The Procter & Gamble Company Consumer Product Compositions
CA2941253A1 (en) 2014-03-27 2015-10-01 Frank Hulskotter Cleaning compositions containing a polyetheramine
EP3122850A1 (en) 2014-03-27 2017-02-01 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
US9365805B2 (en) 2014-05-15 2016-06-14 Ecolab Usa Inc. Bio-based pot and pan pre-soak
EP3152288A1 (en) 2014-06-06 2017-04-12 The Procter & Gamble Company Detergent composition comprising polyalkyleneimine polymers
CN116103096A (en) 2014-06-30 2023-05-12 宝洁公司 laundry detergent composition
US9913927B2 (en) 2014-07-14 2018-03-13 University Of Utah Research Foundation In situ solidifying complex coacervates and methods of making and using thereof
US9809782B2 (en) 2014-08-27 2017-11-07 The Procter & Gamble Company Detergent composition comprising a cationic polymer and anionic/nonionic surfactant mixture
CA2956095C (en) 2014-08-27 2019-10-08 The Procter & Gamble Company Detergent composition comprising a cationic polymer
WO2016032995A1 (en) 2014-08-27 2016-03-03 The Procter & Gamble Company Method of treating a fabric
JP6728132B2 (en) 2014-08-27 2020-07-22 ザ プロクター アンド ギャンブル カンパニーＴｈｅ Ｐｒｏｃｔｅｒ ＆ Ｇａｍｂｌｅ Ｃｏｍｐａｎｙ Detergent composition containing cationic polymer
EP3197992B1 (en) 2014-09-25 2023-06-28 The Procter & Gamble Company Fabric care compositions containing a polyetheramine
US9506019B2 (en) 2015-01-28 2016-11-29 The Procter & Gamble Company Silicone nanoemulsion comprising alkylene glycol alkyl ether
US9982223B2 (en) 2015-01-28 2018-05-29 The Procter & Gamble Company Amino silicone nanoemulsion
US10182980B2 (en) 2015-01-28 2019-01-22 The Procter & Gamble Company Method of making an amino silicone nanoemulsion
US20160230124A1 (en) 2015-02-10 2016-08-11 The Procter & Gamble Company Liquid laundry cleaning composition
US9902923B2 (en) 2015-10-13 2018-02-27 The Procter & Gamble Company Polyglycerol dye whitening agents for cellulosic substrates
US9745544B2 (en) 2015-10-13 2017-08-29 The Procter & Gamble Company Whitening agents for cellulosic substrates
US9777250B2 (en) 2015-10-13 2017-10-03 Milliken & Company Whitening agents for cellulosic substrates
US10597614B2 (en) 2015-10-13 2020-03-24 The Procter & Gamble Company Whitening agents for cellulosic substrates
US10155868B2 (en) 2015-10-13 2018-12-18 Milliken & Company Whitening agents for cellulosic substrates
US9976035B2 (en) 2015-10-13 2018-05-22 Milliken & Company Whitening agents for cellulosic substrates
US10308900B2 (en) 2015-12-22 2019-06-04 Milliken & Company Occult particles for use in granular laundry care compositions
WO2017127258A1 (en) 2016-01-21 2017-07-27 The Procter & Gamble Company Fibrous elements comprising polyethylene oxide
US9719056B1 (en) 2016-01-29 2017-08-01 The Procter & Gamble Company Bis-azo colorants for use as bluing agents
US20180072970A1 (en) 2016-09-13 2018-03-15 The Procter & Gamble Company Stable violet-blue to blue imidazolium compounds
WO2018085378A1 (en) 2016-11-01 2018-05-11 Milliken & Company Leuco polymers as bluing agents in laundry care compositions
US10676699B2 (en) 2016-11-01 2020-06-09 The Procter & Gamble Company Leuco colorants as bluing agents in laundry care compositions
EP3535361B1 (en) 2016-11-01 2020-12-30 The Procter & Gamble Company Leuco polymers as bluing agents in laundry care compositions
US10472595B2 (en) 2016-11-01 2019-11-12 The Procter & Gamble Company Leuco polymers as bluing agents in laundry care compositions
WO2018085388A1 (en) 2016-11-01 2018-05-11 Milliken & Company Leuco polymers as bluing agents in laundry care compositions
EP3535320A1 (en) 2016-11-01 2019-09-11 Milliken & Company Leuco polymers as bluing agents in laundry care compositions
EP3535372B1 (en) 2016-11-01 2020-09-09 The Procter & Gamble Company Leuco polymers as bluing agents in laundry care compositions
JP6926202B2 (en) 2016-11-01 2021-08-25 ミリケン・アンド・カンパニーＭｉｌｌｉｋｅｎ ＆ Ｃｏｍｐａｎｙ Roy copolymer as a bluish agent in laundry care compositions
JP2020506975A (en) 2016-11-01 2020-03-05 ミリケン・アンド・カンパニーＭｉｌｌｉｋｅｎ ＆ Ｃｏｍｐａｎｙ Roy copolymers as bluing agents in laundry care compositions
EP3535363B1 (en) 2016-11-01 2022-08-31 The Procter & Gamble Company Leuco polymers as bluing agents in laundry care compositions
EP3535366A1 (en) 2016-11-01 2019-09-11 The Procter and Gamble Company Reactive leuco compounds and compositions comprising the same
EP3535324A1 (en) 2016-11-01 2019-09-11 Milliken & Company Leuco polymers as bluing agents in laundry care compositions
EP3535374B1 (en) 2016-11-01 2020-09-30 The Procter and Gamble Company Leuco polymers as bluing agents in laundry care compositions
US20180119058A1 (en) 2016-11-01 2018-05-03 The Procter & Gamble Company Leuco triphenylmethane colorants as bluing agents in laundry care compositions
EP3535376B1 (en) 2016-11-01 2022-06-15 The Procter & Gamble Company Methods of using leuco colorants as bluing agents in laundry care compositions
US20180119057A1 (en) 2016-11-01 2018-05-03 The Procter & Gamble Company Methods of using leuco colorants as bluing agents in laundry care compositions
EP3535330A1 (en) 2016-11-01 2019-09-11 Milliken & Company Leuco polymers as bluing agents in laundry care compositions
BR112019006608A2 (en) 2016-11-01 2019-07-02 Milliken & Co leuco reactive compounds and compositions comprising the same
EP3535371B1 (en) 2016-11-01 2020-09-09 The Procter & Gamble Company Leuco polymers as bluing agents in laundry care compositions
JP7009474B2 (en) 2016-11-01 2022-01-25 ミリケン・アンド・カンパニー Roy copolymer as a bluish agent in laundry care compositions
US10479961B2 (en) 2016-11-01 2019-11-19 The Procter & Gamble Company Leuco polymers as bluing agents in laundry care compositions
US10385294B2 (en) 2016-11-01 2019-08-20 The Procter & Gamble Company Leuco polymers as bluing agents in laundry care compositions
WO2019075143A1 (en) 2017-10-12 2019-04-18 The Procter & Gamble Company Leuco colorants as bluing agents in laundry care compositions
US11697905B2 (en) 2017-01-27 2023-07-11 The Procter & Gamble Company Active agent-containing articles that exhibit consumer acceptable article in-use properties
US11697904B2 (en) 2017-01-27 2023-07-11 The Procter & Gamble Company Active agent-containing articles that exhibit consumer acceptable article in-use properties
GB2572720B (en) 2017-01-27 2022-06-22 Procter & Gamble Active agent-containing articles that exhibit consumer acceptable article in-use properties
US11697906B2 (en) 2017-01-27 2023-07-11 The Procter & Gamble Company Active agent-containing articles and product-shipping assemblies for containing the same
CA3075094A1 (en) 2017-10-12 2019-04-18 The Procter & Gamble Company Laundry care compositions comprising a leuco composition and an amine, and related methods for treating textile articles
TW201922942A (en) 2017-10-12 2019-06-16 美商美力肯及公司 Triarylmethane leuco compounds and compositions comprising the same
EP3694969B1 (en) 2017-10-12 2021-08-18 The Procter & Gamble Company Laundry care compositions comprising leuco compounds
EP3694979A1 (en) 2017-10-12 2020-08-19 The Procter & Gamble Company Methods of using leuco colorants as bluing agents in laundry care compositions
EP3694978A1 (en) 2017-10-12 2020-08-19 The Procter & Gamble Company Leuco colorants with extended conjugation as bluing agents in laundry care formulations
EP3694928A1 (en) 2017-10-12 2020-08-19 Milliken & Company Leuco compounds
JP7071496B2 (en) 2017-10-12 2022-05-19 ミリケン・アンド・カンパニー A composition containing a leuco compound and a leuco compound.
CN111479880B (en) 2017-10-12 2021-10-15 美利肯公司 Leuco Colorants with Extended Conjugation
US11230686B2 (en) 2017-10-12 2022-01-25 The Procter & Gamble Company Laundry care compositions and methods for determining their age
CN111247236A (en) 2017-10-12 2020-06-05 宝洁公司 Method for using leuco colorants as bluing agents in laundry care compositions
US11046920B2 (en) 2017-10-12 2021-06-29 The Procter & Gamble Company Methods of using leuco colorants as bluing agents in laundry care compositions
AU2019212513B2 (en) 2018-01-26 2024-10-31 Fluidx Medical Technology, Llc Apparatus and method of using in situ solidifying complex coacervates for vascular occlusion
CA3106528A1 (en) 2018-07-27 2020-01-30 The Procter & Gamble Company Leuco colorants as bluing agents in laundry care compositions
US11987552B2 (en) 2018-07-27 2024-05-21 Milliken & Company Polymeric phenolic antioxidants
WO2020023897A1 (en) 2018-07-27 2020-01-30 Milliken & Company Stabilized compositions comprising leuco compounds
EP3830159A1 (en) 2018-07-27 2021-06-09 Milliken & Company Polymeric amine antioxidants
US20200078758A1 (en) 2018-09-07 2020-03-12 The Procter & Gamble Company Methods and Systems for Forming Microcapsules
US20200078759A1 (en) 2018-09-07 2020-03-12 The Procter & Gamble Company Methods and Systems for Forming Microcapsules
US20200078757A1 (en) 2018-09-07 2020-03-12 The Procter & Gamble Company Methods and Systems for Forming Microcapsules
WO2020061242A1 (en) 2018-09-21 2020-03-26 The Procter & Gamble Company Active agent-containing matrix particles and processes for making same
US20200123475A1 (en) 2018-10-18 2020-04-23 Milliken & Company Polyethyleneimine compounds containing n-halamine and derivatives thereof
US11299591B2 (en) 2018-10-18 2022-04-12 Milliken & Company Polyethyleneimine compounds containing N-halamine and derivatives thereof
US11466122B2 (en) 2018-10-18 2022-10-11 Milliken & Company Polyethyleneimine compounds containing N-halamine and derivatives thereof
US20200123319A1 (en) 2018-10-18 2020-04-23 Milliken & Company Polyethyleneimine compounds containing n-halamine and derivatives thereof
US20200123472A1 (en) 2018-10-18 2020-04-23 Milliken & Company Polyethyleneimine compounds containing n-halamine and derivatives thereof
US11518963B2 (en) 2018-10-18 2022-12-06 Milliken & Company Polyethyleneimine compounds containing N-halamine and derivatives thereof
US11732218B2 (en) 2018-10-18 2023-08-22 Milliken & Company Polyethyleneimine compounds containing N-halamine and derivatives thereof
JP2022505301A (en) 2018-11-16 2022-01-14 ザ プロクター アンド ギャンブル カンパニー Compositions and methods for removing stains from fabrics
CN113166680A (en) 2018-12-14 2021-07-23 宝洁公司 Foamed fibrous structures comprising particles and methods of making the same
EP3894528A1 (en) 2018-12-14 2021-10-20 The Procter & Gamble Company Water disintegrable, foam producing article
US11485934B2 (en) 2019-08-02 2022-11-01 The Procter & Gamble Company Foaming compositions for producing a stable foam and methods for making same
US20210148044A1 (en) 2019-11-15 2021-05-20 The Procter & Gamble Company Graphic-Containing Soluble Articles and Methods for Making Same
HUE065856T2 (en) 2020-02-14 2024-06-28 Basf Se Biodegradable graft polymers
MX2022010150A (en) 2020-02-21 2022-09-12 Basf Se ALCOXYLATED POLYALKYLENIMINES OR ALCOXYLATED POLYAMINES WITH IMPROVED BIODEGRADABILITY.
US11718814B2 (en) 2020-03-02 2023-08-08 Milliken & Company Composition comprising hueing agent
US12195703B2 (en) 2020-03-02 2025-01-14 Milliken & Company Composition comprising hueing agent
US12031113B2 (en) 2020-03-02 2024-07-09 Milliken & Company Composition comprising hueing agent
BR112023002786A2 (en) 2020-08-26 2023-03-14 Unilever Ip Holdings B V SOLID DETERGENT COMPOSITION FOR WASHING CLOTHES, METHOD OF WASHING A TEXTILE SURFACE WITH THE DETERGENT COMPOSITION AND USE
EP4011933A1 (en) 2020-12-11 2022-06-15 Basf Se Improved biodegradable polymer with primary washing performance benefit
EP4263777B1 (en) 2020-12-15 2026-04-22 Basf Se Biodegradable polymers
US20240132668A1 (en) 2020-12-23 2024-04-25 Basf Se Amphiphilic alkoxylated polyalkylene imines or alkoxylated polyamines
JP2024507319A (en) 2020-12-23 2024-02-19 ビーエーエスエフ ソシエタス・ヨーロピア Novel alkoxylated polyalkyleneimine or alkoxylated polyamine
WO2022197295A1 (en) 2021-03-17 2022-09-22 Milliken & Company Polymeric colorants with reduced staining
CN117677689A (en) 2021-05-18 2024-03-08 诺力昂化学品国际有限公司 Polyester Polyquats in Cleaning Applications
EP4341317A1 (en) 2021-05-20 2024-03-27 Nouryon Chemicals International B.V. Manufactured polymers having altered oligosaccharide or polysaccharide functionality or narrowed oligosaccharide distribution, processes for preparing them, compositions containing them, and methods of using them
US12371820B2 (en) 2021-05-28 2025-07-29 The Procter & Gamble Company Natural polymer-based fibrous elements comprising a surfactant and methods for making same
WO2022263354A1 (en) 2021-06-18 2022-12-22 Basf Se Biodegradable graft polymers
WO2023275269A1 (en) 2021-06-30 2023-01-05 Nouryon Chemicals International B.V. Chelate-amphoteric surfactant liquid concentrates and use thereof in cleaning applications
CA3228918A1 (en) 2021-08-10 2023-02-16 Nippon Shokubai Co., Ltd. Polyalkylene-oxide-containing compound
US20250129197A1 (en) 2021-08-12 2025-04-24 Basf Se Biodegradable graft polymers
EP4134421B1 (en) 2021-08-12 2025-05-21 The Procter & Gamble Company Detergent composition comprising detersive surfactant and graft polymer
US20240352383A1 (en) 2021-08-12 2024-10-24 Basf Se Biodegradable graft polymers
US20250136740A1 (en) 2021-08-12 2025-05-01 Basf Se Biodegradable graft polymers for dye transfer inhibition
HUE072325T2 (en) 2021-08-12 2025-11-28 Procter & Gamble Detergent composition comprising detersive surfactant and biodegradable graft polymers
WO2023021101A1 (en) 2021-08-19 2023-02-23 Basf Se Modified alkoxylated polyalkylene imines
US20240360280A1 (en) 2021-08-19 2024-10-31 Basf Se Modified alkoxylated polyalkylene imines or modified alkoxylated polyamines
US20250122337A1 (en) 2021-08-19 2025-04-17 Basf Se Modified alkoxylated polyalkylene imines and modified alkoxylated polyamines obtainable by a process comprising the steps a) to d)
JP2024531330A (en) 2021-08-19 2024-08-29 ビーエーエスエフ ソシエタス・ヨーロピア Modified alkoxylated oligoalkyleneimines and modified alkoxylated oligoamines
WO2023117494A1 (en) 2021-12-20 2023-06-29 Basf Se Polypropylene imine polymers (ppi), their preparation, uses, and compositions comprising such ppi
WO2023117888A1 (en) 2021-12-21 2023-06-29 Basf Se Chemical product passport for emission data
EP4558536A1 (en) 2022-07-21 2025-05-28 Basf Se Biodegradable graft polymers useful for dye transfer inhibition
WO2024042005A1 (en) 2022-08-22 2024-02-29 Basf Se Process for producing sulfatized esteramines
JP2025538407A (en) 2022-11-15 2025-11-28 ミリケン・アンド・カンパニー Optical brightener compositions and laundry care compositions containing same
WO2024119440A1 (en) 2022-12-08 2024-06-13 Basf Se Biodegradable multi-block copolymers comprising linking units derived from cyclic ketene acetal
EP4634249A1 (en) 2022-12-12 2025-10-22 Basf Se Biodegradable graft polymers as dye transfer inhibitors
CN120569420A (en) 2022-12-12 2025-08-29 巴斯夫欧洲公司 Biodegradable graft polymers for dye transfer inhibition
CN120344576A (en) 2022-12-12 2025-07-18 巴斯夫欧洲公司 Biodegradable graft polymers
DE102023135175A1 (en) 2022-12-16 2024-06-27 Basf Se Process for the preparation of amino acid esters and organic sulfonic acid salts as well as amino acid esters and their salts
WO2024175401A1 (en) 2023-02-21 2024-08-29 Basf Se Modified alkoxylated polyalkylene imines or modified alkoxylated polyamines
WO2024175409A1 (en) 2023-02-21 2024-08-29 Basf Se Modified hyperbranched alkoxylated polyalkylene imines
CN120731240A (en) 2023-02-21 2025-09-30 巴斯夫欧洲公司 Modified alkoxylated polyalkylene imine or modified alkoxylated polyamine
WO2024188713A1 (en) 2023-03-13 2024-09-19 Basf Se Alkoxylated nitrogen containing polymers and their use
EP4688728A1 (en) 2023-03-24 2026-02-11 Basf Se Process for the preparation of amino acid esters as organoether sulfate salts from alkoxylated alcohols
WO2024213626A1 (en) 2023-04-12 2024-10-17 Basf Se Vinyl acetate having low deuterium content
MX2025013215A (en) 2023-05-05 2025-12-01 Basf Se Biodegradable polyol propoxylates, their preparation, uses, and compositions comprising them
CN121335969A (en) 2023-06-13 2026-01-13 巴斯夫欧洲公司 Stable cleaning compositions containing EDDS and enzymes and their uses
WO2025055891A1 (en) 2023-09-11 2025-03-20 Basf Se Alkoxylated iso-nonanol
EP4549621A1 (en) 2023-10-31 2025-05-07 Basf Se Process for making amines from alcohols using hydrogen having low deuterium content produced with non-fossil energy
WO2025125117A1 (en) 2023-12-15 2025-06-19 Basf Se Biodegradable propoxylated ethylenediamines, their preparation, uses, and compositions comprising them
WO2025131888A1 (en) 2023-12-19 2025-06-26 Basf Se Modified alkoxylated polyalkylene imines or modified alkoxylated polyamines
WO2025180874A1 (en) 2024-02-27 2025-09-04 Basf Se Substituted 1,3-dioxolane sulfates and their use
WO2025195856A1 (en) 2024-03-19 2025-09-25 Basf Se Compositions of guerbet alkyl sulfates and their use
WO2025202032A1 (en) 2024-03-26 2025-10-02 Basf Se Biodegradable alkoxylated polyols, their preparation, uses, and compositions comprising them
WO2025201396A1 (en) 2024-03-27 2025-10-02 Basf Se Alkoxylated iso-nonanol
WO2025223955A1 (en) 2024-04-25 2025-10-30 Basf Se Method for producing polyaspartic acid, polyaspartic acid and its use
WO2025238047A1 (en) 2024-05-14 2025-11-20 Basf Se Cellulose acetate with low degree of substitution
WO2026061874A1 (en) 2024-09-20 2026-03-26 Basf Se Cleaning composition comprising ketal or acetal diamines and its use
WO2026081981A1 (en) 2024-10-14 2026-04-23 Basf Se Detergent compositions comprising lysine-caprolactam copolymers

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB673212A (en) * 1949-02-15 1952-06-04 Ciba Ltd Manufacture of new quaternary ammonium compounds
GB719610A (en) * 1952-01-29 1954-12-01 Ciba Ltd Manufacture of new azapentylene diammonium compounds
GB866335A (en) * 1956-07-31 1961-04-26 Ciba Ltd Process for the dyeing of fibres of polyacrylonitrile
GB1383127A (en) * 1971-06-11 1975-02-05 Basf Ag Aminoalkylating tertiary amines
GB1521240A (en) * 1976-06-12 1978-08-16 Bayer Ag Quaternary compounds and their use for increasing the affinity of anionic dyestuffs for fibrous materials
GB1539006A (en) * 1975-04-23 1979-01-24 Merck & Co Inc Aminoalkylammonium compound
EP0104984A2 (en) * 1982-09-24 1984-04-04 Societe Nationale Des Poudres Et Explosifs Vinylcarbamic acid esters and their preparation

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4248827A (en) * 1978-06-12 1981-02-03 The Procter & Gamble Company Method for sanitizing toilets
US4960526A (en) * 1985-07-25 1990-10-02 Colgate-Polmolive Company Diammonium compound containing fabric softening and antistatic detergent composition
US4824867A (en) * 1986-08-08 1989-04-25 Smith Kim R Quaternary ammonium compounds
JPH0726118B2 (en) * 1987-10-28 1995-03-22 ライオン株式会社 Bleach composition
USH1313H (en) * 1991-08-30 1994-05-03 Minnesota Mining And Manufacturing Company Process of making poly(glycidyl azide) product and compounds useful therein
JP3021997B2 (en) * 1992-10-08 2000-03-15 花王株式会社 Soft finish
US5259990A (en) * 1993-03-25 1993-11-09 Xerox Corporation Electrically conductive polyurethane elastomer

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB673212A (en) * 1949-02-15 1952-06-04 Ciba Ltd Manufacture of new quaternary ammonium compounds
GB719610A (en) * 1952-01-29 1954-12-01 Ciba Ltd Manufacture of new azapentylene diammonium compounds
GB866335A (en) * 1956-07-31 1961-04-26 Ciba Ltd Process for the dyeing of fibres of polyacrylonitrile
GB1383127A (en) * 1971-06-11 1975-02-05 Basf Ag Aminoalkylating tertiary amines
GB1539006A (en) * 1975-04-23 1979-01-24 Merck & Co Inc Aminoalkylammonium compound
GB1521240A (en) * 1976-06-12 1978-08-16 Bayer Ag Quaternary compounds and their use for increasing the affinity of anionic dyestuffs for fibrous materials
EP0104984A2 (en) * 1982-09-24 1984-04-04 Societe Nationale Des Poudres Et Explosifs Vinylcarbamic acid esters and their preparation

Also Published As

Publication number Publication date
BR9807832A (en) 2000-09-19
GB9702731D0 (en) 1997-04-02
CN1252091A (en) 2000-05-03
JP2001511209A (en) 2001-08-07
EP0975720A1 (en) 2000-02-02
EP0975720A4 (en) 2002-08-21
CA2279882A1 (en) 1998-08-13
AU6149698A (en) 1998-08-26
WO1998035003A1 (en) 1998-08-13

Similar Documents

Publication Publication Date Title
GB2321900A (en) Cationic surfactants
CA1316641C (en) Stable biodegradable fabric softening compositions containing 2-hydroxypropyl monoester quaternized ammonium salts
US4416793A (en) Liquid detergent compositions containing amino-silanes
EP4168472A1 (en) Amphiphilic alkoxylated polyethylene/-propylene imine copolymers for multi-benefit detergent formulations
CA1309925C (en) Laundry detergent compositions
KR100336148B1 (en) Color care compositions
EP1419230A1 (en) Complexed surfactant system
JPH10510287A (en) Succinic acid derivatives and their use as surfactants
CA2357756A1 (en) Cationic gemini and related multiple hydrophilic/hydrophobic functional compounds and their use as surfactants
EP2328997B1 (en) Gel surfactant composition
EP0416686B1 (en) Process for preparing quaternized imidazoline fabric conditioning compounds
EP3898577B1 (en) Glucamide-based surfactants
CA2285538A1 (en) Composition useful for fabric softening applications and processes for the preparation thereof
US7348303B2 (en) Quaternary ammonium composition
US4395373A (en) Phosphated amine oxides
EP0763088A1 (en) Liquid detergent composition containing oleoyl sarcosinates and anionic surfactants
WO1998045394A2 (en) Composition useful for fabric softening applications and processes for the preparation thereof
US3385858A (en) High molecular weight fatty piperazine amphoteric surfactants
JP2566177B2 (en) Textile softening composition and method for producing the same
MXPA99007386A (en) Detergent compound
CA2352118A1 (en) Cationic ester surfactants which are suitable for both liquid and powder formulations
AU643858B2 (en) Polyamide salts
US6031132A (en) Amide-group-containing polyacetal and its production process and use
EP0648835A1 (en) Use of alkaline polyammonium salts to increase cationic density in fabric softeners
CA2191315A1 (en) Detergent compositions comprising oleoyl sarcosinate and enzymes

Legal Events

Date Code Title Description
WAP Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1)