ES2245819T3 - TENSIOACTIVE AGLOMERATES. - Google Patents

Abstract

A surfactant conglomerate is presented which has a reduced tendency to gelation after contact with water and which has an improved water dissolution profile. The surfactant conglomerate comprises a water soluble salt of acetate attached to the surfactant.

Description

Surfactant agglomerates.

Technical field

The present invention relates to agglomerates of surfactant that are suitable for formulating detergent products. The agglomerates of the present invention have a lower tendency to gel when they come into contact with water as well as a profile Improved dissolution.

Background of the invention

Surfactants are important components of detergent compositions. Surfactant Raw Materials They are generally available as liquids. When they are formulated in solid detergent compositions are typically powdered on a solid component of the composition or added to the composition in the form of a chipboard. The agglomerates are obtained agglomerating a liquid or pasty surfactant with a vehicle in powder. The agglomerates have the advantage that they allow formulating very active compositions since they comprise a greater amount of surfactant by weight of the total composition. The agglomerates of Surfactants are known in the art.

The problems encountered with the agglomerates of surfactant during use is that they tend to gel when they enter in contact with water and may have dissolution profiles poor These two problems tend to increase when you increases agglomerate activity and are especially acute in nonionic surfactants. Therefore an object of the present invention is to provide surfactant agglomerates with a lower tendency to gel when in contact with water and a profile Improved dissolution in water.

In EP-A-O 403 084 Zeolite particles prepared by a process of agglomeration, the particles comprising a charge and a salt inorganic with low absorptivity to maximize the effectiveness of binder.

It has now been found that this object can be fulfilled by formulating a surfactant agglomerate comprising a surfactant and a vehicle and also comprising an acetate salt Water soluble very close to the surfactant. This close proximity it is preferably obtained by mixing the acetate with the surfactant or the vehicle before agglomerating them together, or spraying the acetate, or a portion thereof, on a previous agglomeration of the surfactant and the vehicle and, optionally, the other portion of the acetate.

Summary of the invention

The present invention encompasses a chipboard of surfactant comprising a surfactant and a vehicle, and which It also includes a water-soluble acetate salt very close to surfactant The present invention also encompasses a composition. granular or tablet detergent comprising the agglomerate. The invention also encompasses processes for preparing the agglomerate. Finally, the invention encompasses a powder mixture that It comprises a water-soluble acetate salt that is suitable for preparing the chipboard

Detailed description of the invention Chipboard

The agglomerate of the present invention comprises at least three ingredients: the surfactant, a vehicle and the salt water soluble acetate.

The agglomerate of the present invention can be prepared with any surfactant although the surfactants Preferred for use in the present invention are non-surfactants. ionic

Suitable nonionic surfactants include compounds obtained by condensation of alkylene oxide groups (hydrophilic type) with a hydrophobic organic compound, which can be aliphatic or aromatic alkyl. Group length polyoxyalkylene that condenses with any hydrophobic group is You can easily adjust to obtain a water-soluble compound with the desired degree of balance between the hydrophilic elements and the hydrophobic

Especially preferred for use in the The present invention is non-ionic surfactants such as condensates of poly (ethylene oxide) of alkyl phenols, e.g. eg the condensation products of alkyl phenols having a group alkyl containing from about 6 to 16 carbon atoms, in a linear or branched chain configuration, with of approximately 4 to 25 moles of ethylene oxide per mole of alkyl phenol.

Preferred non-ionic surfactants are those water-soluble condensation products of aliphatic alcohols that contain from 8 to 22 carbon atoms, in chain configuration linear or branched, with an average of up to 25 moles of oxide ethylene per mole of alcohol. Especially preferred are the condensation products of alcohols having an alkyl group containing about 9 to 15 carbon atoms with of about 2 to 10 moles of ethylene oxide per mole of alcohol; and the condensation products of propylene glycol with oxide ethylene. The most preferred are the condensation products of alcohols having an alkyl group containing approximately 12 to 15 carbon atoms with an average of approximately 3 moles of ethylene oxide per mole of alcohol.

Other class of suitable non-ionic surfactants it is the kind of fatty acid polyhydroxyamides that can prepare by reacting a fatty acid ester and a N-alkyl polyhydroxy amine. The preferred amine for use in the present invention is N- (R 1) - CH 2 (CH 2 OH) 4 -CH 2 -OH, wherein R 1 is typically an alkyl group, e.g. eg methyl; and the preferred ester is a methyl ester C 12 -C 20 fatty acid.

Methods of manufacturing polyhydroxyamides from Fatty acid are described in WO 92 6073, published on 16 April 1992. This application describes the preparation of fatty acid polyhydroxyamides in the presence of solvents. In a very preferred embodiment of the invention is reacted N-methyl glucamine with a methyl ester C_ {12} -C_ {20}. The document also states that the formulator of granulated detergent compositions can consider it convenient to carry out the amidation reaction in presence of solvents comprising alcohols C 12 -C 14 alkoxylated and especially ethoxylates (OE 3-8) (page 15, lines 22-27). This can directly provide nonionic surfactant systems that are preferred herein invention, such as those comprising N-methyl glucosamide and C 12 -C 14 alcohols with a average of 3 ethoxylate groups per molecule.

Other non-ionic surfactants that may be used as components of the surfactant systems of the Present invention include glycerol ethers, glucosamides, glycerol amides, glycerol esters, fatty acids, fatty acid esters, fatty amides, alkyl polyglycosides, alkyl polyglycol ethers, polyethylene glycols, alkyl ethoxylated phenols and mixtures of same.

Although the present invention is realized preferably with nonionic surfactants, preferably ethoxylated alcohols, or mixtures of non-ionic surfactants, also can be performed with the following surfactants that are anionic or other type.

Anionic surfactants suitable for use In the present invention include:

- Alkylsulfonate ester surfactants include linear acid esters C 8 -C 20 carboxylic (ie acids fatty) that are sulphonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society "52 (1975), p. 323-329. The appropriate starting materials would include natural fatty substances such as sebum derivatives, palm oil, etc.

The alkyl sulphonate ester surfactant preferred, especially for laundry applications, comprises alkyl sulfonate ester surfactants with the formula structural:

500

where R 3 is a hydrocarbyl C 8 -C 20, preferably an alkyl or a combination thereof, R 4 is a hydrocarbyl C 1 -C 6, preferably an alkyl or a combination thereof, and M is a cation that forms a salt Water soluble with the alkyl sulfonate ester. The training cations Suitable salts include metals such as sodium, potassium and lithium and substituted and unsubstituted ammonium cations, such as monoethanolamine, diethanolamine and triethanolamine. Preferably, R 3 is C 10 -C 16 alkyl and R 4 is methyl, ethyl or isopropyl. Especially preferred are esters. methylsulfonate in which R 3 is alkyl C_ {14} -C_ {16}.

- The alkyl sulfate surfactants in the present invention are water soluble or acidic salts of formula ROSO 3 M where R is preferably a hydrocarbyl C 10 -C 24, preferably an alkyl or hydroxyalkyl with an alkyl component C 10 -C 20, more preferably an alkyl or C 12 -C 18 hydroxyalkyl, and M is H or a cation, p. e.g., an alkali metal cation (e.g., sodium, potassium, lithium) or ammonium or substituted ammonium (e.g., methyl ammonium cations, dimethyl ammonium and trimethyl ammonium and quaternary ammonium cations such such as tetramethyl ammonium and dimethyl cations piperidinium and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures of the same, and the like). Typically, chains are preferred C 12-16 alkyl for wash temperatures lower (for example, below 50 ° C) and C 16-18 alkyl chains for temperatures of higher washing (for example, greater than about 50 ° C).

- The alkoxylated alkyl sulfate type surfactants of the present invention are water soluble or acid salts of formula RO (A) m SO 3 M wherein R is a C 10 -C 24 alkyl or hydroxyalkyl group substituted having a C 10 -C 24 alkyl component, preferably C 12 -C 20 alkyl or hydroxyalkyl, more preferably C 12 -C 18 alkyl or hydroxyalkyl, A is an ethoxy unit or propoxy, m is greater than zero, typically from about 0.5 to about 6, more preferably from about 0.5 to about 3, and M is H or a cation that can be, for example, a metal cation ( e.g., sodium, potassium, lithium, calcium, magnesium, etc.) or a substituted ammonium or ammonium cation. In the present invention both ethoxylated alkyl sulfates and propoxylated alkyl sulfates are contemplated. Specific examples of substituted ammonium cations include methylammonium, dimethylammonium, trimethylammonium and quaternary ammonium cations, such as tetramethylammonium or dimethyl piperidinium, and alkanolamine derived cations, such as ethylamine, diethylamine or triethylamine, mixtures thereof and the like. Illustrative surfactants are C 12 -C 18 alkyl ether (1.0) sulfate, C 12 -C 18 alkyl ether (2.25) sulfate, C 12 -C 18 alkyl ether (3,0) sulfate and C 12 -C 18 alkyl ether (4,0) sulfate, wherein the counterion is conveniently selected from sodium and
potassium.

- In detergent compositions for washing clothes of the present invention may also include other anionic surfactants useful for detersive purposes. These can include salts (including, for example, sodium, potassium salts, ammonium and substituted ammonium such as monoethanolamine salts, diethanolamine and triethanolamine) of soap, alkyl C 9 -C 20 linear benzenesulfonates, alkane C 8 -C 22 primary or secondary sulfonates, C 8 -C 24 olefin sulfonates, acids sulfonated polycarboxylic acids prepared by sulfonation of the product pyrolysate of alkaline earth metal citrates, e.g. eg, as per described in patent GB-1,082,179, alkyl C 8 -C 24 polyglycol ether sulfates (which contain up to 10 moles of ethylene oxide); methyl ester sulphonates (MONTH); acyl glycerol sulphonates, oily glycerol sulfates, alkylphenol ether ethylene oxide sulfates, paraffin, alkyl phosphates, isethionates such as acyl isethionates, N-acyl taurates, alkylsuccinamates and sulfosuccinates, sulphosuccinate monoesters (especially C 12 -C 18 saturated monoesters e unsaturated), sulphosuccinate diesters (especially diesters C 6 -C 14 saturated and unsaturated), acylsarcosinates, alkylpolysaccharide sulfates such as alkyl polyglucoside sulfates, primary alkyl sulfates branched, alkyl polyethoxy carboxylates such as those of formula RO (CH 2 CH 2 O) k CH 2 COO-M + where R is a C 8 -C 22 alkyl, k is a integer from 0 to 10, and M is a soluble salt forming cation. Resin acids and acids are also suitable hydrogenated resins such as rosin, hydrogenated rosin and hydrogenated resin acids present in coniferous oil or derivatives thereof. Other examples can be found in "Surface Active Agents and Detergents "(vol. I and II, by Schwartz, Perry and Berch) Some of said surfactants are also described in general manner in US Patent 3,929,678, granted on December 30, 1975 to Laughlin et al., of column 23, line 58, to column 29, line 23.

The agglomerates of the present invention also may contain cationic, ampholytic, ionic surfactants hybrid and semi-polar.

- Cationic detersive surfactants suitable for use in washing detergent compositions of clothing of the present invention are those that have a group long chain hydrocarbyl. Examples of these surfactants cationic include ammonium surfactants such as alkyldimethylammonium halides and surfactants of formula:

[R 2 (OR 3) and] [R 4 (OR 3) and] 2 R 5 N + X-

wherein R 2 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R 3 is selected from the group consisting of -CH 2 CH 2 } -, -CH 2 CH (CH 3) -,
-CH 2 CH (CH 2 OH) -, -CH 2 CH 2 CH 2 -, and mixtures thereof; each R 4 is selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, benzyl ring structures formed by the union of two R 4 groups , -CH 2 COH-CHOHCOR 6 CHOHCH 2 OH wherein R 6 is any hexose or hexose polymer with a molecular weight of less than about 1000 and hydrogen when and is not 0; R 5 is the same as R 4 or is an alkyl chain in which the total number of carbon atoms of R 2 plus R 5 is not more than about 18; each y is from 0 to about 10 and the sum of all values and is from 0 to about 15; and X is any compatible anion.

Other cationic surfactants useful in the present invention are also described in US 4,228,044, granted to Cambre on October 14, 1980.

- Ampholytic surfactants also result suitable for use in the agglomerate of the present invention. These surfactants can be generally described as aliphatic derivatives of secondary or tertiary amines or derivatives aliphatic secondary and tertiary heterocyclic amines in where the aliphatic radical can be a linear or branched chain. One of the aliphatic substituents contains at least 8 atoms of carbon, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic group water soluble, e.g. eg, carboxy, sulphonate or sulfate. For examples of ampholytic surfactants see patent 3,929,678, granted to Laughlin et al. on 30 of December 1975, column 19, lines 18-35.

- Hybrid ion surfactants are also suitable for use in the agglomerates of the present invention. These surfactants can be widely described as derivatives. of secondary and tertiary amines, derivatives of secondary amines and tertiary heterocyclics or derivatives of ammonium compounds quaternary, quaternary phosphonium or tertiary sulfonium. For examples of hybrid ion surfactants see 3,929,678, granted to Laughlin et al. on 30 of December 1975, column 19, line 38 to column 22, line 48.

- Semi-polar non-ionic surfactants are a special category of non-ionic surfactants that include water-soluble amine oxides containing an alkyl moiety of about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl and hydroxyalkyl groups containing about 1 to about 3 carbon atoms; Water-soluble phosphine oxides containing an alkyl moiety of about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing about 1 to about 3 atoms of
carbon.

Semi-polar nonionic surfactants detergents include amine oxide surfactants that They have the formula:

501

where R 3 is a group alkyl, hydroxyalkyl or alkylphenyl or mixtures thereof that it contains from about 8 to about 22 atoms of carbon; R 4 is an alkylene or hydroxyalkylene group that contains from about 2 to about 3 carbon atoms or mixtures thereof; x is 0 to about 3; and every R 5 is an alkyl or hydroxyalkyl group containing about 1 to about 3 carbon atoms or a group polyethylene oxide containing about 1 to approximately 3 ethylene oxide groups. R 5 groups can be linked together, for example by an oxygen atom or nitrogen, to form a structure of ring.

The amine oxide type surfactants in Particularly include alkyl oxides C 10 -C 18 dimethylamine and oxides of C 8 -C 12 alkoxyethyl dihydroxyethyl amine.

The surfactant described above needs be agglomerated with a vehicle that is a powder. The system viscous surfactant contacts a powdered vehicle finely divided which causes the powders to stick together (it is say, agglomerate). The result is a granulated composition that generally has a particle size distribution in the range of 250 to 1200 micrometers and an apparent density of at minus 650 g / l. The appropriate mixers to make the agglomerate They are well known to the person skilled in the art. Can be chosen any suitable vehicle, like any of the ingredients mentioned below that can be conveniently handled in powder form, or mixtures thereof. The right materials include zeolite, bentonite clay, carbonate, silica, silicate, sulfate, phosphate, citrate and citric acid.

The agglomerate of the present invention requires also the use of a water-soluble acetate salt. There are different commercial acetate salts that can be used herein invention, including sodium acetate, ammonium acetate, acetate calcium, potassium acetate, rubidium acetate and magnesium acetate. Mixtures of different salts can also be used. Not desirable that the acetate introduces water into the agglomerate, so that a Preferred form of acetate salt is the anhydrous form. Acetate Anhydrous sodium is marketed by Verdugt.

Acetate also has the advantage of being Available in different grain sizes. For the purpose of the present invention and to ensure that acetate is found closest to the surfactant, it is desirable to use a very fine acetate powder, preferably a powder with a size of average particles less than 150 micrometers, preferably less than 100 micrometers and more preferably less than 50 micrometers

A particular problem encountered with the use of acetate, especially in its anhydrous form, is that it is a material hygroscopic which, therefore, has a strong tendency to form a paste, even when conditioned in containers with protection anti humidity. The problem is especially acute in fine materials, which are preferred for use in the present invention It has now been found that the trend of acetate to form a paste can be avoided or reduced if the acetate is mixed with aluminosilicates, also called zeolites, especially dried zeolites. The result is a powder mixture of a water-soluble acetate salt and zeolite which is suitable for the manufacture of the agglomerate of the present invention. The powder mixture has better flow properties and does not significantly affect the profile of acetate solution. The powder mixture may comprise from 1% to 30% by weight of the zeolite mixture, and the remainder acetate. For the In general, an amount of 1% to 10% zeolite is sufficient to Get the desired result. Both materials can be mixed together with any suitable equipment and it is preferred to mix both ingredients at a temperature in the range of 10 ° C to 50 ° C, preferably from 15 ° C to 30 ° C. In fact, the use of these Lower temperatures prevent or reduce moisture collection.

Suitable zeolites for use herein invention are zeolites of ion exchange material of crystalline aluminosilicate of formula

Na_ {z} [(AlO_2) {z} \ cdot (SiO 2) y] xH_ {2} O

where z and y are at least approximately 6, the molar relationship between z and y is about 1.0 to about 0.4, and z is about 10 to about 264. Aluminosilicate materials hydrated amorphous useful in the present invention have the formula empirical

M_ {z} (zAlO_ {2} \ cdot ySiO_ {2})

where M is sodium, potassium, ammonium or substituted ammonium, z is about 0.5 to about 2 e and is 1, said material having a capacity of magnesium ion exchange of at least about 50 equivalent milligrams of CaCO 3 hardness per gram of aluminosilicate anhydrous.

The ion exchange materials of crystalline aluminosilicate are also characterized by having a particle size diameter of about 0.1 micrometers at about 10 micrometers. Amorphous materials have a often a smaller particle size diameter, e.g. eg less than about 0.01 micrometers. The materials of Preferred ion exchange have a size diameter of particles from about 0.2 micrometers to about 4 micrometers The term "particle size diameter" in the present specification means the particle size diameter average by weight of a given ion exchange material determined by conventional analytical techniques such as, by example, microscopic determination using a microscope Scanning electronic The ion exchange materials of crystalline aluminosilicate in the present invention usually They are also characterized by their ion exchange capacity calcium, which is at least about 200 mg equivalents of CaCO 3 hardness of water / g aluminosilicate, calculated with regarding the anhydrous substance, and that is usually in the range of 300 mg eq./g to 352 mg eq./g. The materials of ion exchange of aluminosilicate of the present invention They are also characterized by their ion exchange rate calcium that is at least 9.0 ppm equiv. CaCO_ {3} / 1 minute / gram / liter (2 grains Ca ++ / gallon / minute / gram / gallon) of aluminosilicate (with respect to the anhydrous substance), and It is generally within the range of 9.0 ppm equiv. CaCO_ {3} / minute / gram / liter (2 grams / gallon / minute / gram / gallon) a 27.1 ppm equiv. CaCO_ {3} / minute / gram / liter (6 grains / gallon / minute / gram / gallon), with respect to the hardness of the ion calcium. Optimum aluminosilicates as reinforcing additives of the detergency have a calcium ion exchange rate of at least 18.1 ppm equiv. CaCO_ {3} / minute / gram / liter (4 grains / gallon / minute / gram / gallon).

The amorphous ion exchange materials of aluminosilicate usually have an exchange of Mg ++ of at least about 50 mg equiv. CaCO 3 / g (12 mg Mg ++ / g) and an exchange rate of Mg ++ of at least 4.5 ppm equiv. CaCO_ {3} / minute / gram / liter (1 grain / gallon / minute / gram / gallon). Amorphous materials do not present a visible diffraction pattern when examined by Cu radiation (1.54 Angstrom units).

The ion exchange materials of aluminosilicate useful in the practice of this invention are commercial. The aluminosilicates useful in this invention can have crystalline or amorphous structure and can be aluminosilicates natural or synthetic A method to produce materials from ion exchange of aluminosilicate is described in US 3,985,669, granted to Krummel et al. on 12 of October 1976. The ion exchange materials of Synthetic crystalline aluminosilicate preferred for use in the The present invention are marketed under the names of zeolite A, zeolite B and zeolite X. In one embodiment especially Preferred, aluminosilicate ion exchange materials crystalline have the formula

Na 12 [(AlO 2) 12 (SiO2) 12] \ cdot xH_ {2} O

where x is about 20 to about 30, especially about 27 and have a particle size generally less than about 5 micrometers

The agglomerates of the present invention can Understand different optional ingredients. An ingredient especially preferred option is a cationic compound water soluble. The water-soluble cationic compound of the present invention useful in detergent compositions includes monoamines ethoxylated cationic, ethoxylated cationic diamines and polyamines ethoxylated cationic as defined below.

- Water-soluble cationic compounds suitable include compounds selected from the group consisting in:

(1) ethoxylated cationic monoamines that have the formula:

\melm{\delm{\para}{R ^{2} }}{N}{\uelm{\para}{R ^{2} }}

^{+} --- L --- XR2 ---

 \ melm {\ delm {\ para} {R 2}} {N} {\ uelm {\ para} {R 2}}} 

^ + --- L --- X

       \ newpage
    

(2) ethoxylated cationic diamines having the formula:

one

where M 1 is an N + or group N; each M 2 is an N + or N group, and at least one M 2 is a group N +;

(3) ethoxylated cationic polyamines of formula:

100

(4) ethoxylated cationic polymers that they comprise a polymeric main chain, at least 2 M groups and at minus an L-X group, where M is a cationic group attached to, or integral part of, the main chain and contains a N + center positively charged; and L joins groups M and X or joins a group X to the polymeric main chain; Y

(5) mixtures thereof;

where A 1 is

\hskip0.3cm

--

\delm{N}{\delm{\para}{R}}

\hskip-0.1mm

\uelm{C}{\uelm{\dpara}{O}}

--,

\hskip0.3cm

--

\delm{N}{\delm{\para}{R}}

\hskip-0.1mm

\uelm{C}{\uelm{\dpara}{O}}

O --,

\hskip0.3cm

--

\delm{N}{\delm{\para}{R}}

\hskip-0.1mm

\uelm{C}{\uelm{\dpara}{O}}

\hskip-0.1mm

\delm{N}{\delm{\para}{R}}

--,

\hskip0.3cm

--

\uelm{C}{\uelm{\dpara}{O}}

\hskip-0.1mm

\delm{N}{\delm{\para}{R}}

--,

\hskip0.3cm

-- O

\uelm{C}{\uelm{\dpara}{O}}

\hskip-0.1mm

\delm{N}{\delm{\para}{R}}

--,

\hskip0.3cm

--

\uelm{C}{\uelm{\dpara}{O}}

O --,

\hskip0.3cm

-- O

\uelm{C}{\uelm{\dpara}{O}}

O --,

\hskip0.3cm

-- O

\uelm{C}{\uelm{\dpara}{O}}

--,

\hskip0.3cm

--

\uelm{C}{\uelm{\dpara}{O}}

\hskip-0.1mm

\delm{N}{\delm{\para}{R}}

\hskip-0.1mm

\uelm{C}{\uelm{\dpara}{O}}

--

 \ hskip0.3cm 

-

 \ delm {N} {\ delm {\ para} {R}} 

 \ hskip-0.1mm 

 \ uelm {C} {\ uelm {\ dpara} {O}} 

-

 \ hskip0.3cm 

-

 \ delm {N} {\ delm {\ para} {R}} 

 \ hskip-0.1mm 

 \ uelm {C} {\ uelm {\ dpara} {O}} 

O -,

 \ hskip0.3cm 

-

 \ delm {N} {\ delm {\ para} {R}} 

 \ hskip-0.1mm 

 \ uelm {C} {\ uelm {\ dpara} {O}} 

 \ hskip-0.1mm 

 \ delm {N} {\ delm {\ para} {R}} 

-

 \ hskip0.3cm 

-

 \ uelm {C} {\ uelm {\ dpara} {O}} 

 \ hskip-0.1mm 

 \ delm {N} {\ delm {\ para} {R}} 

-

 \ hskip0.3cm 

- O

 \ uelm {C} {\ uelm {\ dpara} {O}} 

 \ hskip-0.1mm 

 \ delm {N} {\ delm {\ para} {R}} 

-

 \ hskip0.3cm 

-

 \ uelm {C} {\ uelm {\ dpara} {O}} 

O -,

 \ hskip0.3cm 

- O

 \ uelm {C} {\ uelm {\ dpara} {O}} 

O -,

 \ hskip0.3cm 

- O

 \ uelm {C} {\ uelm {\ dpara} {O}} 

-

 \ hskip0.3cm 

-

 \ uelm {C} {\ uelm {\ dpara} {O}} 

 \ hskip-0.1mm 

 \ delm {N} {\ delm {\ para} {R}} 

 \ hskip-0.1mm 

 \ uelm {C} {\ uelm {\ dpara} {O}} 

-

or -O-, R is H or alkyl or hydroxyalkyl C 1 -C 4, R 1 is alkylene C 2 -C 12, hydroxyalkylene, alkenylene, arylene or alkarylene, or an oxyalkylene moiety C 2 -C 3 having 2 to about 20 oxyalkylene units provided no bonds are formed O-N; each R2 is alkyl or hydroxyalkyl C_ {1} -C_ {4}, the rest -L-X or two R2 together form the rest (CH 2) r-A 2 - (CH 2) s-, in where A 2 is -O- or -CH 2 -, r is 1 or 2, s is 1 or 2 and r + s is 3 or 4; each R3 is alkyl or hydroxyalkyl C 1 -C 8, benzyl, the rest L-X, or two R 3 or one R 2 and one R 3 together they form the rest - (CH 2) r-A 2 - (CH 2) s-; R 4 is an alkyl, hydroxyalkyl, alkenyl, aryl or C_ {3} -C_ {12} substituted alkylaryl having substitution sites p; R 5 is alkylene, hydroxyalkylene, C 1 -C 12 alkenylene, arylene or alkylene, or a C2-C3 oxyalkylene moiety having 2 to about 20 oxyalkylene units provided it is not form O-O or O-N links; X is a non-ionic group selected from the group consisting of H, groups C 1 -C 4 alkyl or hydroxyalkyl ester or ether, and mixtures thereof; L is a hydrophilic chain that contains the polyoxyalkylene moiety - [(R 6 O) m (CH 2 CH 2 O) n] -; where R 6 is alkylene or hydroxyalkylene C_ {3} -C_ {4} and m and n are numbers so that the remainder - (CH2CH2O) n- understand at least about 50% by weight of said polyoxyalkylene moieties; d is 1 when M2 is N + and is 0 when M2 is N; n is at least about 12 for said cationic monoamines, at least about 6 for said cationic diamines and at least about 3 for said cationic polyamines and polymers cationic; p is from 3 to 8; q is 1 or 0; t is 1 or 0 as long as t is 1 when q is 1.

In the above formulas for cationic amines, R1 can be branched (e.g., 2
200 ; cyclic (e.g. 201 or most preferably alkylene, hydroxyalkylene, alkenylene, alkarylene or linear oxyalkylene (e.g., -CH2CH2-, -CH2 -CH2 -CH2-, 3 R 1 is preferably C 2 -C 6 alkylene for ethoxylated cationic diamines. Each R2 is preferably methyl or the residue -LX; each R 3 is preferably C 1 -C 4 alkyl or hydroxyalkyl and most preferably methyl.

The positive charge of the N + groups is offset by the appropriate number of counter-anions. The Suitable counter-anions include CL <->, Br <->, SO_3 <2>, SO4 {-2-, PO4 {-2-}, MeOSO_ {3} - and the like. The counteranions especially Preferred are Cl <-> and Br <->.

X can be a non-ionic group selected from hydrogen (H), alkyl or hydroxyalkyl groups C 1 -C 4 ester or ether or mixtures of the same. Preferred esters or ethers are the acetic ester and the methyl ether, respectively. Non-ionic groups especially Preferred are H and methyl ether.

In the above formulas, the hydrophilic chain L usually it consists entirely of the polyoxyalkylene moiety - [R 6 O) m (CH 2 CH 2 -O n) -]. The remains - (R 6 O) m - and - (CH 2 CH 2 O) n - from the polyoxyalkylene moiety can mix together or preferably form blocks of debris - (R 6 O) m - and - (CH 2 CH 2 O) n -. R 6 is preferably C 3 H 6 (propylene); month preferably 0 to about 5 and most preferably 0, that is, the polyoxyalkylene moiety is completely formed by the remainder - (CH 2 CH 2 O) n -. The rest - (CH 2 CH 2 O) n - preferably comprises less about 85% by weight, and most preferably 100% in weight (m is 0), of the polyoxyalkylene moiety.

In the above formulas, M1 and each M 2 are preferably an N + group in the case of Cationic diamines and polyamines.

Ethoxylated cationic monoamines and diamines Preferred have the formula:

       \ vskip1.000000 \ baselineskip
    

4

where X and n are according to defined above, a is from 0 to 4 (e.g., ethylene, propylene, hexamethylene) and b is 1 or 0. In preferred cationic monoamines (b = 0), n is preferably at least about 12, with a typical range of about 15 to about 35. In the preferred cationic diamines (b = 1), n is at least about 12 with a typical range of about 12 to approximately 42

\hskip0.3cm

--

\uelm{C}{O}

\hskip-0.1mm

\delm{N}{H}

--; n es
{}\hskip17cm preferiblemente al menos aproximadamente 12, con un intervalo típico de aproximadamente 12 a aproximadamente 42; p es preferiblemente de 3 a 6. Cuando R^{4} es un grupo arilo o alquilarilo sustituido, q es preferiblemente 1 y R^{5} es preferiblemente alquileno C_{2}-C_{3}.In the above formula in the case of ethoxylated cationic polyamines, R 4 (linear, branched or cyclic) is preferably a substituted C 3 -C 6 alkyl or hydroxyalkyl or aryl group; A 1 is preferably

 \ hskip0.3cm 

-

 \ uelm {C} {O} 

 \ hskip-0.1mm 

 \ delm {N} {H} 

-; n is
preferably at least about 12, with a typical range of about 12 to about 42; p is preferably 3 to 6. When R 4 is a substituted aryl or alkylaryl group, which is preferably 1 and R 5 is preferably C 2 -C 3 alkylene.

When R 4 is an alkyl group, hydroxyalkyl or substituted alkenyl and when q is 0, R 5 is preferably an oxyalkylene moiety C 2 -C 3; when q is 1, R 5 is preferably C2-C3 alkylene.

These ethoxylated cationic polyamines can Obtain polyamine amides such as:

5

These ethoxylated cationic polyamines also they can be obtained from polyamine propylene oxide derivatives such how

6

where each c is a number from 2 to approximately twenty.

Methods for preparing cationic amines

A. Method one

The cationic amines of the present invention They can be prepared according to the following scheme:

7

The synthesis of one of these cationic amines is Describe as follows:

Example 1

Stage one

Ethoxylation

Is introduced N-2-hydroxyethylmorpholino (0.8 mol) in a flask equipped with mechanical stirrer, condenser, inlet argon, ethylene oxide bubble tube and internal thermometer. After purging with argon, NaH (0.2 mol) is added to the flask. Be Stir the reaction mixture until the NaH reacts. Later add ethylene oxide vigorously stirring while maintaining the temperature at about 80 ° C-120 ° C. The reaction is interrupted when the ethoxylated compound reaches a degree of ethoxylation of approximately 11.

Stage 2

Quaternization

The ethoxylated compound (0.03 mol) of step 1 It is mixed with 1,6-dibromohexane (0.015 mol). The reaction mixture is stirred, sealed in a container and heat at 80 ° C for ten days to obtain dibromide of 1,6-bis [(-N-morpholinium polyethoxylate (11)] - quaternized crude hexane.

B. Method 2

The ethoxylated cationic amines of the present invention can also be prepared by standard methods of ethoxylation and quaternization of amines. There is preferably a initial stage to condense enough ethylene oxide to obtain 2-hydroxyethyl groups at each site of reaction (hydroxyethylation). This initial stage can be omitted if part of a 2-hydroxyethylamine. Then it condenses the right amount of ethylene oxide with these 2-hydroxyethylamines using as catalyst a alkali metal (e.g., sodium, potassium), or a hydride or hydroxide of the same, to obtain the respective ethoxylated amines. The grade Total ethoxylation per reaction site (n) can be determined by the following formula:

Grade of ethoxylation = E / (A x R)

where E is the total number of moles of condensed ethylene oxide (including hydroxyethylation), A is the number of moles of the initial amine and R is the number of reaction sites (typically 3 for the monoamine, 4 for diamine and 2 x p for polyamines) of the initial amine The amines can then be quaternized ethoxylated with an alkyl halide such as methyl bromide for form cationic amines ethoxylated.

Representative Cationic Amines Syntheses Ethoxylates of the present invention by this method are the following:

Example 2a

Stage one

Ethoxylation

1,6-hexamethylenediamine was placed (100 g, 0.86 mol) in a flask and heated under argon at 85 ° C. Ethylene oxide (OE) was bubbled into the flask. The reaction temperature was gradually increased to 120 ° C during a period of time of approximately 7.5 hours and then briefly increased to 158 ° C to cool again to 100 ° C. He H-NMR indicated that at this point they had incorporated approximately 4 moles of OE.

Sodium spheres (1.24 g, 0.05 were added moles) and the reaction was stirred overnight, after which He had consumed sodium. The addition of OE and the reaction temperature rose to 120 ° C. After about 3 hours, the H-NMR indicated that they had been incorporated approximately 10 moles of OE per mole of the diamine. An additional portion of sodium spheres (3.6 g, 0.15 was added moles) and ethoxylation was continued. He let the temperature amounted to 125 ° C-130 ° C. Ethoxylation was continued for about 22 hours. The reaction ended when they had dissolved about 96 moles of OE per mole of diamine obtaining a total degree of ethoxylation of approximately 24.

Stage 2

Quaternization

A portion of the ethoxylated diamine was quaternized (25 g, 0.0057 mol) of step 1 by dissolving the diamine in methanol (100 ml) containing some NaOH. An excess of methyl bromide using a dry ice condenser. Left stand the reaction mixture overnight, after which the pH had dropped to approximately 4. NaOH was added in methanol to increase the pH to approximately 9. The quaternized compound purifying methanol and methyl bromide remaining The resulting wet material was washed with several portions of dichloromethane. Combined dichloromethane washes are filtered to remove solids and then purified obtaining 27.5 g of a yellow oil that solidified to room temperature. This oil contained the quaternized diamine ethoxylated.

Example 2b

Stage one

Ethoxylation

Dry triethanolamine (TEA) was catalyzed (16.01 g, 0.107 moles) with 0.5 g (0.0125 moles) of 60% NaH in oil mineral. Then ethylene oxide (OE) was added under pressure atmospheric stirring at 150 ° C-170 ° C. After 23 hours it added 36.86 g (8.38 moles) of OE to obtain a total degree of Ethoxylation calculated from 26.1. Ethoxylated ASD (PEI 17) was a light brown waxy solid.

Stage 2

Quaternization

A portion of the ethoxylated ASD was dissolved (31.68 g, 0.0088 moles) of step 1 in H2O to obtain approximately a 50% solution. The solution was heated to 60ºC-70ºC stirring magnetically. One passed stream of methyl bromide gas through the reactor during 8 hours, adding sodium bicarbonate if necessary to keep the pH at a value of 7 or higher. After quaternization, The solution was dialyzed for 3 hours to remove salts. TO The solution was then diluted to obtain an aqueous solution. 10% slightly cloudy golden color containing ASD quaternized ethoxylated.

Cationic polymers

The water-soluble cationic polymers of the The present invention comprises a polymeric main chain, at at least 2 M groups and at least one L-X group, where M is a cationic group attached to, or integral part of, the chain principal; X is a non-ionic group selected from the group that It consists of H, alkyl or hydroxyalkyl groups C 1 -C 4 ester or ether and mixtures of the themselves; and L is a hydrophilic chain that links groups M and X or that links X to the main polymer chain.

Here, the expression "string polymeric principal "refers to the polymeric moiety to which M and L-X groups are attached or of which they are part member. This expression includes the main chains oligomeric (2 to 4 units) and the main chains true polymers (of 5 or more units).

Here, the term "attached to" means that the group hangs from the polymeric main chain of according to the following general structures A and B:

       \ vskip1.000000 \ baselineskip
    

8

Here, the expression "part member of "means that the group is part of the chain polymeric main according to structures C and D following:

9

Any main chain can be used polymeric provided the cationic polymer formed is water soluble and have stain removal properties clay / anti-redeposition. The main polymer chains Suitable may be derived from polyurethanes, polyesters, polyethers, polyamides, polyimides and the like; polyacrylates, polyacrylamides, polyvinyl ethers, polyethylenes, polypropylenes and Similar; polyalkylenes, polystyrenes and the like; polyalkarylenes, polyalkyleneamines, polyalkyleneimines, polyvinylamines, polyallylamines, polydiallamines, polyvinylpyridines, polyamotriazoles, vinyl polyols, aminopolyurethylenes and mixtures thereof.

M can be any compatible cationic group comprising a positively charged N + (quaternary) center. The positively charged quaternary center may be represented by the following general structures E and F:

10

Especially preferred M groups are those that contain a quaternary center represented by the general structure E. The cationic group is preferably placed near, or is an integral part of, the main chain polymeric

The positive charge of the N + centers is compensated by an adequate number of counter-anions. The Suitable counter-anions include Cl -, Br -, SO_ {3} {-2}, SO_ {4} -2, PO_ {4} -2, MeOSO_ {3} - and the like Especially preferred counter-anions are Cl - and Br <->.

X can be a non-ionic group selected from hydrogen (H), alkyl or hydroxyalkyl groups C 1 -C 4 ester or ether, and mixtures of the same. Preferred ester or ether groups are the acetic ester and the methyl ether, respectively. Non-ionic groups especially Preferred are H and methyl ether.

The cationic polymers of the present invention they usually have a relationship between cationic groups M and groups nonionic X from about 1: 1 to about 1: 2. Without However, for example, by proper copolymerization of nonionic cationic monomers (i.e., containing the group L-X) and mixed cationic / non-ionic, it is possible modify the relationship between cationic groups M and non-ionic groups X. The relationship between groups M and groups X can usually oscillate from about 2: 1 to about 1:10. In the polymers Preferred cationic the ratio is about 1: 1 to approximately 1: 5. The polymers formed with this copolymerization are typically random, that is, the mixed cationic, nonionic and cationic / nonionic monomers are copolymerize in a non-repetitive sequence.

Units containing M groups and groups L-X can comprise 100% of the polymers cationic of the present invention. However, in polymers Other units may also be included (preferably not ionic). Examples of other units include acrylamide, vinyl ether and those containing tertiary amine groups without quaternize (M1) containing a center N. These others units may comprise from 0 to about 90% of the polymer (where approximately 10 to 100% of the polymer are units that contain M and L-X groups, including groups M 1 -L-X). Normally you are other units comprise from 0 to about 50% of the polymer (where approximately 50 to 100% of the polymer are units that they contain groups M and L-X).

The number of M groups and groups L-X is usually, in each case, of about 2 to about 200. Typically, the number of groups M and of groups L-X is, in each case, of about 3 to about 100. Preferably, the number of groups M and of groups L-X is, in each case, of about 3 to about 40.

Instead of the remains to join groups M and X or to join the polymeric main chain, the hydrophilic chain L usually consists only of the polyoxyalkylene moiety - [(R'O) m (CH2CH2O) n] -. The residues - (R'O) m - and (CH 2 CH 2 O) n - of polyoxyalkylene moiety can be mixed with each other or preferably forming blocks of moieties - (R'O) m - and - (CH 2 CH 2 O) n -. R 'is preferably C 3 H 6 (propylene); m is preferably 0 to about 5, and most preferably 0; that is, the rest polyoxyalkylene consists solely of the rest - (CH 2 CH 2 O) n -. The rest - (CH 2 CH 2 O) n - preferably comprises less about 85% by weight, and most preferably 100% in weight (m is 0), of the polyoxyalkylene moiety. In the rest -CH 2 CH 2 O) n -, n is usually of about 3 to about 100. Preferably, n is of about 12 to about 42.

They can also hook a plurality together (2 or more) of -L-X residues to join them to a group M or to the main polymer chain, examples of which are represented by the following general structures G and H:

eleven

Structures such as G and H can be formed, by example, by reacting glycidol with an M group or with the chain polymer main, and ethoxylating the hydroxy groups formed to continuation.

Representative classes of polymers Cationic of the present invention are as follows:

A. Polyurethane, polyester, polyether, polyamide or similar polymers

A class of suitable cationic polymers is derived from polyurethanes, polyesters, polyethers, polyamides and Similar. These polymers comprise units selected from those that have formulas I, II and III:

       \ vskip1.000000 \ baselineskip
    

12

       \ vskip1.000000 \ baselineskip
    

13

       \ vskip1.000000 \ baselineskip
    

14

       \ vskip1.000000 \ baselineskip
    

where A 1 is

\hskip3cm

---

\delm{N}{\delm{\para}{R}}

\hskip-0.1mm

\uelm{C}{\uelm{\dpara}{O}}

---,

\hskip0.3cm

---

\uelm{C}{\uelm{\dpara}{O}}

\hskip-0.1mm

\delm{N}{\delm{\para}{R}}

---,

\hskip0.3cm

---

\uelm{C}{\uelm{\dpara}{O}}

O ---,

\hskip0.3cm

--- O

\uelm{C}{\uelm{\dpara}{O}}

---

\hskip0.3cm

o

\hskip0.3cm

---

\uelm{C}{\uelm{\dpara}{O}}

---;

 \ hskip3cm 

---

 \ delm {N} {\ delm {\ para} {R}} 

 \ hskip-0.1mm 

 \ uelm {C} {\ uelm {\ dpara} {O}} 

---,

 \ hskip0.3cm 

---

 \ uelm {C} {\ uelm {\ dpara} {O}} 

 \ hskip-0.1mm 

 \ delm {N} {\ delm {\ para} {R}} 

---,

 \ hskip0.3cm 

---

 \ uelm {C} {\ uelm {\ dpara} {O}} 

Or ---,

 \ hskip0.3cm 

--- OR

 \ uelm {C} {\ uelm {\ dpara} {O}} 

---

 \ hskip0.3cm 

or

 \ hskip0.3cm 

---

 \ uelm {C} {\ uelm {\ dpara} {O}} 

---;

\hskip0.3cm

--- (OR^{8})_{y} ---,

\hskip0.3cm

--- OR^{5} ---,
{}\hskip17cm ---

\delm{C}{\delm{\dpara}{O}}

OR^{5} ---,

\hskip0.3cm

--- O

\delm{C}{\delm{\dpara}{O}}

R^{5} ---,

\hskip0.3cm

--- O

\delm{C}{\delm{\dpara}{O}}

OR^{5},

\hskip0.3cm

---

\delm{N}{\delm{\para}{R}}

\hskip-0.1mm

\delm{C}{\delm{\dpara}{O}}

R^{5} ---,

\hskip0.3cm

---

\delm{N}{\delm{\para}{R}}

\hskip-0.1mm

\delm{C}{\delm{\dpara}{O}}

OR^{5} ---,

\hskip0.3cm

---

\delm{C}{\delm{\dpara}{O}}

\hskip-0.1mm

\delm{N}{\delm{\para}{R}}

R^{5} ---,

\hskip0.3cm

o 17
{}\hskip17cm y R^{3} es -R^{5}-; R^{4} es alquilo o hidroxialquilo C_{1}-C_{4}, o el resto -(R^{5})_{k} -[(C_{3}H_{6}O)_{m}(CH_{2}CH_{2}O)_{n}]-X; R^{5} es alquileno, hidroxialquileno, alquenileno, arileno, o alcarileno C_{1}-C_{12}; cada R^{6} es alquilo o hidroxialquilo C_{1}-C_{4}, o el resto -(CH_{2})_{r}
{}\hskip17cm -A^{2}-(CH_{2})_{s}-, en donde A^{2} es -O- o -CH_{2}-; R^{7} es H o R^{4}; R^{8} es alquileno o hidroxialquileno C_{2}-C_{3}; X es H, --

\uelm{C}{\uelm{\dpara}{O}}

R^{9}, -R^{9} o una mezcla de los mismos, en donde R^{9} es alquilo o hidroxialquilo C_{1}-C_{4}; k es 0 ó 1; m y n son números de forma que el resto (CH_{2} CH_{2}O)_{n}- comprenda al menos aproximadamente 85% en peso del resto -[(C_{3}H_{6}O)_{m}(CH_{2}CH_{2}O)_{n}]-; m es de 0 a aproximadamente 5; n es al menos aproximadamente 3; r es 1 ó 2, s es 1 ó 2, y r + s es 3 ó 4; y es de 2 a aproximadamente 20; el número de u, v y w son de forma que existan al menos 2 centros N^{+} y al menos 2
grupos X.x is 0 or 1; R is H or C 1 -C 4 alkyl or hydroxyalkyl; R 1 is alkyl, hydroxyalkyl, alkenylene, cycloalkylene, arylene or C 2 -C 12 alkylene, or a C 2 -C 3 oxyalkylene moiety having 2 to about 20 oxyalkylene units provided
{} that OO or ON bonds are not formed with A 1; when x is 1, R2 is -R5 - except when A1 is fifteen or is - (OR 8) Y - or
{}? -OR 5 - provided that OO or NO bonds are not formed with A 1, and R 3 is -R 5 - except when A 1 is, 16 or is - (R 8 O) Y -
or -R 5 O- provided that OO or NO bonds are not formed with A 1; when x is 0, R2 is

 \ hskip0.3cm 

--- (OR 8) y ---,

 \ hskip0.3cm 

--- OR5 ---,
{} \ hskip17cm ---

 \ delm {C} {\ delm {\ dpara} {O}} 

OR5 ---,

 \ hskip0.3cm 

--- OR

 \ delm {C} {\ delm {\ dpara} {O}} 

R 5 ---,

 \ hskip0.3cm 

--- OR

 \ delm {C} {\ delm {\ dpara} {O}} 

OR 5,

 \ hskip0.3cm 

---

 \ delm {N} {\ delm {\ para} {R}} 

 \ hskip-0.1mm 

 \ delm {C} {\ delm {\ dpara} {O}} 

R 5 ---,

 \ hskip0.3cm 

---

 \ delm {N} {\ delm {\ para} {R}} 

 \ hskip-0.1mm 

 \ delm {C} {\ delm {\ dpara} {O}} 

OR5 ---,

 \ hskip0.3cm 

---

 \ delm {C} {\ delm {\ dpara} {O}} 

 \ hskip-0.1mm 

 \ delm {N} {\ delm {\ para} {R}} 

R 5 ---,

 \ hskip0.3cm 

or 17
{r} and R3 is -R5-; R 4 is C 1 -C 4 alkyl or hydroxyalkyl, or the remainder - (R 5) k - [(C 3 H 6 O) m (CH 2 CH 2 O) n] - X; R 5 is alkylene, hydroxyalkylene, alkenylene, arylene, or C 1 -C 12 alkylene; each R 6 is C 1 -C 4 alkyl or hydroxyalkyl, or the remainder - (CH 2) r
{} - A2 - (CH2) s -, where A2 is -O- or -CH2-; R 7 is H or R 4; R 8 is C 2 -C 3 alkylene or hydroxyalkylene; X is H, -

 \ uelm {C} {\ uelm {\ dpara} {O}} 

R 9, -R 9 or a mixture thereof, wherein R 9 is C 1 -C 4 alkyl or hydroxyalkyl; k is 0 or 1; m and n are numbers so that the remainder (CH 2 CH 2 O) n - comprises at least about 85% by weight of the remainder - [(C 3 H 6 O) m (CH 2 CH 2 O) n]; m is from 0 to about 5; n is at least about 3; r is 1 or 2, s is 1 or 2, and r + s is 3 or 4; and is from 2 to about 20; the number of u, v and w are such that there are at least 2 N + centers and at least 2
X groups.

\hskip0.3cm

---

\delm{N}{\delm{\para}{R}}

\hskip-0.1mm

\uelm{C}{\uelm{\dpara}{O}}

---

\hskip0.3cm

o

\hskip0.3cm

---

\uelm{C}{\uelm{\dpara}{O}}

\hskip-0.1mm

\delm{N}{\delm{\para}{R}}

---;

\hskip0.3cm

A^{2} es preferiblemente -O-; x
{}\hskip17cm es preferiblemente 1; y R es preferiblemente H. R^{1} puede ser alquileno, hidroxialquileno, alquenileno, cicloalquileno, alcarileno u oxialquileno lineal (p. ej 180 o ramificado (p. ej 18 cuando R^{1} es un resto oxialquileno C_{2}-C_{3}, el número de unidades oxialquileno es preferiblemente de aproximadamente 2 a aproximadamente 12; R^{1} es preferiblemente alquileno o fenileno C_{2}-C_{6} y con máxima preferencia alquileno C_{2}-C_{6} (p. ej., etileno, propileno, hexametileno). R^{2} es preferiblemente -OR^{5}- o -(OR^{8})_{y}; R^{3} es preferiblemente -R^{5}O- o
-(R^{8}O)_{y}-; R^{4} y R^{6} son preferiblemente metilo. Al igual que R^{1}, R^{5} puede ser una cadena lineal o ramificada y preferiblemente alquileno C_{2}-C_{3}; R^{7} es preferiblemente H o alquilo C_{1}-C_{3}; R^{8} es preferiblemente etileno; R^{9} es preferiblemente metilo; X es preferiblemente H o metilo; k es preferiblemente 0; m es preferiblemente 0; r y s son cada uno preferiblemente 2 y preferiblemente de 2 a aproximadamente 12.In the above formulas, A 1 is preferably

 \ hskip0.3cm 

---

 \ delm {N} {\ delm {\ para} {R}} 

 \ hskip-0.1mm 

 \ uelm {C} {\ uelm {\ dpara} {O}} 

---

 \ hskip0.3cm 

or

 \ hskip0.3cm 

---

 \ uelm {C} {\ uelm {\ dpara} {O}} 

 \ hskip-0.1mm 

 \ delm {N} {\ delm {\ para} {R}} 

---;

 \ hskip0.3cm 

A 2 is preferably -O-; x
{} is preferably 1; and R is preferably H. R1 may be alkylene, hydroxyalkylene, alkenylene, cycloalkylene, alkarylene or linear oxyalkylene (e.g. 180 or branched (e.g. 18 when R 1 is a C 2 -C 3 oxyalkylene moiety, the number of oxyalkylene units is preferably from about 2 to about 12; R 1 is preferably C 2 -C 6 alkylene or phenylene and most preferably C 2 -C 6 alkylene (eg, ethylene, propylene, hexamethylene). R 2 is preferably -OR 5 - or - (OR 8) y; R 3 is preferably -R 5 O- or
- (R 8 O) y -; R 4 and R 6 are preferably methyl. Like R 1, R 5 can be a straight or branched chain and preferably C 2 -C 3 alkylene; R 7 is preferably H or C 1 -C 3 alkyl; R 8 is preferably ethylene; R 9 is preferably methyl; X is preferably H or methyl; k is preferably 0; m is preferably 0; rys are each preferably 2 and preferably 2 to about 12.

In the formulas above, n is preferably at least about 6 when the number of N + centers and X groups it is 2 or 3; n is most preferably at least about 12, with a typical range of about 12 to about 42 for all intervals of u + v + w. In homopolymers (v and w are 0), u is preferably from about 3 to about 40 and most preferably from about 3 to about 20. In random copolymers (u is at least 1 or preferably 0), v and w are each preferably about 3 to approximately 40).

B. Polyacrylate, polyacrylamide, polyvinyl ether or similar polymers

Another class of suitable cationic polymers is derived from polyacrylates, polyacrylamides, polyvinyl ethers and Similar. These polymers comprise units selected with the formulas IV, V and VI:

19

\hskip0.3cm

-O-,

\hskip0.3cm

---

\delm{N}{\delm{\para}{R}}

\hskip-0.1mm

\uelm{C}{\uelm{\dpara}{O}}

---,

\hskip0.3cm

---

\delm{N}{\delm{\para}{R}}

\hskip-0.1mm

\uelm{C}{\uelm{\dpara}{O}}

O ---,

\hskip0.3cm

---

\uelm{C}{\uelm{\dpara}{O}}

\hskip-0.1mm

\delm{N}{\delm{\para}{R}}

\hskip-0.1mm

\uelm{C}{\uelm{\dpara}{O}}

---,

\hskip0.3cm

---

\uelm{C}{\uelm{\dpara}{O}}

\hskip-0.1mm

\delm{N}{\delm{\para}{R}}

---,

\hskip0.3cm

--- O

\uelm{C}{\uelm{\dpara}{O}}

\hskip-0.1mm

\delm{N}{\delm{\para}{R}}

---,

\hskip0.3cm

--- O

\uelm{C}{\uelm{\dpara}{O}}

---,
{}\hskip17cm --- O

\uelm{C}{\uelm{\dpara}{O}}

O ---,

\hskip0.3cm

---

\uelm{C}{\uelm{\dpara}{O}}

O ---

\hskip0.3cm

o

\hskip0.3cm

---

\delm{N}{\delm{\para}{R}}

\hskip-0.1mm

\uelm{C}{\uelm{\dpara}{O}}

\hskip-0.1mm

\delm{N}{\delm{\para}{R}}

---;

\hskip0.3cm

R es H o alquilo o hidroxialquilo C_{1}-C_{4}; R^{1} es C_{2}-C_{12} sustituido
{}\hskip17cm alquileno, hidroxialquileno, alquenileno, arileno o alcarileno u oxialquileno C_{2}-C_{3}; cada R^{2} es alquileno, hidroxialquileno, alquenileno, arileno o alcarileno C_{1}-C_{12}; cada R^{3} es alquilo o hidroxialquilo C_{1}-C_{4}, el resto -(R^{2})_{k}-[(C_{3}H_{6}O)_{m}(CH_{2}CH_{2}O)_{n}]-X o combinados forman el resto -(CH_{2})_{r} -A^{2}-(CH_{2})_{s}-, en donde A^{2} es -O- o -CH_{2}-; cada R^{4} es alquilo
{}\hskip17cm o hidroxialquilo C_{1}-C_{4}, o dos R^{4} juntos forman el resto -(CH_{2})_{r} -A^{2}-(CH_{2})_{s}-; X es H ---

\uelm{C}{\uelm{\dpara}{O}}

R^{5}, -R^{5} o mezclas de los mismos, en donde R^{5} es alquilo o hidroxialquilo C_{1}-C_{4}; j es 1 ó 0; k es 1 ó 0; m y n son números de forma que el resto -(CH_{2}CH_{2}O)_{n}- comprenda al menos aproximadamente 85% en peso del resto -[(C_{3}H_{6}O)_{m}(CH_{2}CH_{2}O)_{n}]-; m es de 0 a aproximadamente 5; n es al menos aproximadamente 3; r es 1 ó 2; s es 1 ó 2 y r + s es 3 ó 4; el número de u, v y w es de forma que existan al menos 2 centros N+ y al menos 2 grupos X.where A 1 is

 \ hskip0.3cm 

-OR-,

 \ hskip0.3cm 

---

 \ delm {N} {\ delm {\ para} {R}} 

 \ hskip-0.1mm 

 \ uelm {C} {\ uelm {\ dpara} {O}} 

---,

 \ hskip0.3cm 

---

 \ delm {N} {\ delm {\ para} {R}} 

 \ hskip-0.1mm 

 \ uelm {C} {\ uelm {\ dpara} {O}} 

Or ---,

 \ hskip0.3cm 

---

 \ uelm {C} {\ uelm {\ dpara} {O}} 

 \ hskip-0.1mm 

 \ delm {N} {\ delm {\ para} {R}} 

 \ hskip-0.1mm 

 \ uelm {C} {\ uelm {\ dpara} {O}} 

---,

 \ hskip0.3cm 

---

 \ uelm {C} {\ uelm {\ dpara} {O}} 

 \ hskip-0.1mm 

 \ delm {N} {\ delm {\ para} {R}} 

---,

 \ hskip0.3cm 

--- OR

 \ uelm {C} {\ uelm {\ dpara} {O}} 

 \ hskip-0.1mm 

 \ delm {N} {\ delm {\ para} {R}} 

---,

 \ hskip0.3cm 

--- OR

 \ uelm {C} {\ uelm {\ dpara} {O}} 

---,
{} \ hskip17cm --- O

 \ uelm {C} {\ uelm {\ dpara} {O}} 

Or ---,

 \ hskip0.3cm 

---

 \ uelm {C} {\ uelm {\ dpara} {O}} 

Or ---

 \ hskip0.3cm 

or

 \ hskip0.3cm 

---

 \ delm {N} {\ delm {\ para} {R}} 

 \ hskip-0.1mm 

 \ uelm {C} {\ uelm {\ dpara} {O}} 

 \ hskip-0.1mm 

 \ delm {N} {\ delm {\ para} {R}} 

---;

 \ hskip0.3cm 

R is H or C 1 -C 4 alkyl or hydroxyalkyl; R 1 is C 2 -C 12 substituted
alkylene, hydroxyalkylene, alkenylene, arylene or alkylene or C2-C3 oxyalkylene; each R 2 is alkylene, hydroxyalkylene, alkenylene, arylene or C 1 -C 12 alkylene; each R 3 is C 1 -C 4 alkyl or hydroxyalkyl, the remainder - (R 2) k - [(C 3 H 6 O) m (CH2CH2O) n] -X or combined form the remainder - (CH2) r -A2- (CH2) _ { s -, wherein A 2 is -O- or -CH 2 -; each R 4 is alkyl
{} \ Hskip17cm or C 1 -C 4 hydroxyalkyl, or two R 4 together form the remainder - (CH 2) r -A 2 - (CH 2) ) s -; X is H ---

 \ uelm {C} {\ uelm {\ dpara} {O}} 

R 5, -R 5 or mixtures thereof, wherein R 5 is C 1 -C 4 alkyl or hydroxyalkyl; j is 1 or 0; k is 1 or 0; myn are numbers so that the remainder - (CH 2 CH 2 O) n - comprises at least about 85% by weight of the remainder - [(C 3 H 6 O) _ { m} (CH2CH2O) n] -; m is from 0 to about 5; n is at least about 3; r is 1 or 2; s is 1 or 2 and r + s is 3 or 4; the number of u, v and w is such that there are at least 2 N + centers and at least 2 X groups.

\hskip0.3cm

---

\uelm{C}{\uelm{\dpara}{O}}

\hskip-0.1mm

\delm{N}{\delm{\para}{R}}

---,

\hskip0.3cm

---

\uelm{C}{\uelm{\dpara}{O}}

O ---

\hskip0.3cm

ó

\hskip0.3cm

-O-; A^{2} es preferiblemente O-;
R es preferiblemente H. R^{1} puede ser una cadena lineal (p.ej -CH2-CH-CH2-, 20 o ramificado (p.ej. 210 202 de alquileno, hidroxialquileno, alquenileno, alcarileno u oxialqui-
{}\hskip17cm leno sustituidos; R^{1} es preferiblemente alquileno C_{2}-C_{6} sustituido u oxialquileno C_{2}-C_{6} sustituido, y con máxima
{}\hskip17cm preferencia 21 Cada R^{2} es preferiblemente alquileno C_{2}-C_{3}; cada R^{3} y R^{4} son preferiblemente metilo; R^{5} es preferiblemente metilo; X es preferiblemente H o metilo; j es preferiblemente 1; k es preferiblemente 0; m es preferiblemente 0; r y s son cada uno preferiblemente 2.In the above formulas, A 1 is preferably

 \ hskip0.3cm 

---

 \ uelm {C} {\ uelm {\ dpara} {O}} 

 \ hskip-0.1mm 

 \ delm {N} {\ delm {\ para} {R}} 

---,

 \ hskip0.3cm 

---

 \ uelm {C} {\ uelm {\ dpara} {O}} 

Or ---

 \ hskip0.3cm 

or

 \ hskip0.3cm 

-OR-; A 2 is preferably O-;
R is preferably H. R 1 can be a linear chain (eg -CH2-CH-CH2-, twenty or branched (e.g. 210 202 of alkylene, hydroxyalkylene, alkenylene, alkylene or oxyalkyl
{} substituted leno; R 1 is preferably substituted C 2 -C 6 alkylene or substituted C 2 -C 6 oxyalkylene, and with maximum
{} \ hskip17cm preference twenty-one Each R2 is preferably C2-C3 alkylene; each R 3 and R 4 are preferably methyl; R 5 is preferably methyl; X is preferably H or methyl; j is preferably 1; k is preferably 0; m is preferably 0; rys are each preferably 2.

In the above formulas you can vary n, u, v and w according to the values of n, u, v and w of the polyurethane and the similar polymers.

C. Polyalkyleneamine, polyalkyleneimine or polymers Similar

Another class of suitable cationic polymers is they are derived from polyalkyleneamines, polyalkyleneimines and the like. These polymers comprise units selected from those of formulas VII and VIII and IX:

22

2. 3

\delm{C}{\delm{\dpara}{O}}

R^{4}, -R^{4} o una mezcla de los mismos,
{}\hskip17cm en donde -R^{4} es alquilo o hidroxialquilo C_{1}-C_{4}; d es 1 cuando M' es N+ y es 0 cuando M' es N; e es 2 cuando M' es N+ es 1 cuando M' es N; k es 1 ó 0; m y n son números de forma que el resto -(CH_{2}CH_{2}O)_{n}- comprenda al menos aproximadamente 85% en peso del resto -[(C_{3}H_{6}O)_{m}(CH_{2}CH_{2}O)_{n}; m es de 0 a aproximadamente 5; n es al menos aproximadamente 3; los valores de x, y, z son de forma que existan al menos 2 grupos M', al menos 2 centros N^{+} y al menos 2 grupos X.wherein R 1 is alkylene, hydroxyalkylene, alkenylene, cycloalkylene, arylene or C 2 -C 12 alkylene or a C 2 -C 3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units provided that ON links are not formed; each R 2 is C 1 -C 4 alkyl or hydroxyalkyl, or the remainder - (R 3) k - [(C 3 H 6 O) m (CH 2 CH 2 O) n] - X; R 3 is alkylene, hydroxyalkylene, alkenylene, arylene or C 1 -C 12 alkylene; M 'is an N + or N center; X is H, ---

 \ delm {C} {\ delm {\ dpara} {O}} 

R 4, -R 4 or a mixture thereof,
where -R 4 is C 1 -C 4 alkyl or hydroxyalkyl; d is 1 when M 'is N + and is 0 when M' is N; e is 2 when M 'is N + is 1 when M' is N; k is 1 or 0; myn are numbers so that the remainder - (CH 2 CH 2 O) n - comprises at least about 85% by weight of the remainder - [(C 3 H 6 O) _ { m (CH 2 CH 2 O) n; m is from 0 to about 5; n is at least about 3; the values of x, y, z are such that there are at least 2 M 'groups, at least 2 N + centers and at least 2 X groups.

In the formulas above, R 1 can varied as the R1 of polyurethane and polymers Similar; each R2 is preferably methyl or the rest - (R 3) k - [(C 3 H 6 O) m (CH 2 CH 2 O) n] - X; R3 is preferably C 2 -C 3 alkylene; R 4 it is preferably methyl; X is preferably H; what is preferably 0; m is preferably 0.

In the formulas above, n is preferably at least 6 when the number of groups M 'and X is 2 or 3; n is with highest preference at least about 12, with an interval typical of about 12 to about 42 for all x + y + z intervals. Typically, x + y + z is 2 to about 40 and preferably from 2 to about 20. In The short chain polymers, x + y + z can be from 2 to 9 with from 2 to 9 N + centers and 2 to 11 X groups. In the chain polymers long, x + y + z is at least 10, with a preferred range of 10 to approximately 42. In short chain and chain polymers long groups M 'are typically a mixture of approximately 50 to 100% of N + centers and 0 to approximately 50% of N. centers

Preferred cationic polymers within this class are derived from polyalkylene C 2 -C 3 amines (x + y + z is 2 to 9) and polyalkyleneimines (x + y + z is at least 10, preferably 10 to about 42). Polyalkyleneamines and polyalkyleneimines Especially preferred cationic are polyethyleneamines (PEAs) and cationic polyethyleneimines (PEIs). These cationic polymers Preferred comprise units having the general formula:

       \ vskip1.000000 \ baselineskip
    

24

       \ vskip1.000000 \ baselineskip
    

wherein R2 (preferably methyl), M ', X, d, x, y, z and n are as defined previously; a is 1 or 0.

Before ethoxylation, the PEAs used to preparing the cationic polymers of the present invention have the following general formula:

       \ vskip1.000000 \ baselineskip
    

\hskip0.3cm

-[CH_{2}CH_{2}

\delm{N}{\delm{\para}{}}

]-_{x}

\hskip0.3cm

-[CH_{2}CH_{2}

\delm{N}{H}

]_{y}-

\hskip0.3cm

-[CH_{2}CH_{2}NH_{2}]_{z}[H 2 N] -_ {a}

 \ hskip0.3cm 

- [CH 2 CH 2

 \ delm {N} {\ delm {\ para} {}} 

] -_ {x}

 \ hskip0.3cm 

- [CH 2 CH 2

 \ delm {N} {H} 

]_{Y}-

 \ hskip0.3cm 

- [CH 2 CH 2 NH 2] z

where x + y + z is from 2 to 9 and a is 0 or 1 (molecular weight from about 100 to about 400). Each hydrogen atom attached to each nitrogen atom It represents an active site for subsequent ethoxylation. In the Preferred PEAs, x + y + z is about 3 to about 7 (molecular weight from about 140 to about 310). These PEAs can be obtained by reaction with ammonia and dichloride. ethylene followed by fractional distillation. PEAs commonly obtained are triethylene tetramine (TETA) and tetraethylene pentamine (TEPA). In the case of compounds higher than pentamines, it is that is, hexamines, heptamines, octamines and possibly nonamines, the cogenically derived mixture seems not to be distilled off and may include other materials such as cyclic amines and especially piperazines. Amines may also be present cyclic with side chains with nitrogen atoms. See the US-2,792,372, issued to Dickson on the 14th of May 1957, where the preparation of PEAs

The minimum degree of ethoxylation necessary to obtain the ability to remove clayey dirt
Preferred position may vary depending on the number of units of the PEA. If y + z is 2 or 3, n is preferably at least about 6. If y + z is from 4 to 9, suitable advantages are obtained when n is at least about 3. In the preferred cationic PEAs, n is at least about 12, with a typical range of about 12 to about 42.

The PEIs used to prepare the polymers of the present invention have a molecular weight of at least approximately 440 before ethoxylation, which represents the minus about 10 units. Preferred PEIs used to prepare these polymers have a molecular weight of about 600 to about 1800. The main chain polymeric of these PEIs may be represented by the formula general:

\hskip0.3cm

-[-CH_{2}CH_{2}

\delm{N}{\delm{\para}{}}

-]-_{x}

\hskip0.3cm

-[-CH_{2}CH_{2}

\uelm{N}{H}

-]-_{y}

\hskip0.3cm

-[-CH_{2}CH_{2}NH_{2}]_{z}H 2 N-

 \ hskip0.3cm 

- [- CH2CH2

 \ delm {N} {\ delm {\ para} {}} 

-] -_ {x}

 \ hskip0.3cm 

- [- CH2CH2

 \ uelm {N} {H} 

-]-_{Y}

 \ hskip0.3cm 

- [- CH 2 CH 2 NH 2] z

where the sum of x + y + z represents a value of sufficient magnitude to obtain a polymer with the molecular weights specified above. Although it is possible to obtain linear polymeric main chains, Branched chains can also be obtained. The proportions relative between primary, secondary and tertiary amine groups present in the polymer may vary depending on the mode of preparation. Typically the distribution of the amine groups is the next:

       \ dotable {\ tabskip \ tabcolsep # \ hfil \ + # \ hfil \ + # \ hfil \ tabskip0ptplus1fil \ dddarstrut \ cr} {
 -CH 2 CH 2 -NH 2 \ + \ hskip2cm
\ + 30% \ cr -CH2CH2-NH- \ + \ + 40% \ cr
-CH 2 CH 2 - \ delm {N} {\ para} - \ + \ +
30% \ cr}
    

Each hydrogen atom attached to each atom of PEI nitrogen represents an active site for subsequent ethoxylation These PEIs can be prepared, for example, polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, peroxide hydrogen, hydrochloric acid, acetic acid, etc. Methods specific to prepare PEIs are described in the patents US 2,182,306, granted to Ulrico et al. on 5 of December 1939; US-3,033,746, granted to Mayle and cabbage. on May 8, 1962; US 2,208,095, granted to Esselmann et al. on July 16, 1940; US 2,806,839, issued to Crowther on 17 September 1957; and US 2,553,696, granted to Wilson on May 21, 1951 (incorporated all of them in the present memory for reference).

As defined in the previous formulas, n it is at least about 3 in the case of cationic PEIs. Without However, it should be noted that the minimum degree of ethoxylation necessary for proper dirt removal performance clay / antiredeposition may increase as the PEI molecular weight, especially if the weight is much greater than approximately 1800. Also, the degree of ethoxylation of Preferred polymers increase as molecular weight increases of the PEIs. In PEIs with a molecular weight of at least about 600, n is preferably at least about 12, with a typical range of about 12 to about 42. In PEIs with a molecular weight of at least 1800, n is preferably at least about 24, with a typical range from about 24 to about 42.

D. Diallylamine Polymers

Another class of suitable cationic polymers are those derived from diallylamines. These polymers comprise units selected from those that have formulas X and XI:

       \ vskip1.000000 \ baselineskip
    

25

       \ vskip1.000000 \ baselineskip
    

\delm{C}{\delm{\dpara}{O}}

R^{4}, R^{4} o mezclas de los mismos, en donde R^{4} es alquilo
{}\hskip17cm o hidroxialquilo C_{1}-C_{4}; k es 1 ó 0; m y n son números de forma que el resto -(CH_{2}CH_{2}O)_{n}- comprenda al menos aproximadamente 85% en peso del resto [(C_{3}H_{6}O)_{m}(CH_{2}CH_{2}O)_{n}]-; m es de 0 a aproximadamente 5; n es al menos aproximadamente 3; r es 1 ó 2, s es 1 ó 2, y r + s es 3 ó 4; x es 1 ó 0; y es 1 cuando x es 0, y 0 cuando x es 1; el número de u y v es tal que existen al menos 2 centros N+ y al menos 2 grupos X.wherein R 1 is C 1 -C 4 alkyl or hydroxyalkyl, or the remainder - (R 2) k - [(C 3 H 6 O) _ {m} (CH2CH2 -O) n] -X; R 2 is alkylene, hydroxylalkylene, arylene or C 1 -C 12 alkylene; each R 3 is C 1 -C 4 alkyl or hydroxyalkyl, or together they form the remainder - (CH 2) r -
A- (CH 2) s -, where A is -O- or -CH 2 -; X is H, ---

 \ delm {C} {\ delm {\ dpara} {O}} 

R 4, R 4 or mixtures thereof, wherein R 4 is alkyl
{{}} or C 1 -C 4 hydroxyalkyl; k is 1 or 0; m and n are numbers so that the remainder - (CH 2 CH 2 O) n - comprises at least about 85% by weight of the remainder [(C 3 H 6 O) m (CH 2 CH 2 O) n]; m is from 0 to about 5; n is at least about 3; r is 1 or 2, s is 1 or 2, and r + s is 3 or 4; x is 1 or 0; y is 1 when x is 0, and 0 when x is 1; the number of u and v is such that there are at least 2 N + centers and at least 2 X groups.

In the formulas above, A is preferably -OR-; R1 is preferably methyl; each R2 is preferably C 2 -C 3 alkylene; every R 3 is preferably methyl; R 4 is preferably methyl; X is preferably H; k is preferably 0; month preferably 0; r and s are each preferably 2.

In the formulas above, n is preferably at least about 6 when the number of N + centers and X groups are each 2 or 3, n is preferably at least 12, with a typical range of about 12 to about 42 for u + v. Typically, v is 0, and u is 2 to about 40, and preferably from 2 to about 20.

Methods for preparing cationic polymers A. Polyurethane

The polyurethane versions of this invention can be prepared according to the following general scheme.

26

Example 3

Stage one

Ethoxylation

The diethylene glycol monotetrahydropyranyl ether (1.77 mol) is ethoxylated [Compt. Rend., 260 , 1399-1401 (1965)] using 5 mol% NaH to generate a catalytic amount of the corresponding alkoxide. The ethoxylation is carried out at 90 ° C-120 ° C until approximately 22 moles (n = 22) of ethylene oxide have dissolved for each mole of the initial alcohol to form the ethoxylated compound.

Stage 2

Tosylation

The ethoxylated compound of step 1 dissolves in 1000 ml of acetonitrile and then cooled to approximately 10 ° C To this solution are added 2.67 moles of tosyl chloride dissolved in 500 ml of acetonitrile and cooled to 10 ° C and then add 2.9 moles of triethylamine. Once the reaction is complete, H2O is added to decompose tosyl chloride remaining

Stage 3

Amination

To the reaction mixture of step 3 are added 3.4 moles of diethanolamine. After heating for 18 hours at 80 ° C, The reaction mixture is cooled and acidified carefully with HCl to a pH just above 7 and then extracted with ether. TO the aqueous phase is then extracted twice with a mixture of ether: acetonitrile (with a ratio of approximately 5: 2). Be Separate the aqueous phase and alkalize with 50% NaOH. This phase Aqueous is extracted with dichloromethane (2000 ml). The bottom layer is separate and then extracted 3 times with 2000 ml portions of Saturated NaCl solution in ¼ while adding an amount enough of 50% NaOH to make the aqueous phase pass to strongly basic (pH of approximately 11). The layer is debugged organic lower to obtain the desired aminated compound. Be add toluene (200 ml) and refine the mixture to obtain the desired aminated monomer.

Stage 4

Polymerization

The monomer of step 3 is dissolved in chloroform free of ethanol stabilizer. The monomer is previously evacuated in a Kugelrohr at 80ºC-90ºC at vacuum (pressure of 1 mm.) for at least 18 hours. Dries on monomer in the chloroform overnight with molecular sieves 3 \ ring {A} and then transferred to a dry flask (equipped with mechanical stirrer) in argon atmosphere.

Dibutyltin catalyst is added to the monomer dilaurate (0.058 mol equiv.) in chloroform under argon. To the stirred reaction mixture is added 0.7 moles of hexamethylene diisocyanate per mole of aminated monomer during a 5 minute period. The reaction mixture is stirred at temperature ambient for 18 hours. The chloroform is removed under vacuum at approximately 70 ° C to obtain the resulting polymer.

Stage 5

Quaternization and elimination of protective groups

The polymer of step 4 is dissolved in methanol and an excess of methyl bromide is passed. After about 5 hours, the pH is adjusted to approximately 4 with aqueous solution of HCl and then allowed to stand overnight to produce the Sololysis of the tetrahydropyranyl protecting group. Later neutralize the solution with NaOH and purify to obtain the raw polyurethane This crude polyurethane is dissolved in chloroform and filter to remove any salt. The chloroform is purified to obtain the polymer free of salts wanted.

       \ newpage
    

B. Random copolymer of ethoxylated acrylate and a cationic methacrylamide

The random copolymer versions of the The present invention can be prepared according to the following scheme general:

27

The following describes the synthesis of one of These random copolymers:

Example 4

Decanylene Glycol Monomer Dissolve monomethacrylate (0.008 mol) and monomer of N- (3-dimethylaminopropyl) -methacrylamide (0.011 mol) in 40 ml acetonitrile. The reaction mixture is oxygen purge bubbling argon through it. It dissolves separately a 0.23 g portion of benzoyl peroxide in 10 ml of acetonitrile and similarly purged. Reaction mixture it is heated to reflux and then the solution of benzoyl peroxide for 0.5 hours. Then they are added to the reaction mixture 0.28 g of azobisisobutyronitrile in 5 ml of acetonitrile and heating is maintained overnight. Be a stream of methyl bromide passes through the mixture of reaction and then heat slightly for 1 hour. He Desired random copolymer is isolated by purifying the solvent.

C. Quaternized polyethyleneamines and polyethyleneimines

Polyethyleneamines and polyethyleneimines quaternized can be prepared using standard methods of ethoxylation of amines and subsequent quaternization. The syntheses Representative of these polyethyleneamines and polyethyleneimines are the following:

       \ newpage
    

Example 5a

Stage one

Ethoxylation

Tetraethylenepentamine (TEPA) (PM 189, 13.5 g, 0.071 mol) was placed in a nominally dry flask and dried under stirring for 0.5 hours at 110 ° C-120 ° C under vacuum (pressure less than 1 mm Hg.). The vacuum was removed by introducing ethylene oxide (OE) from a previously purged trap connected to a supply tank. Once the flask was filled with OE, an exit stopcock was carefully opened to a trap connected to an exhaust bubbler. After 3 hours stirring at 115 ° C-125 ° C, the H-NMR analysis showed an ethoxylation degree of 1 per reaction site. The reaction mixture was cooled by passing a stream of argon at the same time and then 0.5 g (0.0125 mol) of 60% sodium hydride in mineral oil was added. The stirred reaction mixture was treated with a stream of argon until the evolution of hydrogen ceased. An OE stream at atmospheric pressure and a temperature of 117 ° C-135 ° C were then passed through the mixture applying moderately rapid agitation. After 31 hours, 459 g (10.43 mol) of OE had been added to obtain a total degree of ethoxylation calculated
of 21

Stage 2

Quaternization

A portion of 34.8 g (0.0052 mol) was dissolved of the ethoxylated TEPA of stage 1, which was a brown waxy solid, in D 2 O to obtain a 50% solution. The pH of the solution it was about 8. The solution was heated to 60 ° C and passed a stream of gaseous methyl bromide through the vessel reaction whose output was connected to a bubbler. Several times during the reaction, the pH became acidic and was added NaHC03 to the reaction to maintain the pH at about 8. After approximately 20 hours a power bubbler was placed below the surface of the reaction mixture so that the methyl bromide will pass through the mixture while agitation speed increased. After a total of 22 hours, the reaction mixture was diluted to 25% and dialyzed to remove you go out. The reaction mixture was then lyophilized to get a light yellowish tan crystalline solid that it was the quaternized ethoxylated TEPA.

Example 5b

Stage one

Ethoxylation

By a procedure similar to that of Example 3a, PEI (21.5 g, PM 600, 0.5 mol) was dried at 120 ° C under vacuum and A stream of OE passed until hydroxyethylation was completed (3 hours). The hydroxyethylated compound was cooled under argon. and 0.1 g (0.0022 mol) of 50% NaH in mineral oil was added. The reaction mixture was heated to approximately 70 ° C and passed an OE stream for 13 hours until a total of 88.5 g of OE, obtaining a calculated degree of ethoxylation of 3.4.

A 53 g portion (0.0173 moles) of this compound in a similar device, heated to 120 ° C and evacuated for 0.5 hours, cooled under argon and added another 0.5 g (0.010 mol) of 50% NaH. A stream of OE was passed for 11 hours until 103 g of OE has been added, obtaining a Total degree of ethoxylation of 11.6.

A 74 g (0.0082 mol) portion of the ethoxylated PEI was placed at 11.6 in a similar apparatus and an OE stream was passed for 6 hours at 170 ° C until 70 g of OE was added to obtain a total degree of ethoxylation from
23.4.

Stage 2

Quaternization

By a procedure similar to the example 3a, 20 g (0.00114 mol) of the ethoxylated PEI was dissolved at 23.4 of step 1 in D2 0, was heated to 50 ° C-60 ° C and was a stream of methyl bromide passed for 9 hours in total to obtain quaternized ethoxylated PEI.

       \ newpage
    

D. Diallylamine Polymers

Polymer versions of diallylamine of the present invention according to the following scheme general:

28

The synthesis of one of these polymers is described. as follows:

Example 6

Stage one

Ethoxylation

The diallylamine (1.7 mol) is dissolved in methanol (160 ml) under argon and then heated to 45 ° C. Then ethylene oxide is added for 2.5 hours. The methanol is then removed by heating the reaction mixture at 100 ° C under vacuum . To the residue is added sodium hydride in mineral oil (6.6 g, 0.165 moles) while stirring until the evolution of hydrogen ceases. Then ethylene oxide is added until the degree of ethoxylation (n) is approximately 7.

Stage 2

Quaternization

The crude ethoxylated diallylamine from step 1 is dissolved in about an equal volume of 1 N methanolic NaOH and then methyl bromide is added. This addition of methyl bromide is continued until the H-NMR analysis indicates the complete disappearance of methylene hydrogens adjacent to tertiary nitrogen. If necessary, additional portions of 1 N methanolic NaOH are added to maintain the pH of the reaction mixture at approximately 9. Methanol is removed, obtaining a wet mass. This wet mass is washed with several portions of dichloromethane. The combined washings are concentrated to obtain the desired quaternized compound.

       \ newpage
    

Stage 3

Polymerization

The quaternized monomer of step 2 is mixed with D2 0 (20 ml) and heated at 95 ° C under an argon atmosphere for 1 hour. Then tert-butylhydroperoxide (25 drops) is added and the reaction is continued at 90 ° C for 18 hours. Then another 20 drops of the hydroperoxide are added. After heating for another 3 days, the water is removed under vacuum (50 ° C-60 ° C at a pressure of 0.1 mm) to obtain the crude polymer.

The cationic compounds of use herein invention are water soluble. Here, the term "water soluble" preferably means that at least 30 g of the compound are dissolved in 100 g of water at 20 ° C.

In fact, the use of a small amount of a Water-soluble cationic compound allows formulating agglomerates that they are much more active, that is, they comprise a greater amount of surfactant without thereby significantly affecting the water solubility of the agglomerate or without increasing its tendency to gel when they come in contact with water. It is believed that the fact of premixing the compound and the surfactant makes the paste of surfactant forms a mass of greater viscosity and lower adhesion. This allows to use a smaller amount of vehicle and the result In general, it is an agglomerate of greater activity.

The agglomerates of the present invention they comprise from 10% to 50%, preferably from 20% to 40% and with maximum preferably from 25% to 35%, by weight of the agglomerate of a surfactant. The agglomerates of the present invention comprise from 10% to 50%, preferably from 20% to 40% and most preferably from 25% to 35% by weight of the agglomerate of a vehicle. The agglomerates of the The present invention comprises from 10% to 50%, preferably from 20% to 40% and most preferably from 25% to 35% by weight of the agglomerate of acetate. Finally, the agglomerates of the present invention comprise from 0% to 40%, preferably from 2% to 30% and with maximum preference of 3% to 15% by weight of the compound agglomerate water-soluble cationic.

A preferred agglomerate comprises from 10% to 50% in surfactant agglomerate weight, from 10% to 40% by weight of vehicle agglomerate, 10% to 40% acetate and 0% to 20% in Agglomerate weight of water-soluble cationic compound. A most preferred agglomerate comprises from 25% to 35% by weight of the surfactant agglomerate, 25% to 35% by weight of the agglomerate of vehicle, from 25% to 35% of acetate and from 0% to 15% by weight of agglomerate of water-soluble cationic compound.

An optional preferred ingredient for surfactant agglomerate is a polymer that has a point of melting above 35 ° C, preferably above 45 ° C, more preferably above 55 ° C and most preferably above 60 ° C, including for example the PEGs (polyethylene glycol), the PEG 4000 is more preferred. This type of ingredient is especially useful when the agglomerate comprises a surfactant, more preferably a nonionic surfactant, which has a melting temperature below 35 ° C, where this surfactant which has a melting temperature below 35 ° C it is likely that cover when the chipboard is placed in a high environment temperature, in which case the addition of the polymer with a point of melting above 35 ° C will increase the melting point of the mixing thus avoiding the formation of a liquid phase. During the process to prepare the chipboard this polymer is preferably treated at the same time as the surfactant and is preferably present in proportions of at least 3% and up to 20% by weight of agglomerated, more preferably in proportions of at least 4% and up to 6%

Another preferred optional ingredient is a salt Water soluble citrate to further improve the profile of solution of the agglomerate of the present invention. A variety of these citrate salts are on the market and can used in the present invention. Can also be used mixtures of different salts. It is not desirable for citrate to enter water in the chipboard, so a preferred form of salt Citrate is the anhydrous form.

As for acetate, citrate should be as close as possible to the surfactant.

A particular problem encountered with the use of Citrate, especially in its anhydrous form, is that it is a material hygroscopic and therefore has a strong tendency to form a paste, even when conditioned in containers protected from humidity. The problem is especially acute in fine materials. which are preferred for use in the present invention. It has been found now that the tendency of the citrate to form a paste if the citrate is mixed with aluminosilicates, also called zeolites, especially dried zeolites. The result is a powder mixture of a salt of water-soluble citrate and zeolite, suitable for the manufacture of agglomerate of the present invention. The powder mixture has better flow properties and no negative effects significant on the dissolution profile of citrate. Mix powder may comprise from 1% to 30% by weight of the mixture of zeolite and the rest citrate, acetate or a mixture of both. For the In general, an amount of 1% to 10% zeolite is sufficient to Get the desired result. These materials can be mixed with any suitable equipment and it is preferred to mix these ingredients, that is, acetate and / or citrate and zeolite at temperatures in the range of 10 to 50 ° C, preferably 15 to 30 ° C. From In fact, the use of these low temperatures avoids or reduces the moisture collection

It should be noted that an advantage of citrate is that It has a function in washing as it acts as a reinforcing additive of detergency. Preferably, the agglomerate comprises a mixture of acetate and citrate instead of acetate only. The mixture of citrate and acetate may comprise 1 to 100% by weight citrate, and more preferably from 40 to 60% by weight citrate.

The process to prepare the chipboard

The critical aspect of the process according to the invention is that this should ensure that acetate is very close to agglomerate surfactant. This close proximity could not achieved through the dry addition of acetate with the agglomerated to form a final composition. However, this close proximity can be achieved by different means that They include the following two embodiments:

In a first embodiment, the acetate, or a portion thereof, is intimately mixed with the surfactant before of agglomerating it with the vehicle. In a variant of this first embodiment, the acetate is intimately mixed with the vehicle before agglomerating it with the surfactant.

In the second embodiment, the surfactant and the vehicle are previous agglomerations and then the acetate on the previous agglomeration to form the agglomerate final. Both embodiments can be combined so that only one portion of the acetate is intimately mixed with the surfactant or the vehicle. Then, the surfactant and the vehicle and the acetate portion to finally spray the rest of the acetate on the previous agglomeration do to form the final chipboard.

The optional ingredients in the chipboard they can be formulated in different ways, except in the case of water-soluble cationic compound that must be mixed with the surfactant before mixing the surfactant with the vehicle. If he acetate is also mixed with the surfactant, it is preferred to mix first the surfactant and the water-soluble cationic compound, then the acetate and finally agglomerate this mixture with the vehicle.

In addition to these particularities, the process of The present invention includes mixing a fluid (the surfactant) with powders (acetate, vehicle), a fluid (the surfactant) with a fluid (the water-soluble cationic compound), a powder (the acetate) with a powder (the vehicle) and this can be done by any means well known to the person skilled in the art. The suitable equipment to perform these stages include the Fukae® FS-G series mixers manufactured by Fukae Powtech Kogyo Co., Japan. This device is practically a bowl-shaped container accessible through a port top located near its base with an agitator that has a shaft basically vertical and a cutter placed on a side wall. He agitator and cutter can be operated independently between Yes and at different speeds each. The container can be equipped with a cooling jacket or, if necessary, with A cryogenic unit.

Other similar mixers found are suitable for use in the process of the invention include Diosna® V series from Dierks & Söhne, Germany; and Pharma Matrix® of T K Fielder Ltd., England. Other mixers that are believed are Suitable for use in the process of the invention are Fuji® series VG-C of Fuji Sangyo Co., Japan; and Roto® by Zanchetta & Co srl, Italy.

Other suitable preferred equipment may include Eirich®, RV series, manufactured by Gustau Eirich Hardheim, Germany; Lödige®, FM series for batch mixing, Baud KM series for continuous mixing / agglomeration, manufactured by Lödige Maschinenbau GmbH, Paderborn, Germany; Drais® T160 series, manufactured by Drais Werke GmbH, Mannheim, Germany; and Winkworth® RT 25 series, manufactured by Winkworth Machinery Ltd., Berkshire, England.

The Littleford mixer, model FM-130-D-12, with internal cutting blades and the Cuisinart Food Processor, model DCX-Plus, with 19.7 cm (7.75 in) blades are two Examples of suitable mixers. Any other can be used. mixer with dispersion fine mixing capability and granulation and with a residence time of 0.1 to 10 minutes. Be he prefers the "turbine type" drive mixer, which has several blades on a rotating shaft. The invention can be carried out as a process in batch mode or in continuous mode.

In the embodiment of the present invention in the that the acetate is sprayed on a previous agglomeration of the surfactant and the vehicle (and optionally the cationic compound water soluble), it is necessary to first form a powder solution acetate so that it becomes a spray solution. The Suitable sprayable solutions comprise from 30 g / l to 60 g / l of acetate, preferably from 40 g / l to 50 g / l acetate. Acetate it can be dissolved in different liquid vehicles, including water and polyethylene glycol In this embodiment, any spray equipment and it is preferred to dry the chipboard after spray it with the acetate solution. Again, it can be used. For this purpose any conventional drying equipment.

Once the surfactant agglomerate formed, it may be desirable to subject it to a heating and / or drying stage followed by a cooling stage. This will allow to eliminate the excess moisture.

Also, before mixing the surfactant, or the water-soluble cationic surfactant / compound premix with the vehicle, it is desirable to take the surfactant, or premix of water-soluble cationic surfactant / compound, up to a viscosity from about 15 to 35 Pas (15,000 to 35,000 cP), preferably from 20 to 25 Pas (from 20,000 to 25,000 cP). This can be achieved controlling the temperature of the surfactant or premix of water-soluble cationic surfactant / compound. This will allow obtain a more convenient mixing of the surfactant or of the surfactant / polymer premix with the vehicle.

The dissolution profile of the agglomerate of Surfactant can be measured as follows:

1. A Sotax beaker is filled with 1 liter of deionized water and placed in a temperature bath constant set at 10 ° C. In the beaker a agitator with a marine propeller so that the marine propeller will find ± 1 mm below the surface of the water. He mixer is set at a rotation speed of 20.9 rad / s (200 rpm).

2. 10 g of the agglomerate of the surfactant to be examined in the beaker Sotax

3. 30 seconds after entering the a surfactant agglomerate is taken a 2 ml solution sample with a syringe equipped with a filter unit (with a size of 0.45 micrometer mesh). The filter is used to avoid analyze undissolved particles, which could affect the Outcome.

4. Step 3 is repeated after 1 min, 2.5 min, 5 and 10 minutes after entering the agglomerate.

In all samples the content of active material and this is compared to the maximum amount calculated theoretically of surfactant in the sample.

The compositions in which the agglomerate can be formulated

Although normally it is not distinguished between the two forms, the agglomerate according to the present invention can be formulated in granulated detergent compositions or in tablets. Depending of its final use, typically dishwashing or washing of clothing, these detergent compositions may comprise different ingredients including non-exclusive other surfactants, detergency builders, chelators, bleaches, bleach activators, polymers for dirt release, controlling agents or boosters Soaps, pH regulators, enzymes, stabilizers enzymes, perfumes, brighteners, inhibitors of dye transfer and the like.

In the preferred compositions herein invention, at least 40%, preferably at least 60% and with maximum preferably at least 90%, of the surfactant is incorporated by the chipboard

Granulated detergent compositions

To form a granulated detergent composition, surfactant agglomerates can simply be mixed with the rest of the ingredients that are in the form of particles or can be subjected to other stages of liquid spraying and coating with fine powders.

Although the performance of the particles described in the present invention it remains excellent regardless from the rest of the product matrix, it may be advantageous to finish the granulated detergent composition so as to maximize the performance and high flexibility to formulate a wide variety of products without changes important in the process. This can be achieved by performing a modular approach to the product matrix structure finish.

The modular approach is based on manufacturing of very specific particles in one or at most two ingredients of the formulation that are then mixed in the relationships desired to form the finished products. These particles, at be very specific in the ingredient they must supply, they can be used in a wide range of products without the need to be modified. These particles can be prepared with a combination optimal ingredients that maximize their properties regardless of the complete product formulations finish.

Detergent tablet compositions

Detergent tablets can be prepared simply mixing the solid ingredients together and compressing the mixture in a conventional tablet press like the ones used, for example, in the pharmaceutical industry.

Detergent tablets can be manufactured in any size or shape and, if desired, can be coated.

Materials in the form of particles (different to the agglomerates of the invention) used to prepare the tablet can be prepared by any process of particulation or granulation. An example of such a process is drying by spray (in a spray-drying tower under current or countercurrent), which typically results in values low bulk density of 600 g / l or less. The materials in the form of higher density particles can be prepared by granulation and densification in a high mixer / granulator batch shear or by granulation procedures and continuous densification (for example, with Lodige® CB mixers and / or Lodige® KM). Other suitable procedures include the fluid bed procedures and compaction processes (for example, roller compaction), extrusion as well as any particulate material prepared by any process chemical such as flocculation or sintering by crystallization. The individual particles can also be any other type of particles, granules, spheres or grains.

Particle-shaped materials can be mix with each other by any conventional means. The lot can be prepared properly, for example, in a mixer horizontal, a Nauta mixer, a tape mixer or any other. Another alternative is to perform the mixing process so continue dosing by weight and dispensing each component on a moving tape and mixing them in one more drums or mixers A non-gelling binder can be sprayed on the mixture of part or all of the materials in the form of particles Other liquid ingredients can also be sprayed on the mixture of particulate materials, either by previously separated or mixed. For example, they can be sprayed Perfumes and aqueous suspensions of optical brighteners. After By spraying the binder, it can be added to the products in particle form a finely divided fluidizer (an agent lubricant, such as zeolites, carbonates, silicas), preferably towards the end of the process, so that the mixture results less sticky

The tablets can be manufactured using any compaction process such as compression, briquetting or extrusion, preferably compression. The right equipment includes a standard piston or rotary press (such as Courtoy®, Korch®, Manesty® or Bonals®). Prepared pills should have preferably a diameter of 40 mm to 60 mm and a weight of 25 to 100 g. The relationship between the height and the diameter (or width) of the tablet is preferably greater than 1: 3, more preferably greater than 1: 2. The compaction pressure used to prepare These tablets should not exceed 5000 kPa (5000 kN / m2), preferably it should not exceed 3000 kPa (3000 kN / m2) and most preferably it should not exceed 1000 kPa (1000 kN / m2).

Suitable non-gelling binders include synthetic organic polymers such as polyethylene glycols, polyvinylpyrrolidones, polyacrylates and acrylate copolymers water soluble. In the Handbook of Pharmaceutical Excipients, 2nd ed., the following classification of binders is offered: gum arabic, alginic acid, carbomer, sodium carboxymethyl cellulose, dextrin, ethyl cellulose, gelatin, guar gum, hydrogenated vegetable oil type I, hydroxyethylcellulose, hydroxypropyl methylcellulose, glucose liquid, magnesium aluminum silicate, maltodextrin, methylcellulose, polymethacrylates, povidone, sodium alginate, starch and zein The most preferred binders also have a function cleanser active in washing clothes like polymers cationic, for example, quaternary compounds of ethoxylated hexamethylenediamine, bishexamethylenetriamines or others as pentaamines, ethoxylated polyethyleneamines and polymers Acrylic / Maleic

Non-gelling binder materials preferably they are pulverized and therefore have a temperature suitable melting point below 70 ° C and preferably below 50 ° C to avoid damaging or degrading the other principles parent assets. The most preferred binders are the non-aqueous liquid binders (i.e., not in solution aqueous) that can be sprayed in molten form. But nevertheless, they can also be solid binders incorporated into the matrix by dry addition, but which have binding properties within The pill.

Non-gelling binder products are preferably used in an amount of 0.1 to 15% of the composition, more preferably less than 5% and, especially if it is an active product not intended for washing clothes, in a amount less than 2% by weight of the tablet.

The tablets can be coated so that the tablet does not absorb moisture or absorb moisture only at a very slow speed. The coating is also sufficiently resistant so that moderate mechanical shocks to which is subjected to the pads during handling, the conditioning and transport only produce very low levels of breakage or wear. Finally, the coating is preferably brittle so that the tablet is broken when undergo stronger mechanical shocks. It also turns out advantageous for the coating material to dissolve in alkaline conditions that is easily emulsified by surfactants This helps to avoid the problem of waste visible in the window of a front loading washing machine during wash cycle and also prevents non-particle deposition dissolved or lumps of coating material in the load of clothes.

Water solubility is measured by the protocol Test ASTM E1148-87 titled "Test Method standard for the determination of water solubility "

Suitable coating materials are those dicarboxylic acids. Dicarboxylic acids especially Suitable are selected from the group consisting of oxalic acid, Malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, subic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid and tridecanedioic acid and mixtures thereof.

The coating material has a point of melting preferably from 40 ° C to 200 ° C.

The coating can be applied in different shapes. Two preferred coating methods are a) coating with a molten material and b) coating with a solution of material.

In a) the coating material is applied to a temperature higher than its melting point and solidifies on The pill. In b) the coating is applied as a solution and The solvent is dried to leave a uniform coating. He virtually insoluble material can be applied to the tablet, by example, by spraying or immersion. Normally when the molten material is sprayed on the tablet, it solidifies quickly forming a uniform coating. When the pills they are immersed in the molten material and then removed, the fast cooling again produces rapid solidification of the coating material. Obviously, the products practically insoluble with a melting point below 40 ° C not they are sufficiently solid at room temperature and it has been observed that materials that have a melting point higher than approximately 200 ° C cannot be used. Preferably, the products melt in the temperature range of 60ºC to 160ºC, more preferably from 70 ° C to 120 ° C.

"Melting point" means the temperature at which the material when heated slowly, by example in a capillary tube, it becomes a liquid transparent.

According to the present invention, a coating with any desired thickness. For most of the For purposes, the coating represents 1 to 10%, preferably of 1.5% to 5%, of the weight of the tablet.

These tablet coatings are very hard and They provide additional resistance to the tablet.

In a preferred embodiment the fracture of the coating in the wash solution is improved by adding a disintegrating to the coating. This disintegrant will swell on entering in contact with water and will break the coating into small chunks This will favor the dissolution of the coating in the wash solution The disintegrant is suspended in the melt of coating up to 30%, preferably 5% to 20% and with maximum 5% to 10% preference, by weight. In the Handbook of Pharmaceutical Excipients (1986) describe possible disintegrants. Examples of Suitable disintegrants include starch (natural starch, modified or pregelatinized, sodium starch gluconate), the gums (agar rubber, guar gum, locust bean gum, karaya gum, rubber of pectin, gum tragacanth), croscarmellose sodium, crospovidone, cellulose, carboxymethyl cellulose, alginic acid and its salts as sodium alginate, silicone dioxide, clay, polyvinylpyrrolidone, soy polysaccharides, exchange resins ionic and mixtures thereof.

Depending on the composition of the material of starting and the shape of the pads will adjust the force of compaction used so that it does not affect the resistance (tension of diametral fracture) or at the time of disintegration in the washing machine. This procedure can be used to prepare pills homogeneous or laminar of any size and shape.

In another preferred embodiment of the present invention the tablets also contain an effervescent agent.

Effervescence, as defined herein memory, indicates the release of gas bubbles in a liquid as a result of a chemical reaction between an acid source soluble and an alkali metal carbonate, with dioxide production carbon gas,

p. \ ex. \ C_ {H} {8} O_ {7} + 3NaHCO_ {3} → Na_ {3} C_ {6} H_ {5} + 3CO_ {2} \ uparrow + 3H 2 O

The tablets can also be used in a washing method comprising preparing an aqueous solution of a laundry detergent for use in a washing machine front-loading clothes, having the front-loading clothes washer a dispenser drawer and a laundry drum, where the solution aqueous laundry detergent is formed by placing the tablet in the dispenser drawer before the water passes through of the dispenser drawer so that the tablet is dispensed as an aqueous solution of a laundry detergent and going on then the aqueous solution to the laundry drum.

In a preferred embodiment, the agglomerate of surfactant comprises an anionic surfactant and an acetate together with any other structuring agent, where these components they are placed in close proximity through a process that produces high shear force, such as extrusion. In fact, it has observed that this type of surfactant agglomerate has a high activity and at the same time processability satisfactory, said processability being provided satisfactory due to the hardness and low adhesion of the paste obtained. The structuring agent used can be, for example, zeolite, silicate, or a mixture of these. It should be noted that the processability satisfactory is obtained with surprisingly low levels of acetate, preferably anhydrous sodium acetate, with preferably less than 10% by weight of the agglomerate. The chipboard preferably it also comprises more than 40%, more preferably more than 50%, in weight of anionic surfactant.

The present invention is illustrated by following examples.

Examples Example A

The surfactant particle of the Composition indicated in Table 1 as follows:

1. A high mixer / agglomerator was loaded shear (Lodige FM 130) with a mixture comprising acetate anhydrous powder (with an average particle size less than 100 µm) and finely divided sodium carbonate (with a size of average particles less than 200 µm).

2. Then non-ionic surfactant was added ethoxylated (C14-C15 OE7) to the dry mixture of carbonate / acetate.

3. The surfactant and dry powders are agglomerated in the mixer / agglomerator with the paddles set to 18 rad / s (175 rpm) and the cutter at 314 rad / s (3000 rpm) until it They formed discrete granules.

4. The agglomerates were transferred to then to a horizontal rotating mixer and they were treated for 30 s. with zeolite fluidizer.

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TABLE 1

Composition by weight Anhydrous sodium acetate 40 Sodium carbonate 30 Nonionic surfactant (C45 AE7) twenty Fluidifier (zeolite) 10

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Example B

The surfactant particle of the composition indicated in Table 2 as indicated by continuation:

1. A high mixer / agglomerator was loaded shear (Lodige FM 130) with a mixture comprising 40 parts of anhydrous acetate powder (with an average particle size less than 100 µm) and 20 parts finely sodium carbonate divided (with an average particle size less than 200 \ mum).

2. Then it was added to the dry mixture of carbonate / acetate a premix comprising 26 parts of ethoxylated non-ionic surfactant (C14-C15 OE7) and 6 BASF Lutensit KHD96 cationic polymer parts (a compound quaternary of ethoxylated hexamethylene diamine).

3. The premix of Surfactant-polymer and dry powders will agglomerated in the mixer / agglomerator with the paddles set to 18 rad / s (175 rpm) and the cutter at 314 rad / s (3000 rpm) until it They formed discrete granules.

4. The agglomerates were transferred to then to a horizontal rotating mixer and they were treated for 30 s. with 8 parts of zeolite fluidizer.

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TABLE 2

Composition by weight Anhydrous sodium acetate 40 Sodium carbonate twenty Nonionic surfactant (C45 AE7) 26 Lutensit KHD96 6 Fluidifier (zeolite) 8

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Example C

The process used in example A was repeated using the composition of Table 3. In this example, acetate Anhydrous powder from Example A was replaced by a premix of anhydrous acetate powder and dried zeolite in a ratio of 9 parts of anhydrous acetate powder and 1 part of zeolite desiccated

TABLE 3

Composition by weight Sodium Acetate Premix anhydrous / zeolite 40 Carbonate sodium twenty Surfactant no ionic (C45 AE7) 26 Lutensit KHD96 6 Fluidizer (zeolite) 8

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Examples FROM

The process of Example C was repeated replacing anhydrous sodium acetate by anhydrous magnesium acetate or acetate sodium trihydrate powder. The acetate premix of magnesium-zeolite comprised 1 part of acetate Anhydrous magnesium powder per 9 parts of dried zeolite.

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TABLE 4

Example D% by weight Example E% in weigh Acetate premix anhydrous magnesium / zeolite 40 Sodium Acetate Trihydrate 40 Sodium carbonate twenty 36 Nonionic surfactant (C45 AE7) 26 13 Lutensit KHD96 6 3 Fluidifier (zeolite) 8 8

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Examples F-G

The process of example A was repeated replacing C45 AE7 surfactant by other surfactants as indicated in the Table 5. The LAS surfactant is linear alkylbenzene sulfonate and the surfactant AS is a alkyl- (C12-C15) -sulfate.

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TABLE 5

Example F (LAS) Example G (AS) Composition in weigh Composition by weight Anhydrous sodium acetate 30 30 Sodium carbonate 25 twenty LAS Pasta 35 - AS Pasta - 40 Fluidifier (zeolite) 10 10

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Example H

Example A was repeated using a process of different particle preparation. The process allowed to increase the particle activity without using a cationic polymer:

1. A high mixer / agglomerator was loaded shear (EIRICH type RV02) with a mixture comprising acetate anhydrous powder (with an average particle size less than 100 µm) and finely divided sodium carbonate (with a size of average particles less than 200 µm).

2. Then non-ionic surfactant was added ethoxylated (C14-C15 OE7) to the dry mixture of carbonate / acetate.

3. The surfactant and dry powders are agglomerated in the mixer / agglomerator with the cutter set to 157 rad / s (1500 rpm) and the bowl rotating at 8.7 rad / s (84 rpm).

4. Then the mixture was transferred to an extruder dome (Fuji Puadal type Dg-L1) for the extrusion.

5. The extrudates formed were transferred to then to a rotating mixing drum and treated during 30 sec. with zeolite fluidizer.

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TABLE 6

Composition by weight Anhydrous sodium acetate 40 Sodium carbonate 30 Nonionic surfactant (C45 AE7) 25 Fluidifier (zeolite) 5

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Example I

With respect to the previous examples, it was used a different process to intimately mix the acetate with the surfactant

1. A high mixer / agglomerator was loaded shear (Lodige FM 130 with a mixture comprising zeolite and finely divided sodium carbonate (with a particle size average less than 200 µm).

2. Then LAS surfactant was added to the mixture dry carbonate / acetate.

3. The surfactant and dry powders are pre-agglomerated in the mixer / agglomerator with the vanes fixed to 18 rad / s (175 rpm) and the cutter set at 314 rad / s (3000 rpm) until microgranules formed in the mixer / agglomerator.

4. During the agglomeration it was sprayed on the microgranules an aqueous solution of 50% by weight of sodium acetate. The Lodige was set at a turning speed of 17 rad / s (170 rpm) and the cutter at 314 rad / s (3000 rpm) until they formed agglomerates

5. Then the agglomerates were dried in a fluid bed dryer at 80 ° C for 20 minutes.

After drying, the chipboard presented the composition indicated in Table 7

TABLE 7

Composition by weight Sodium carbonate 30 Zeolite 25 LAS in powder twenty

TABLE 7 (continued)

Composition by weight 50% solution of sodium acetate 10 Water 4 Fluidifier (zeolite) eleven

Example J

A detergent base powder of a finished laundry detergent mixing the components that They are listed in Table 8, except for polyethylene glycol and perfume they pulverized.

TABLE 8

Component Example J (% by weight) Non-ionic surfactant agglomerate of the example B 9.9 Chipboard anionic surfactant 28.1 Laminated silicate compacted granule 9.0 Granulated carbonate 13.4 Granulated percarbonate 14.2 Citric acid anhydrous 7.0 Chipboard suppressor suds 1.9 Soap on powder 1.4 Polymer for granulated dirt release 4,5 Activator chipboard bleach 5.5 Others 1.1 Enzymes 2.2 Sulfate sodium - Sprayed of polyethylene glycol 1.3 Sprayed perfume 0.5

Anionic agglomerates comprise 38% of anionic surfactant, 22% zeolite and 40% carbonate

The bleach activator agglomerates comprise 81% TAED (tetraacetylethylene diamine), 17% of acrylic / maleic copolymer (acid form) and 2% water.

Zinc phthalocyanine encapsulates Sulfonated have an activity of 10%.

The agglomerate of suds suppressor comprises 11.5% silicone oil (from Dow Corning) and 88.5% of starch.

The compacted laminar silicate granule comprises 78% of SKS-6, of Hoechst, and 22% of acid citric.

The same finished detergent was prepared for laundry washing replacing the non-ionic surfactant agglomerate by sodium sulfate as filler, as indicated in Table 8.

Example K

1. 80 parts were mixed in a mixing drum of base powder of composition J with 11 parts citric acid anhydrous and 11 parts of sodium carbonate.

2. The tablets were prepared in the manner next: 55 g of the mixture was introduced in a circular mold with a diameter of 5.5 cm and were compacted to obtain tablets of 2cm tall Tensile strength (or fracture stress diametral) of the tablet was 9 kPa

Example L

After preparing the tablets of example K, the tablets were immersed in a bath comprising 90 parts of dodecanedioic acid mixed with 10 parts of Nymcel zsb16 heated to 140 ° C. The time that was to remain was adjusted submerged the tablet in the heated bath so that they can apply 5 g of the mixture described on the tablet. The pill is allowed to cool to an ambient temperature of 25 ° C for 24 hours.

Example M

i) A detergent base powder of the M composition as follows: all materials in form of particles of the base composition M were mixed in a drum mixer to form a mixture in the form of homogeneous particles. During this mixing the sprays were performed. After the Powdered sodium diisoalkylbenzenesulfonate (DIBS) was added to the rest of the matrix.

ii) The tablets were prepared as follows way. 43 g of the mixture was introduced into a circular mold with a diameter of 5.5 cm and were compressed to obtain a resistance to traction (or diametral fracture tension) in the 15 pill kPa.

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Composition M (%) Agglomerates anionic 1 9.1 Agglomerates anionic 2 22.5 Agglomerates nonionic 9.1 Agglomerates cationic 4.6 Silicate laminate 9.7 Percarbonate sodium 12.2 Agglomerates of bleach activator 6.1 Sodium carbonate 7.27 EDDS / Sulfate Particles 0.5 Tetrasodium salt of hydroxyethane acid diphosphonic 0.6 Polymer for dirt release 0.3 Fluorescent 0.2 Zinc Phthalocyanine Encapsulation sulphonated 0.03 Soap on powder 1.2 Suppressor of suds 2.8 Acid citric 5.5 Protease one

(Continuation)

Composition M Lipase 0.35 Cellulase 0.2 Amylase 1.1 System of binder spray 3.05 Sprayed perfume 0.5 DIBS 2.1

Anionic agglomerates 1 comprise 40% of anionic surfactant, 27% zeolite and 33% carbonate.

Anionic agglomerates 2 comprise 40% of anionic surfactant, 28% zeolite and 32% carbonate.

The non-ionic agglomerate comprises 26% of non-ionic surfactant, 6% Lutensit K-HD 96, 40% of anhydrous sodium acetate, 20% carbonate and 8% zeolite.

Cationic agglomerates comprise 20% of cationic surfactant, 56% zeolite and 24% sulfate.

The laminar silicate comprises 95% of SKS 6 and 5% silicate

The bleach activator agglomerates comprise 81% TAED, 17% acrylic / maleic copolymer (form acid) and 2% water.

Acid Sodium Salt Particles ethylenediamine-N, N-disuccinic / sulfate comprise 58% acidic sodium salt ethylenediamine-N, N-disuccinic, 23% sulfate and 19% water.

Zinc phthalocyanine encapsulates Sulfonated have an activity of 10%.

The suds suppressor comprises 11.5% of silicone oil (from Dow Corning); 59% zeolite and 29.5% of Water.

The binder spray system comprises 0.5 parts of Lutensit K-HD 96 and 2.5 PEG parts.

Claims (14)

1. A surfactant agglomerate comprising from 10% to 50% by weight of the agglomerate of a surfactant and a vehicle, characterized in that it also comprises a water-soluble acetate salt in close proximity to the surfactant. 2. An agglomerate according to claim 1, in the that the surfactant is a nonionic surfactant. 3. An agglomerate according to claims 1 or 2, which also comprises a polymer with a higher melting point at 35 ° C. 4. An agglomerate according to claim 2, in the that the nonionic surfactant is an ethoxylated alcohol. 5. An agglomerate according to any of the claims 1-4, which also comprises a water-soluble cationic compound. 6. A chipboard according to any of the previous claims, comprising from 10% to 50% by weight of the surfactant agglomerate, 10% to 40% by weight of the agglomerate of vehicle, and 10% to 40% of acetate and 0% to 20% by weight of agglomerate of water-soluble cationic compound. 7. An agglomerate according to claim 6, which comprises from 25% to 35% by weight of the surfactant agglomerate, of 25% to 35% by weight of the vehicle agglomerate, from 25% to 35% of the acetate and from 0% to 15% by weight of the cationic compound agglomerate water soluble. 8. A process to prepare a chipboard according to the preceding claims, wherein the acetate, or a portion thereof, mixed with the surfactant or the vehicle before agglomerate the surfactant with the vehicle. 9. A process to prepare a chipboard according to any of claims 1-7, wherein the acetate, or a portion thereof, is sprayed on a prior agglomeration of the surfactant and the vehicle and, optionally, the other portion of acetate. 10. A process according to claims 8 or 9, in which the water-soluble cationic compound is mixed with the surfactant before mixing the surfactant with the vehicle. 11. A granulated detergent composition, which comprises an agglomerate according to any of the claims 1-7 and other detergent ingredients. 12. A detergent tablet composition, which comprises an agglomerate according to any of the claims 1-7 and other detergent ingredients. 13. A composition according to claims 11 or 12, in which at least 40%, preferably 60% and with maximum preferably at least 90%, of the surfactant is incorporated into the composition by agglomerate. 14. A chipboard according to claims 1 to 7, in which the water-soluble acetate salt is mixed with zeolite.