MXPA00012542A - Alkoxylated polyalkyleneimine dispersants - Google Patents

Abstract

The present invention relates to an alkoxylated polyalkyleneimine soil dispersant having formula (I), wherein R is C2-C6 linear alkylene, C3-C6 branched alkylene, and mixtures thereof;B is a continuation by branching;E is an alkyleneoxy unit having the formula:-(R1O)m(R2O)nR3, wherein R1 is 1,2-propylene, 1,2-butylene, and mixtures thereof;R2 is ethylene;R3 is hydrogen, C1-C4 alkyl, and mixtures thereof;m is from about 1 to about 10;n is from about 10 to about 40;w, x and y are each independently from about 4 to about 200;provided at least one -(R1O) unit is attached to the backbone prior to attachment of an -(R2O) unit and further provided m + n is at least 12.

Description

DISPERSANTS OF ALCOXYLATED POLYALYKYLENIMINE FIELD OF THE INVENTION The present invention relates to dispersants of hydrophobic polyalkyleneimine alkoxylated impurities which are suitable for use as impurity dispersants in applications.

BACKGROUND OF THE INVENTION A convenient dispersant is required, the hydrophobic (eg, oil) and hydrophilic (clay) impurities that are removed during the laundry step of the laundry process can be redeposited on the clean fabric. The impurity dispersants act by sequestering the powder once it is dissolved or dispersed in the laundry liquid and keep the impurities suspended in the laundry liquid where it can be removed during the normal rinsing process. Usually, if bleaching agents, especially peroxygen bleach which are formulated in liquid and granular laundry detergent compositions are present, the formulator must take into account the instability of a specific impurity dispersant towards the bleach. Many suitable dispersants have polyalkyleneamine or polyalkyleneimine structures that are susceptible to oxidation in the amines functionalities, and are potentially broken or fragmented by the bleaching agents that may be present. From another point of view, the interaction of the bleaching agents with these dispersants based on polyalkyleneimine exhausts the amount of bleach present, thereby affecting the bleaching performance. Accordingly, there remains a need in the art for highly efficient hydrophobic impurity dispersants, compatible with bleaches. Surprisingly, it has been found that certain higher molecular weight polyalkyleneimines comprising a mixture of alkyleneoxy units that are attached to a polyalkyleneimine backbone in a particular order provide hydrophobic dispersants with better compatibility with the bleach as well as better dispersibility.

SUMMARY OF THE INVENTION The present invention meets the aforementioned needs in that it has surprisingly been found that the polyalkyleneimines having a molecular weight in the main structure from about 600 daltons to about 25,000 daltons where in the. Main chain The nitrogens have been replaced by an average degree of alkylenoxylation mixed by the N-H unit of, from 12 to about 50 alkyleneoxy units, provide an improved hydrophobic impurity dispersant which is compatible with the bleach. The polyamine backbone is first modified by substitution of, from 1 to 10 propyleneoxy units, butyleneoxy units and mixtures thereof, followed by ethyleneoxy units so that the total degree of alkylenoxylation does not exceed about 50 units.The alkoxylated polyalkyleneimines of the present invention is suitable for use in high and low density granular detergent compositions, liquid for heavy and light washing, as well as laundry bars The present invention relates to an impurity dispersant having the formula: EB [E2N-R] W [NR] x [NR] yNE2 (I) wherein R is linear C2-C6 alkylene, branched C3-C6 alkylene, and mixtures thereof; B is a continuation by branching, E is an alkylenoxy unit having the formula: - (R10) m (R20) nR3 wherein R1 is 1,2-propylene, 1,2-butylene and mixtures thereof; R2 is ethylene; R3 is hydrogen, C4-C4 alkyl and mixtures thereof; m is from about 1 to about 10; n is from about 10 to about 40; , x and y are each independent from each other from about 4 to about 200; provided that at least one unit - (? XO) is attached to the main chain before joining a unit - (R20) and also provided that m + n is at least 12. These and other objectives, characteristics and advantages will be apparent to those skilled in the art from reading the following detailed description and the accompanying clauses. All percentages, ratios and proportions herein are by weight, unless otherwise specified. All temperatures are in degrees Celsius (° C) unless otherwise specified. All the documents mentioned are in the relevant part, incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polyalkyleneimine dispersants that are substituted with polyalkyleneoxy, wherein the propyleneoxy units, butyleneoxy units and mixtures thereof are bonded to the nitrogens of the main chain before the subsequent joining of the polyethyleneoxy units . The polyamine backbones of the present invention have the general formula: E B [E2N-R] W [N-R] x [N-R] yNE2 The main chains before the subsequent modification, have primary amine, secondary and tertiary amine nitrogens connected by "linker" units R. The main chains are composed mainly of three types of units, which can be randomly distributed along chain. The units that constitute the polyalkyleneimine main chain are primary units having the formula: [H2N-R] - and -NH2 That ends the main chain and any of the branching chains, secondary amine units having the formula: H I - [N-R] - and which, after modification, has its hydrogen atom substituted by from 1 to 10 propyleneoxy units, butyleneoxy units and mixtures thereof followed by from 10 to 40 ethyleneoxy units, and the tertiary amine units having the formula: B I - [N-R] - which are the branch points of the main and secondary skeletal chains, B representing a continuation of the chain structure by branch.

The tertiary units have no substitutable hydrogen atom and therefore are not modified by substitution with an alkylenoxy unit. During the formation of the polyamine backbones, cyclization can occur, therefore, a quantity of cyclic polyamine can be present in the original polyalkyleneimine backbone mixture. Each primary and secondary amine unit of the cyclic alkylenes undergoes modification by the addition of alkyleneoxy units in the same manner as the linear and branched polyalkyleneimines. R is linear C2-Cd alkylene, branched C3-Cd alkylene, and mixtures thereof, the preferred branched alkylene is 1,2-propylene, preferred R is ethylene. The preferred polyalkyleneimines of the present invention have backbones containing the same unit R, for example, all units are ethylene. The most preferred main chain contains R groups which are all ethylene units. The polyalkyleneimines of the present invention are modified by substituting each unit hydrogen N-H with an alkyleneoxy unit having the formula: - (R10) m (R20) nR3 wherein R 1 is 1,2-propylene, 1,2-butylene, and mixtures thereof, preferably 1,2-propylene. R2 is ethylene. R3 is hydrogen, C4-C4 alkyl and mixtures thereof, preferably hydrogen or methyl, more preferably hydrogen. For the purposes of the present invention, at least one propyleneoxy or butyleneoxy unit must be attached to the main chain nitrogen units before replacement with any other alkyleneoxy unit. The value of the index m is from about 1, preferably from about 2. to about 10, preferably up to about 6, most preferably up to about 5. The value of the index n is from about 10, preferably from about 15, most preferably from about 20 to about 40, preferably up to about 35, of greater preference to about 30. The value of m + n is preferably at least 12, more preferably from about 15, more preferably from about 20 to about 40, most preferably up to about 35. An example of a preferred polyalkyleneoxy substituent consists of 3 units 1,2-prspilenoxi before d and the subsequent ethoxylation, especially when the average value of m + n is approximately 30. The preferred molecular weight for the polyamine backbones is from about 600 daltons, preferably from about 1200 daltons, more preferably from about 1800 daltons, more preferably from about 2000 daltons to about 25,000 daltons, preferably up to about 20,000 daltons, more preferably up to about 15,000 daltons, more preferably 5000 daltons. An example of a preferred molecular weight for a polyethyleneimine backbone is 3000 daltons. The indices x and y necessary to achieve the preferred molecular weights will vary depending on the portion R comprising the main chain. For example, when R is ethylene, a main chain unit averages approximately 43 gm [sic] and when R is hexylene, one unit of the main chain averages approximately 99 gm [sic]. The polyamines of the present invention can be prepared, for example, by polymerizing ethylene imine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc. Specific methods for the preparation of these polyamine backbones are described in U.S. Patent 2,182,306, Ulrich et al., Published December 5, 1939; U.S. Patent 3,033,746 to Mayle et al., published May 8, 1962; U.S. Patent 2,208,095 to Esselman et al., published July 16, 1940; US Patent 2,806,839 to Crowther, published on September 17, 1957; and U.S. Patent 2,553,696, Wilson, published May 21, 1951; incorporated herein by reference. The following is an example of a preferred embodiment of the present invention, wherein in formula I, R means -CH2-CH2-, the polyethyleneimine thus represented has an average molecular weight in the main chain of about 3000, E represents - ( R10) m (R20) nR3 wherein R1 is a 1,2-propylene unit having the formula: CH3 CH3 I I CHCH2 -CH2CH- R2 is ethylene, R is hydrogen and m + n is equal to about 30.

The modification of the NH units in the polymer with polypropylene oxide, butylene oxide and ethylene oxide units is carried out by first reacting the polymer, preferably polyethylenimine, with propylene oxide, butylene oxide and mixtures thereof, and then adding ethylene oxide. In greater detail, for example, the polyethyleneimine is first reacted with propylene oxide in the presence of up to about 70% by weight of water at a temperature of from 25 to 150 ° C in an autoclave adapted with a stirrer. In the first step of the reaction, the propylene oxide is added in such an amount that almost all of the hydrogen atoms of the N-H groups of the polyethylene imine are converted to hydroxypropyl groups. The water is then removed from the autoclave. After the addition of a basic catalyst, for example, sodium methylate, potassium terbutylate, potassium hydroxide, sodium hydroxide, sodium hydride, potassium hydride or an alkaline ion exchanger in an amount of 0.1 to 15% by weight , with reference to the addition product obtained in the first step of the propoxylation, other amounts of propylene oxide are added to the reaction product of the first step so that a propoxylated polyethyleneimine containing 1-10, preferably 2, is obtained. to 5, more preferably 3 to 4 units of propylene oxide per NH group of the polymer. The second step is carried out, for example, at temperatures from 60 to 150 ° C. After the addition of propylene oxide to the polyethylene imine in these amounts, the reaction product further reacts at temperatures in the range from 60 to 150 ° C with 10 to 40, preferably 20 to 40, more preferably 25 to 35. moles of ethylene oxide forming the impurity dispersants of the invention. The second step of the propoxylation and the subsequent oxyethylation of the reaction product obtained in the first step can be carried out in an organic solvent such as xylene.

EXAMPLE 1 PEÍ 3000 (PO) 3. (EO) 27 43 g of polyethyleneimine (PEI having an average molecular weight of 3000 and corresponding to 1.0 mole, with reference to ethylene imine) is added as a 54 wt% aqueous solution to an autoclave adapted with a stirrer under a nitrogen blanket. The autoclave is sealed and its contents are heated with agitation at 90 ° C. At this temperature, 58 g (1 mol) of propylene oxide is pressurized. Agitation continues until the pressure remains constant. The contents of the autoclave are then cooled to a temperature of 80 ° C and 12.5 g of potassium hydroxide are added as an aqueous solution at 40 ° C of concentration by weight. The water is then removed by applying a vacuum of approximately 20 mbar. 103 g of a viscous oil are obtained. In the second step of the alkoxylation, 101 g of hydroxypropylated polyethylenimine obtained in the previous step are placed in an autoclave with stirring and heated under nitrogen at 120 ° C. The reactor is pressurized several times with nitrogen and its contents are heated to 140 to 145 ° C. Then 116 g (2 moles) of propylene oxide are introduced under pressure. The reaction mixture is stirred at 140 to 145 ° C until the pressure is constant. The ethylene oxide is then added in the temperature range in an amount of 1180 g (27 moles) with reference to ethylene imine). The reaction mixture is stirred until the pressure is constant and then cooled to 80 ° C. Approximately 1.4 kg of a viscous brown oil is obtained. The alkoxylated product becomes a brown solid at room temperature and has a melting point of 45 to 50 ° C.

Claims (1)

1. CLAIMS A dispersant of impurities that has the formula: E B [E2N-R] W [N-R] x [N-R] and NE2 (I) wherein R is linear C2-Cd alkylene, branched C3-C6 alkylene, and mixtures thereof; B is a continuation by branching, E is an alkyleneoxy unit having the formula: - (R'O ÍR ^ nR3 wherein R1 is 1,2-propylene, 1,2-butylene and mixtures thereof; R2 is ethylene; R3 is hydrogen, C4-C4 alkyl and mixtures thereof; m is from about 1 to about 10; n is from about 10 to about 40; w, x and y are each independent from each other from about 4 to about 200; provided that at least one unit (? XO) is attached to the main chain before the union of a unit (R20) and also provided that m + n is at least 12. The impurity dispersant according to the Claim 1, wherein R is ethylene. The impurity dispersant according to claim 2, wherein R is 1, 2-propylene, R3 is hydrogen, m is from about 1 to about 6, n is from about 15 to about 35 and m + n is from about 20 to about 40. The impurity dispersant according to claim 3, wherein m is from about 2 to about 5, n is from about 20 to about 30, and m + n is from about 25 to about 35. The impurity dispersant of according to claim 4, wherein m is 3 and n is 27. The impurity dispersant according to claim 3, wherein the molecular weight of the main chain before modification is from about 600 daltons to about 25,000 daltons. The impurity dispersant according to claim 6, wherein the molecular weight of the main chain before modification is from about 1200 daltons to about 20,000 daltons. The impurity dispersant according to claim 7, wherein the molecular weight of the main chain before modification is from about 2000 daltons to about 5000 daltons. The impurity dispersant according to claim 8, wherein the molecular weight of the main chain before modification is approximately 3000 daltons. The impurity dispersant according to claim 1, wherein R is ethylene, R1 is 1, 2-propylene, R2 is ethylene, R3 is hydrogen, m is 3, n is 27 and the indices w, x and y are taken together so that the polyalkyleneimine backbone before modification has a molecular weight of about 3000 daltons.