WO1997023546A1 - A process for ethoxylating polyamines - Google Patents

A process for ethoxylating polyamines

Info

Publication number
WO1997023546A1
WO1997023546A1 PCT/US1996/019094 US9619094W WO1997023546A1 WO 1997023546 A1 WO1997023546 A1 WO 1997023546A1 US 9619094 W US9619094 W US 9619094W WO 1997023546 A1 WO1997023546 A1 WO 1997023546A1
Authority
WO
Grant status
Application
Patent type
Prior art keywords
ofthe
gm
preferably
base
present
Prior art date
Application number
PCT/US1996/019094
Other languages
French (fr)
Inventor
Eugene Paul Gosselink
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723Polyamines, polyalkyleneimines
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2618Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
    • C08G65/2621Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
    • C08G65/2624Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aliphatic amine groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02Polyamines

Abstract

A process for preparing low odor, low color, polyethoxylated polyamines is disclosed. The ethoxylated polyamines described herein are useful for cleaning compositions comprising soil release agents, dispersents, and other nonionic surface active agents.

Description

A PROCESS FOR ETHOXYLATING POLYAMINES

FIELD OF THE INVENTION

The present invention relates to a process for ethoxylating polyamines, especially polyethyleneimines. The compounds ofthe present invention comprise low color, low odor ethoxylated amines suitable for use in cleaning compositions. BACKGROUND OF THE INVENTION

Ethoxylates of polyamines have wide utility in the field of cleaning compositions, for example they are useful as soil dispersents and chelators among others. When formulating polyamine ethoxylates into laundry detergent compositions, a number of factors determine the suitability ofthe compounds; among others are viscosity, odor and color.

In the past, higher molecular weight polyamines have been difficult to ethoxylate especially when a narrow degree of average ethoxylation was desired. Longer reaction times and higher process temperatures consistently led to degradation products responsible for the formation of unwanted colors and malodors. In addition, non-reproducible results led to varying levels of final product uniformity which effected the bulk physical properties and thereby hampered uniform processing.

The present invention overcomes many viscosity, color and malodor problems associated with the ethoxylation of polyamines. The reduced off-color of the final product makes the ethoxylated polyamines prepared by the present process, ready for formulation into cleaning compositions comprising other adjunct ingredients and further eliminates the need to use fragrances or colorants to disguise undesirable properties.

While not wishing to be limited by theory, the process according to the present invention reduces the occurrence of side reactions which result in extensive fragmentation ofthe polyamine backbone or formation of polyethoxylate vinyl ethers. The formation of acetaldehyde, which can undergo further chemical reactions, such as those leading to conjugated chromophores, is likewise greatly reduced. The resulting ethoxylated amines are also uniformly ethoxylated to a greater degree and therefore produce a more consistent product.

Surprisingly, the present process is also adaptable to systems where use of a solvent is desirable to the formulator. Use of solvent may be advantageous in allowing good mixing during ethoxylation particularly when the polyamine and/or its ethoxylated products have high viscosity in neat form. The use of a solvent in some instances can aid in the further processing of the ethoxylated polyamines, especially when the product is to undergo subsequent chemical transformations. This optional use of a solvent also provides a convenient method of forming certain anhydrous base catalysts, for example, sodium t-butoxide can be produced in situ when sodium metal is added to a polyamine dissolved in t-butanol.

Processes for preparing ethoxylated amines are well known in the art, for example, U.S. Patent 4,891,160, Vander Meer, issued January 2, 1990 discloses methods for ethoxylating diamines, polyamines, and polyalkyleneimines comprising an initial step of condensing ethylene oxide with the amine, however, Vander Meer fails to disclose the use of solvents or solvent derived (i.e. alkoxide) base catalysts.

In addition, U.S. Patent 4,551,506, Gosselink, issued November 5, 1985 discloses the use of a base catalyst, however the disclosed amounts of base catalyst used for the U.S. Patent 4,551,506 method is outside the range ofthe present invention.

It is an object ofthe present invention to provide a method for ethoxylating polyamino compounds wherein the final product has little or no malodor associated with it. It is a further object ofthe present invention to provide a method for ethoxylating polyamino compounds wherein color formation is reduced.

An object ofthe present invention is to provide a method for ethoxylating polyamino compounds wherein a large choice of anhydrous base catalysts are suitable for use. It is also an object ofthe present invention to provide a base catalyzed method for ethoxylating polyamines wherein the choice of base catalyst allows the formulator to use suitable solvents and catalyst carriers. It is furthermore an object ofthe present invention to provide a method for ethoxylating polyamino compounds wherein the final ethoxylated polyamine comprises a narrow range of ethoxylation and that due to lower fragmentation rates, a lower polydispersity ethoxylated product is obtained.

BACKGROUND ART

In addition to the above identified U.S. Patents describing the ethoxylation of polyamino compounds, further processes are disclosed in: U.S. Patent 4,622,378, Gosselink, issued November 1 1, 1986; EP Application 233,010, Collins, et al., published August 19, 1987.

SUMMARY OF THE INVENTION

The present invention relates to a method for preparing ethoxylated polyamines ofthe formula: wherein R is C2-C22 linear alkylene, C3-C22 branched alkylene, Cg-C22 dialkylsubstituted arylene, C7-C22 substituted arylene, and mixtures thereof; n is from about 2 to about 100, x is from 0 to about 300, y is from 0 to about 600, z is from 1 to about 300; comprising the steps of: a) reacting a polyamine ofthe formula:

with ethylene oxide, optionally in the presence of a solvent, until the average value of n is from about 0.75 to about 1.25; b) adding from about 2% to about 40% of the total number of N-H equivalents, of a base catalyst, said base catalyst optionally comprising a carrier; c) optionally removing the base catalyst carrier by vacuum, heating, or combinations thereof; d) further reacting the composition from step (b) or step (c) with ethylene oxide until the average value of n is from 2 to about 100; e) neutralizing the base catalyst; and f) optionally removing the solvent.

The ethoxylated polyamines ofthe present invention are preferably polyethyleneimines and are generally suitable for use without further purification. The method for preparing the ethoxylated polyamines ofthe present invention is also suitable for preparing ethoxylated polyamines for use in detergent compositions, for example, soil dispersants, soil release polymers, non-ionic surfactants.

All percentages, ratios and proportions herein are by weight, unless otherwise specified. All temperatures are in degrees Celsius (° C). All documents cited are, in relevant part, incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION

The methods for preparing ethoxylated polyamines according to the present invention involve contacting a polyamine with ethylene oxide, followed by addition of a suitable base catalyst, then re-introduction of ethylene oxide into the reaction matrix until the desired degree of ethoxylation has been achieved. The steps are outlined in more detail as follows. Step a: A polyamine ofthe formula

H

[H2N-R]— [N-R]-[N-R]-NH2

wherein R is C2-C22 linear alkylene, C3-C22 branched alkylene, Cg-C22 dialkylsubstituted arylene, C7-C22 substituted arylene, preferably C2-C22 linear alkylene, C3-C22 branched alkylene, more preferably C2-C6 linear alkylene, C3-C6 branched alkylene, still more preferably C2 linear alkylene (ethylene), and C3 branched alkylene (1,2 -propylene), most preferably R is ethylene, x is from 0 to about 300, y is from 0 to about 600, z is from 1 to about 300; is reacted with ethylene oxide, preferably at a temperature from about 5° C to about 250° C, more preferably from about 40° C to about 180° C, yet more preferably from about 55° C to about 150° C, most preferably from about 80° C to about 120° C, until the average degree of ethoxylation at each reactive origional -NH site is from about 0.75 to about 1.25, preferably from about 0.85 to 1.1, more preferably from 0.95 to about 1.

A solvent may be optionally added during step (a). Suitable solvents for use herein are selected from the group consisting of methanol, ethanol, isopropanol, t- butanol, benzene, toluene, xylene, polyethylene glycol having a molecular weight greater than about 100, polypropylene glycol having a molecular weight of from about 100 to about 2000, linear or branched C -C22 alcohols, alkoxylated linear or branched Cg-C22 alcohols, and mixtures thereof

Step b: A base catalyst is added in an amount from about 2% to about 40% ofthe total number of N-H equivalents present in the polyamine. The base catalyst may optionally comprise a base catalyst carrier. Suitable base catalysts are selected from the group consisting of sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium t-butoxide, potassium t-butoxide, sodium metal, potassium metal, and mixtures thereof, however this list is not meant to be exclusive. Preferred base catalysts are sodium metal and potassium hydroxide sodium hydroxide, sodium methoxide and sodium t-butoxide.

For the purposes ofthe present invention the term "base catalyst carrier" is defined as a medium used for the purposes of safely and quantitatively adding the base catalyst. Suitable base catalyst carriers are water, methanol, ethanol, isopropanol, t-butanol, and mixtures thereof, however, this list is not meant to be exclusive. For example, Sodium hydroxide can be suitably introduced into the reaction process via the carrier water. In addition, sodium hydride and potassium hydride may be introduced into the process ofthe present invention as slurries in clear, inert mineral oil.

Step c: Any carrier used to introduce the base catalyst is optionally removed at this point. The formulator may use a vacuum, heating, or a combination of heating under a vacuum. Sparging with an inert gas is also a suitable means of removing any carrier. However, it is an optional step to remove any carrier present.

Step d: Ethylene oxide is then further introduced into the reaction vessel whereby the contents ofthe reaction vessel reacts with ethylene oxide, preferably at a temperature from about 5° C to about 250° C, more preferably from about 40° C to about 180° C, yet more preferably from about 55° C to about 150° C, most preferably from about 80° C to about 130° C, until the average degree of ethoxylation at each reactive site is from about 2 to about 100, preferably from about 2 to about 40, more preferably from about 2 to about 20, even more preferably from about 2 to about 12, most preferably from about 2 to about 7.

Step d: The base catalyst is neutralized with any compatible organic or inorganic acid. For the purposes ofthe present invention the term "compatible organic or inorganic acid" is defined as any acid that serves the purpose of bringing the reaction mixture to a pH suitable for isolation or further processing ofthe reaction products. Examples of suitable acids are the C2-C6 aliphatic acids, mineral acids (e.g., HCl, H2SO4), and others such as methanesulfonic acid, however this list is not limiting. Neutralization may be conducted to any degree that suffices the formulator.

Step e: During this step ofthe process ofthe present invention, any solvents or undesired carrier that remains may be removed. This solvent removal may be conducted by using the aid of a vacuum, heat, or combinations thereof. Stripping gases may also be used to remove volatile solvents. In some cases, molecular sieves or zeolites, may be used by the formulator to remove low molecular weight solvents and carriers.

The reactions that comprise the process ofthe present invention can be carried out in any size reaction vessel. The vessel can be typical laboratory glassware or stainless steel reactors. The reaction can also be carried out in a glass- lined autoclave. The reaction can be conducted on any suitable scale from several hundred milligrams to several thousand kilograms.

Typically the polyamines used for making the ethoxylated polyamines by the process ofthe present invention, can be used without prior purification, however it is common practice to purge the amines with an inert gas such a nitrogen or argon prior to heating or contacting with ethylene oxide. The aid of a vacuum for removing any undesirable materials formed during storage ofthe amines is typical of standard pre-process procedures. The degree to which the polyamine is pre¬ treated is determined to a large degree by the purity ofthe starting polyamine.

Once the polyamine to be ethoxylated has been charged to the reaction vessel, a pre-determined amount of ethylene oxide is added. Preferably enough ethylene oxide is introduced to react with each reactive -NH- site so that between 0.75 and 1.25 moles of ethylene oxide have been added per mole of reactive N-H moiety, preferably 0.85 to about 1.05, more preferably from about 0.95 to 1.

The manner in which the ethylene oxide is introduced into the reaction vessel is ultimately left to the formulator, however, certain highly reactive amines may cause an initial exothermic reaction and caution is due particularly on a large scale. Typically, a vacuum is drawn on the head space ofthe reaction vessel and ethylene oxide is then drawn into the evacuated space through a metered stopcock or pumped in as a liquid and the amount is determined by weight difference or flow meters. Uniformity of reaction is ensured by sufficient mechanical or magnetic stirring.

Once the hydroxyethylation reaction has proceeded to between 0.75 and 1.25 equivalents of ethylene oxide per active -NH- moiety, the base catalyst is added. The term "base catalyst" is defined as any base sufficient to de-protonate the hydroxyl group of a hydroxyethylated amine moiety. The base catalysts can be anhydrous or the base catalysts may be introduced via an aqueous or solvent based carrier. Typical anhydrous base catalysts are sodium metal, sodium hydride or potassium hydride (especially in combination with mineral oil carrier as a dispersion), sodium methoxide, sodium ethoxide, sodium isopropoxide, sodium propoxide, and sodium tert-butoxide, however this list is not meant to be exhaustive. In addftion, sodium methoxide or other suitable alkoxide bases may be formed in situ by the addition of an alkali metal to a solution ofthe hydroxyethylated amine dissolved in an appropriate hydroxylic solvent. Sodium t-butoxide solid is also suitable for use and does not necessarily have to be formed in situ.

The contents ofthe reaction vessel is then further reacted with ethylene oxide at a temperature from about 40° C to about 250° C, preferably from about 55° C to about 150° C, more preferably from about 80° C to about 120° C, until the average degree of ethoxylation at each reactive site is from about 2 to about 100.

The base catalyst is then neutralized using a suitable acid. Any acid that is compatible with the further formulation and processing ofthe ethoxylated polyamine is suitable for use in the present process. A preferred acid is methanesulfonic acid. Next, removal of any solvent present in the reaction mixture is accomplished by any ofthe standard methods known by those skilled in the art. Typically, for laboratory scale operations under several kilogram, a rotary evaporator is suitable for use in removing the solvent. In addition, thin film evaporators are used for larger scale batches, however in both cases the solvent may be optionally retained.

An advantage ofthe process ofthe present invention is that it allows the formulator to prepare a final product that comprises a mixture of more than one laundry product ingredient. Suitable solvents for the process ofthe present invention include polyethylene glycol having a molecular weight greater than about 100, polypropylene glycol having a molecular weight from about 100 to about 2000, and linear or branched C -C22 alcohols. The conditions ofthe present process may be adjusted so that these materials may be co-ethoxylated with the polyamine. Therefore the formulator may produce a mixture of ethoxylate polyamine with other ethoxylated adjunct materials. This step may provide the "intimate mixing" step that is often necessary when formulating water soluble and sparsely water soluble adjunct detersive ingredients.

The Number of Moles of Base Catalyst: Determination of the Percentage ofthe Total -NH Equivalents

In general, the polyamines ofthe present invention will have a ratio of primary amine: secondary amine :tertiary amine of about 1 :2:1, that is the starting polyamines having the general formula

wherein R is the same as defined herein above, and generally have the values of x, y, and z in the ratio of 1 :2: 1. In the case of ethoxylating polyamines of the general formula

wherein x is from 0 to about 300, y is from 0 to about 600, and w is from 0 to about 22, the ratio of x:y will be approximately 1 :2.

The method for calculating "about 2% to about 40% ofthe total -NH equivalents" is defined as follows. Each -NH function capable of being ethoxylated is considered one equivalent. Primary amine moieties, -NH2, comprise two mole equivalents of -NH moieties and secondary amine moieties, -NH-, comprise one mole equivalent of -NH moieties. For example, the following polyethyleneimine, wherein R is ethylene, having the structure:

has a molecular weight of approximately 934 gm/mole and comprises 6 -NH2 moieties and 10 -NH- moieties. The total number of -NH equivalents is:

2 x 6 -NH2 = 12 + l x lO -NH- = 10

22 -NH equivalents The following table gives an example ofthe number of grams of catalyst needed in step (b) ofthe process ofthe present invention for one mole ofthe polyethyleneimine shown above having a molecular of 934 gm/mole (PEI 934). The selected levels are 2%, 5%, 25% and 40% ofthe calculated 22 -NH equivalents present in the polyamine molecule. Calculations are made for four different catalysts.

BASE 2% of -NH 5% of-NH 25% of -NH 40% of -NH moieties moieties moieties moieties

(0.44 moles) (1.1 moles) (5.5 moles) (8.8 moles)

NaH MW = 24 10.56 gm 26.4 gm 132.0 gm 21 1.2 gm

KH MW = 40 17.6 gm 44.0 gm 22.0 gm 352.0 gm

CH3ONa MW = 54 23.76 gm 59.4 gm 297.0 gm 475.2 gm

(CH3)3COK MW=112 49.28 gm 123.2 gm 616.0 gm 985.6 gm

When the PEI 934, as depicted above, is present in a quantity of one mole, then there are present for the purposes ofthe present invention, 22 moles of N-H equivalents. Therefore 22 moles of a base catalyst would be needed to have a level of " 100% of the total number of N-H equivalents" of base present. From the table above, 2% of the total N-H equivalents requires 0.44 moles of base and 40% ofthe total N-H equivalents requires 8.8 moles of base.

A further example, is the following polyethyleneimine with a molecular weight of approximately 1823 gm/mole having the structure:

comprising 11 -NH2 moieties and 23 -NH- moieties. The total number of -NH equivalents is:

2 x 1 1 -NH2 = 22 +1 x 23 -NH- = 23

45 -NH equivalents The following table gives an example ofthe number of grams of catalyst needed in step (b) ofthe process ofthe present invention for one mole ofthe polyethyleneimine shown above having a molecular of 1823 gm/mole (PEI 1823). The selected levels are 2%, 5%, 25% and 40% ofthe calculated 45 -NH equivalents present in the polyamine molecule. Calculations are made for four different catalysts. BASE 2% of-NH 5% of -NH 25% of-NH 40% of -NH moieties moieties moieties moieties

(0.9 moles) (2.26 moles) (11.3 moles) (18.1 moles)

NaH MW = 24 21.65 gm 54.3 gm 271.3 gm 434.4 gm

KH MW = 40 36.08 gm 90.3 gm 451.3 gm 722.4 gm

CH3ONa MW = 54 48.71 gm 121.8 gm 608.9 gm 974.4 gm

(CH3)3COK MW=112 101.02 gm 253.0 gm 1265.0 gm 2024.0 gm

A further example, is the following polyhexyleneamine with a molecular weight of approximately 2393 gm/mole having the structure:

comprising 7 -NH2 moieties and 13 -NH- moieties. The total number of -NH equivalents is:

2 x 7 -NH2 = 14 +I x l3 -NH- = 13

27 -NH equivalents The following table gives an example ofthe number of grams of catalyst needed in step (b) ofthe process ofthe present invention for one mole ofthe polyhexyleneamine shown above having a molecular of 2393 gm/mole (PEA 2393). The selected levels are 2%, 5%, 25% and 40% ofthe calculated 27 -NH equivalents present in the polyamine molecule. Calculations are made for four different catalysts. BASE 2% of-NH 5% of-NH 25% of-NH 40% of -NH moieties moieties moieties moieties

(0.54 moles) (1.35 moles) (6.75 moles) (10.8 moles)

NaH MW = 24 13.0 gm 32.4 gm 162.0 gm 259.2 gm

KH MW = 40 21.6 gm 54.0 gm 270.0 gm 432.0 gm

CH3ONa MW = 54 29.2 gm 72.9 gm 364.5 gm 583.2 gm

(CH3)3COK MW=112 60.5 gm 151.2 gm 756.0 gm 1209.6 gm

The following is an example in which polyethoxylated polyamines are prepared according to the method of present invention.

The ethoxylation is conducted in a 2 gallon stiπed stainless steel autoclave equipped for temperature measurement and control, pressure measurement, vacuum and inert gas purging, sampling, and for introduction of ethylene oxide as a liquid. A -20 lb. net cylinder of ethylene oxide (ARC) is set up to deliver ethylene oxide as a liquid by a pump to the autoclave with the cylinder placed on a scale so that the weight change ofthe cylinder could be monitored.

A 750 g portion of polyethyleneimine (PEI) (Nippon Shokubai, Epomin SP- 018 having a listed average molecular weight of 1800 equating to about 0.417 moles of polymer and 17.4 moles of nitrogen functions) is added to the autoclave. The autoclave is then sealed and purged of air (by applying vacuum to minus 28" Hg followed by pressurization with nitrogen to 250 psia, then venting to atmospheric pressure). The autoclave contents are heated to 130 °C while applying vacuum. After about one hour, the autoclave is charged with nitrogen to about 250 psia while cooling the autoclave to about 105 °C. Ethylene oxide is then added to the autoclave incrementally over time while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate. The ethylene oxide pump is turned off and cooling is applied to limit any temperature increase resulting from any reaction exotherm. The temperature is maintained between 100 and 110 °C while the total pressure is allowed to gradually increase during the course of the reaction. After a total of 750 grams of ethylene oxide has been charged to the autoclave (roughly equivalent to one mole ethylene oxide per PEI nitrogen function), the temperature is increased to 110 °C and the autoclave is allowed to stir for an additional hour. At this point, vacuum is applied to remove any residual unreacted ethylene oxide.

Next, vacuum is continuously applied while the autoclave is cooled to about 50 °C while introducing 376 g of a 25% sodium methoxide in methanol solution (1.74 moles, to achieve a 10% catalyst loading based upon PEI nitrogen functions). The methoxide solution is sucked into the autoclave under vacuum and then the autoclave temperature controller setpoint is increased to 130 °C. A device is used to monitor the power consumed by the agitator. The agitator power is monitored along with the temperature and pressure. Agitator power and temperature values gradually increase as methanol is removed from the autoclave and the viscosity ofthe mixture increases and stabilizes in about 1 hour indicating that most ofthe methanol has been removed. The mixture is further heated and agitated under vacuum for an additional 30 minutes.

Vacuum is removed and the autoclave is cooled to 105 °C while it is being charged with nitrogen to 250 psia and then vented to ambient pressure. The autoclave is charged to 200 psia with nitrogen. Ethylene oxide is again added to the autoclave incrementally as before while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate while maintaining the temperature between 100 and 110 °C and limiting any temperature increases due to reaction exotherm. After the addition of 4500 g of ethylene oxide (resulting in a total of 7 moles of ethylene oxide per mole of PEI nitrogen function) is achieved over several hours, the temperature is increased to 110 °C and the mixture stirred for an additional hour.

The reaction mixture is then collected in nitrogen purged containers and eventually transferred into a 22 L three neck round bottomed flask equipped with heating and agitation. The strong alkali catalyst is neutralized by adding 167 g methanesulfonic acid (1.74 moles). The reaction mixture is then deodorized by passing about 100 cu. ft. of inert gas (argon or nitrogen) through a gas dispersion frit and through the reaction mixture while agitating and heating the mixture to 130 °C.

The final reaction product is cooled slightly and collected in glass containers purged with nitrogen.

' In other preparations the neutralization and deodorization is accomplished in the reactor before discharging the product.

Claims

WHAT IS CLAIMED IS:
1. A method for preparing ethoxylated polyamines ofthe formula:
wherein R is C2-C22 linear alkylene, C3-C22 branched alkylene, Cg-C22 dialkylsubstituted arylene, C7-C22 substituted arylene, and mixtures thereof; n is from 2 to 100, x is from 0 to 300, y is from 0 to 600, z is from 1 to 300; comprising the steps of: a) reacting a polyamine ofthe formula:
with ethylene oxide, optionally in the presence of a solvent, until the average value of n is from 0.75 to 1.25, preferably from 0.85 to 1.1 , more preferably from 0.95 to 1; b) adding from 2% to 40% ofthe total number of N-H equivalents, a base catalyst, said base catalyst optionally comprising a carrier; c) optionally removing the base catalyst carrier by vacuum, heating, or combinations thereof; d) further reacting the composition from step (b) or step (c) with ethylene oxide until the average value of n is from 2 to 100, preferably from 2 to 40, more preferably from 2 to 20, and most preferably from 2 to 7; e) neutralizing the base catalyst; and f) optionally removing the solvent.
2. A method according to Claim 1 wherein R is C2-C22 linear alkylene, C3- C22 branched alkylene, and mixtures thereof; preferably C2-C linear alkylene, C3-C5 branched alkylene, and mixtures thereof; more preferably C2 linear alkylene, C3 branched alkylene, and mixtures thereof; and most preferably C2 linear alkylene.
3. A method according to either of Claims 1 or 2 wherein step (a) is conducted at a temperature of from 5° C to 250° C, preferably from 40° C to 180° C, more preferably from 55° C to 150° C, and most preferably from 80° C to 120° C.
4. A method according to any of Claims 1 - 3 wherein step (d) is conducted at a temperature of from 5° C to 250° C, preferably from 40° C to 180° C, more preferably from 55° C to 150° C, and most preferably from 80° C to 120° C.
5. A method for ethoxylating a polyamino compound having the formula:
wherein w is from 0 to 20, preferably from 0 to 12, more preferably from 0 to 6, most preferably 0 or 1, x is from 0 to 300 and y is from 0 to 600; comprising the steps of: a) reacting said polyamino compound with ethylene oxide at a temperature of from 5° C to 250° C, preferably from 40° C to 180° C, more preferably, from 55° C to 150° C, most preferably from 80° C to 120° C, optionally in the presence of a solvent, until the average degree of ethoxylation is from 0.75 to 1.25, preferably from 0.85 to 1.1, more preferably from 0.95 to 1; b) adding from 2% to 40% ofthe total number of N-H equivalents, a base catalyst, said base catalyst optionally comprising a carrier; c) optionally removing the base catalyst carrier when a base catalyst carrier is present by means of a vacuum, heating, or combinations thereof; d) reacting additional ethylene oxide with the polyamino compound of step (b) or step (c) until said polyamino compound has an average degree of ethoxylation of from 2 to 50, preferably from 2 to 15, more preferably from 5 to 10, at a temperature of from 5° C to 250° C, preferably from 40° C to 180° C, more preferably from 55° C to 150° C, and most preferably from 80° C to 120° C; e) optionally neutralizing the base catalyst; and f) optionally removing the solvent.
6. A method according to any of Claims 1 - 5 wherein the base catalyst is selected from the group consisting of sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium t-butoxide, potassium t-butoxide, sodium metal, potassium metal, and mixtures thereof.
7. A method according to any of Claims 1 - 6 wherein the base catalyst carrier is selected from the group consisting of water, methanol, ethanol, isopropanol, t- butanol, and mixtures thereof.
8. A method according to any of Claims 1 - 7 wherein the solvent is methanol, ethanol, isopropanol, t-butanol, benzene, toluene, xylene, polyethylene glycol having a molecular weight greater than 100, polypropylene glycol having a molecular weight of from 100 to 2000, linear or branched Cg-C22 alcohols, alkoxylated linear or branched Cg-C22 alcohols, and mixtures thereof.
PCT/US1996/019094 1995-12-21 1996-11-27 A process for ethoxylating polyamines WO1997023546A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US57597895 true 1995-12-21 1995-12-21
US08/575,978 1995-12-21

Publications (1)

Publication Number Publication Date
WO1997023546A1 true true WO1997023546A1 (en) 1997-07-03

Family

ID=24302477

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1996/019094 WO1997023546A1 (en) 1995-12-21 1996-11-27 A process for ethoxylating polyamines

Country Status (1)

Country Link
WO (1) WO1997023546A1 (en)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999016811A1 (en) * 1997-09-29 1999-04-08 The Procter & Gamble Company Ethoxylated amino-functional polymers
EP1258502A2 (en) 2001-05-16 2002-11-20 Nippon Shokubai Co., Ltd. Method for production of alkoxylated compound
US6677289B1 (en) 1999-07-16 2004-01-13 The Procter & Gamble Company Laundry detergent compositions comprising polyamines and mid-chain branched surfactants
US6696402B2 (en) 1999-11-09 2004-02-24 The Procter & Gamble Company Laundry detergent compositions comprising zwitterionic polyamines
US6777527B1 (en) 1999-05-19 2004-08-17 Basf Aktiengesellschaft Polymers that contain alcoxylated, condensed alkaline amino acids and method of producing said polymers
WO2006086485A1 (en) * 2005-02-08 2006-08-17 Basf Aktiengesellschaft Method of making an alkoxylated polyethylenimine product
US7163985B2 (en) 2002-09-12 2007-01-16 The Procter & Gamble Co. Polymer systems and cleaning compositions comprising the same
WO2009065805A3 (en) * 2007-11-23 2009-07-09 Ulrich Annen Process for the alkoxylation of amino group containing polymers
DE102011116764A1 (en) 2011-10-22 2013-04-25 Gonzalo Urrutia Desmaison New cationic polymer comprising polycationic section and uncharged water-soluble section obtained by polycondensing amine or heteroaryl with epihalohydrin in water and reacting with polyol, useful e.g. as additives in galvanic copper baths
WO2013076024A1 (en) * 2011-11-25 2013-05-30 Basf Se Alkoxylated polyalkylene polyamines
WO2013076025A1 (en) * 2011-11-25 2013-05-30 Basf Se Lipophilic polyalkylene polyamines obtained by homogeneously catalyzed alcohol amination
US8759277B1 (en) 2013-03-08 2014-06-24 Ecolab Usa Inc. Foam stabilization and oily soil removal with associative thickeners
US8759276B2 (en) 2012-11-28 2014-06-24 Ecolab Usa Inc. Foam stabilization with polyethyleneimine ethoxylates
CN103987757A (en) * 2011-11-25 2014-08-13 巴斯夫欧洲公司 Synthesis of polyalkylene polyamines with low color index by homogeneously catalyzed alcohol amination in the presence of hydrogen
US9029313B2 (en) 2012-11-28 2015-05-12 Ecolab Usa Inc. Acidic viscoelastic surfactant based cleaning compositions comprising glutamic acid diacetate
US9157049B2 (en) 2012-11-28 2015-10-13 Ecolab Usa Inc. Viscoelastic surfactant based cleaning compositions
US9540595B2 (en) 2013-08-26 2017-01-10 The Procter & Gamble Company Compositions comprising alkoxylated polyalkyleneimines having low melting points

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3251778A (en) * 1960-08-04 1966-05-17 Petrolite Corp Process of preventing scale
EP0112593A2 (en) * 1982-12-23 1984-07-04 THE PROCTER & GAMBLE COMPANY Detergent compositions containing ethoxylated amines having clay soil removal/anti-redeposition properties
JPS62131020A (en) * 1985-12-03 1987-06-13 Nippon Oil & Fats Co Ltd Production of polyalkylenepolyamine polyether
EP0539819A2 (en) * 1991-10-29 1993-05-05 BASF Aktiengesellschaft Highly-reactive polyoxyalkylenepolyols with bound tertiary amino groups, method for their production and their use in the production of polyisocyanate-polyaddition products
WO1995032272A1 (en) * 1994-05-25 1995-11-30 The Procter & Gamble Company Compositions comprising ethoxylated/propoxylated polyalkyleneamine polymers as soil dispersing agents

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3251778A (en) * 1960-08-04 1966-05-17 Petrolite Corp Process of preventing scale
EP0112593A2 (en) * 1982-12-23 1984-07-04 THE PROCTER & GAMBLE COMPANY Detergent compositions containing ethoxylated amines having clay soil removal/anti-redeposition properties
JPS62131020A (en) * 1985-12-03 1987-06-13 Nippon Oil & Fats Co Ltd Production of polyalkylenepolyamine polyether
EP0539819A2 (en) * 1991-10-29 1993-05-05 BASF Aktiengesellschaft Highly-reactive polyoxyalkylenepolyols with bound tertiary amino groups, method for their production and their use in the production of polyisocyanate-polyaddition products
WO1995032272A1 (en) * 1994-05-25 1995-11-30 The Procter & Gamble Company Compositions comprising ethoxylated/propoxylated polyalkyleneamine polymers as soil dispersing agents

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 011, no. 361 (C - 459) 25 November 1987 (1987-11-25) *

Cited By (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999016811A1 (en) * 1997-09-29 1999-04-08 The Procter & Gamble Company Ethoxylated amino-functional polymers
US6777527B1 (en) 1999-05-19 2004-08-17 Basf Aktiengesellschaft Polymers that contain alcoxylated, condensed alkaline amino acids and method of producing said polymers
US6677289B1 (en) 1999-07-16 2004-01-13 The Procter & Gamble Company Laundry detergent compositions comprising polyamines and mid-chain branched surfactants
US6903059B2 (en) 1999-07-16 2005-06-07 The Procter & Gamble Company Laundry detergent compositions comprising polyamines and mid-chain branched surfactants
US6696402B2 (en) 1999-11-09 2004-02-24 The Procter & Gamble Company Laundry detergent compositions comprising zwitterionic polyamines
EP1258502A2 (en) 2001-05-16 2002-11-20 Nippon Shokubai Co., Ltd. Method for production of alkoxylated compound
US6762325B2 (en) 2001-05-16 2004-07-13 Nippon Shokubai Co., Ltd. Method for production of alkoxylated compound
EP2333002A1 (en) 2001-05-16 2011-06-15 Nippon Shokubai Co., Ltd. Method for production of alkoxylated compound
US7442213B2 (en) 2002-09-12 2008-10-28 The Procter & Gamble Company Methods of cleaning a situs with a cleaning composition comprising a polymer system
US7163985B2 (en) 2002-09-12 2007-01-16 The Procter & Gamble Co. Polymer systems and cleaning compositions comprising the same
WO2006086492A1 (en) * 2005-02-08 2006-08-17 Basf Aktiengesellschaft Method of making an alkoxylated polyethylenimine product
US7736525B2 (en) 2005-02-08 2010-06-15 Basf Corporation Method of making an alkoxylated polyethylenimine product
WO2006086485A1 (en) * 2005-02-08 2006-08-17 Basf Aktiengesellschaft Method of making an alkoxylated polyethylenimine product
WO2009065805A3 (en) * 2007-11-23 2009-07-09 Ulrich Annen Process for the alkoxylation of amino group containing polymers
US20100286342A1 (en) * 2007-11-23 2010-11-11 Basf Se Process for the alkoxylation of amino group containing polymers
JP2011504529A (en) * 2007-11-23 2011-02-10 ビーエーエスエフ ソシエタス・ヨーロピアBasf Se Alkoxylated method of amino group-containing polymer
US8507613B2 (en) 2007-11-23 2013-08-13 Basf Se Process for the alkoxylation of amino group containing polymers
DE102011116764A1 (en) 2011-10-22 2013-04-25 Gonzalo Urrutia Desmaison New cationic polymer comprising polycationic section and uncharged water-soluble section obtained by polycondensing amine or heteroaryl with epihalohydrin in water and reacting with polyol, useful e.g. as additives in galvanic copper baths
US9328201B2 (en) 2011-11-25 2016-05-03 Basf Se Alkoxylated polyalkylenepolyamines
WO2013076024A1 (en) * 2011-11-25 2013-05-30 Basf Se Alkoxylated polyalkylene polyamines
US9550725B2 (en) 2011-11-25 2017-01-24 Basf Se Lipophilic polyalkylenepolyamines by homogeneously catalyzed alcohol amination
CN103958567B (en) * 2011-11-25 2016-10-12 巴斯夫欧洲公司 Alkoxylated polyalkylene polyamines
CN103958568A (en) * 2011-11-25 2014-07-30 巴斯夫欧洲公司 Lipophilic polyalkylene polyamines obtained by homogeneously catalyzed alcohol amination
CN103987757A (en) * 2011-11-25 2014-08-13 巴斯夫欧洲公司 Synthesis of polyalkylene polyamines with low color index by homogeneously catalyzed alcohol amination in the presence of hydrogen
JP2014534247A (en) * 2011-11-25 2014-12-18 ビーエーエスエフ ソシエタス・ヨーロピアBasf Se Lipophilic polyalkylene polyamines by heterogeneously catalyzed amination of alcohols
WO2013076025A1 (en) * 2011-11-25 2013-05-30 Basf Se Lipophilic polyalkylene polyamines obtained by homogeneously catalyzed alcohol amination
US9127238B2 (en) 2012-11-28 2015-09-08 Ecolab Usa Inc. Foam stabilization with polyethyleneimine ethoxylates
US9157049B2 (en) 2012-11-28 2015-10-13 Ecolab Usa Inc. Viscoelastic surfactant based cleaning compositions
US9029313B2 (en) 2012-11-28 2015-05-12 Ecolab Usa Inc. Acidic viscoelastic surfactant based cleaning compositions comprising glutamic acid diacetate
US9410112B2 (en) 2012-11-28 2016-08-09 Ecolab Usa Inc. Acidic viscoelastic surfactant based cleaning compositions
US8759276B2 (en) 2012-11-28 2014-06-24 Ecolab Usa Inc. Foam stabilization with polyethyleneimine ethoxylates
US9765284B2 (en) 2012-11-28 2017-09-19 Ecolab Usa Inc. Viscoelastic amphoteric surfactant based cleaning compositions
US9765285B2 (en) 2012-11-28 2017-09-19 Ecolab Usa Inc. Acidic amphoteric viscoelastic surfactant based cleaning compositions
US9102902B2 (en) 2013-03-08 2015-08-11 Ecolab Usa Inc. Foam stabilization and oily soil removal with associative thickeners
US8759277B1 (en) 2013-03-08 2014-06-24 Ecolab Usa Inc. Foam stabilization and oily soil removal with associative thickeners
US9540595B2 (en) 2013-08-26 2017-01-10 The Procter & Gamble Company Compositions comprising alkoxylated polyalkyleneimines having low melting points
US9540596B2 (en) 2013-08-26 2017-01-10 The Procter & Gamble Company Compositions comprising alkoxylated polyamines having low melting points

Similar Documents

Publication Publication Date Title
US4085059A (en) Foam type coating remover
US4110266A (en) Process for converting the decomposition products of polyurethane and novel compositions thereby obtained
US4702857A (en) Block polyesters and like compounds useful as soil release agents in detergent compositions
US4207421A (en) Biodegradable, alkali stable, non-ionic surfactants
US5874623A (en) Process for the production of polyether aminoalcohols
US4548744A (en) Ethoxylated amine oxides having clay soil removal/anti-redeposition properties useful in detergent compositions
US4276205A (en) Detergent compositions containing amine oxide and nonionic surfactants and polyethylene glycol
US6717019B2 (en) Glycidyl ether-capped acetylenic diol ethoxylate surfactants
US4303544A (en) Adducts of alcohols and olefin oxides as biodegradable and low-foaming tensides useful in detergents
US6380410B1 (en) Fatty acid derivatives and their use as surfactants in detergents and cleaners
EP0112592A2 (en) Zwitterionic polymers having clay soil removal/anti-redeposition properties useful in detergent compositions
WO1994000508A1 (en) Surfactants derived from polyoxyalkylenes and substituted succinic anhydrides
US5646318A (en) Process for the preparation of hydroxyalkylamides
EP0241984A2 (en) Block polyesters having branched hydrophilic capping groups useful as soil release agents in detergent compositions
GB2305670A (en) Hot melt ink jet vehicles
US4664848A (en) Detergent compositions containing cationic compounds having clay soil removal/anti-redeposition properties
US20040039235A1 (en) Ortho ester-based surfactant, its preparation and use
US5371179A (en) Polysuccinimide polymers and process for preparing polysuccinimide polymers
US4659802A (en) Cationic compounds having clay soil removal/anti-redeposition properties useful in detergent compositions
US4597898A (en) Detergent compositions containing ethoxylated amines having clay soil removal/anti-redeposition properties
US4608197A (en) Alkoxylated ether sulfate anionic surfactants from branched chain plasticizer alcohols
EP0111984A2 (en) Ethoxylated amine polymers having clay soil removal/anti-redeposition properties useful in detergent compositions
US4238373A (en) Process for making detergent compositions containing nitrogenous cationic surfactants
US3539519A (en) Low foaming nonionic detergents
US7429558B2 (en) Azetidinium modified polymers and fabric treatment composition

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): BR CA CN JP MX

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase in:

Ref country code: JP

Ref document number: 97523653

Format of ref document f/p: F

122 Ep: pct application non-entry in european phase