Cleaning compositions for solid surfaces – auxiliary compositions – Cleaning compositions or processes of preparing – Specific organic component
Reexamination Certificate
2000-04-14
2001-10-09
Hardee, John (Department: 1751)
Cleaning compositions for solid surfaces, auxiliary compositions
Cleaning compositions or processes of preparing
Specific organic component
Reexamination Certificate
active
06300304
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to alkoxylated polyalkyleneimine hydrophobic soil dispersants which are suitable for use as soil dispersant in applications.
BACKGROUND OF THE INVENTION
Absent a suitable dispersant, hydrophobic (e.g. grime, oil, soot) and hydrophilic (e.g. clam) soil which is removed during the washing step of the laundry process can re-deposit onto the cleaned fabric. Soil dispersants act by sequestering dirt once it is dissolved or dispersed in the laundry liquor and keeps the suspended soil in the laundry liquor where it can be carried away during the normal rinsing process.
Typically, if bleaching agents are present, especially peroxygen bleaches which are formulated into both liquid and granular laundry detergent compositions, the formulator must consider the instability of a particular soil dispersant toward bleach. Many successful dispersants have polyalkyleneamine or polyalkyleneimine backbones which are susceptible to oxidation at the amine functionalities and potentially to breakdown or fragmentation by bleaching agents which may be present. From another view, the interaction of bleaching agents with these polyalkyleneimine-based dispersants depletes the amount of bleach present therefore affecting the bleaching performance.
Accordingly, there remains a need in the art for bleach compatible, highly effective hydrophobic soil dispersants. Surprisingly, it has been found that certain higher molecular weight polyalkyleneimines which comprise a mixture of alkyleneoxy units which are appended to a polyalkyleneimine backbone in a particular order provide hydrophobic dispersants having enhanced bleach compatibility as well as enhanced dispersancy.
SUMMARY OF THE INVENTION
The present invention meets the aforementioned needs in that is has been surprisingly discovered that polyalkyleneimines having a backbone molecular weight of from about 600 daltons to about 25000 daltons wherein the backbone nitrogens have been substituted by an average degree of mixed alkyleneoxylation per N—H unit of from 12 to about 50 alkyleneoxy units provides an enhanced hydrophilic soil dispersant which is combustible with bleach. The polyamine backbone is first modified by placement of from 1 to 10 propyleneoxy units, butyleneoxy units, and mixtures thereof followed by ethyleneoxy units such that the total degree of alkyleneoxylation does not exceed about 50 units. The alkoxylated polyalkyleneimines of the present invention are suitable for use in high and low density granular, heavy duty and light duty liquids, as well as laundry bar detergent compositions.
The present invention relates to a soil dispersant having the formula:
wherein R is C
2
-C6 linear alkylene, C
3
-C
6
branched alkylene, and mixtures thereof; B is a continuation by branching; E is an alkyleneoxy unit having the formula:
—(R
1
O)
m
(R
2
O)
n
R
3
wherein R
1
is 1,2-propylene, 1,2-butylene, and mixtures thereof; R
2
is ethylene; R
3
is hydrogen, C
1
-C
4
alkyl, and mixtures therof; 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 —(R
1
O) unit is attached to the backbone prior to attachment of an —(R
2
O) unit and further provided m+n is at least 12.
These and other objects, features, and advantages will become apparent to those of ordinary skill in the art from a reading of the following detailed description and the appended claims.
All percentages, ratios and proportions herein are by weight, unless otherwise specified. All temperatures are in degrees Celsius (° C.) unless otherwise specified. All documents cited are in relevant part, incoporated herein by reference.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to polyalkyleneimine dispersants which are polyalkyleneoxy substituted wherein propyleneoxy units, butyleneoxy units, and mixtures thereof are attached to the backbone nitrogens prior to subsequent attachment of polyethyleneoxy units. The polyamine backbones of the present invention have the general formula:
said backbones prior to subsequent modification, comprise primary, secondary and tertiary amine nitrogens connected by R “linking” units. The backbones are comprised of essentially three types of units, which may be randomly distributed along the chain.
The units which make up the polyalkyleneimine backbones are primary units having the formula:
[H
2
N—R]— and —NH
2
which terminate the main backbone and any branching chains, secondary amine units having the formula:
and which, after modification, have their hydrogen atom substituted by from 1 to 10 propyleneoxy units, butyleneoxy units, and mixtures thereof followed by from 10 to 40 ethyleneoxy units, and tertiary amine units having the formula:
which are the branching points of the main and secondary backbone chains, B representing a continuation of the chain structure by branching. The tertiary units have no replaceable hydrogen atom and are therefore not modified by substitution with an alkyleneoxy unit. During the formation of the polyamine backbones cyclization may occur, therefore, an amount of cyclic polyamine can be present in the parent polyalkyleneimine backbone mixture. Each primary and secondary amine unit of the cyclic alkyleneimines undergoes modification by the addition of alkyleneoxy units in the same manner as linear and branched polyalkyleneimines. R is C
2
-C
6
linear alkylene, C
3
-C
6
branched alkylene and mixtures therof, preferred branched alkylene is 1,2-propylene, preferred R is ethylene. The preferred polyalkyleneimines of the present invention have backbones which comprise the same R unit, for example, all units are ethylene. Most preferred backbone comprises R groups which are all ethylene units.
The polyalkyleneimines of the present invention are modified by substitution of each N—H unit hydrogen with an alkyleneoxy unit having the formula:
—(R
1
O)
m
(R
2
O)
n
R
3
Wherein R
1
is 1,2-propylene, 1,2-butylene, and mixtures thereof, preferably 1,2-propylene. R
2
is ethylene. R
3
is hydrogen, C
1
-C
4
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 backbone nitrogen units prior to substitution with any other alkyleneoxy unit. The value of the index m is from about 1, preferably from about 2 to about 10, preferably to about 6, more preferably to about 5. The value of the index n is from about 10, preferably from about 15, more preferably from about 20 to about 40, preferably to about 35, more preferably to about 30. The value of m+n is preferably at least 12, more preferably from about 15, most preferably from about 20 to about 40, more preferably to about 35. An example of a preferred polyalkyleneoxy substituent comprises three 1,2-propyleneoxy units prior to subsequent ethoxylation, especially when the average value of m+n is about 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, most preferably from about 2000 daltons to about 25000 daltons, preferably to about 20000 daltons, more preferably to about 15000 daltons, most preferably 5000 daltons. An example of a preferred molecular weight for a polyethyleneimine backbone is 3000 daltons. The indices x and y needed to achieve the preferred molecular weights will vary depending upon the R moiety which comprises the backbone. For example, when R is ethylene a backbone unit averages about 43 gm and when R is hexylene a backbone unit averages about 99 gm,
The polyamines of the present invention can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid etc. Specific methods for preparing these polyamine backbones are disclosed in U.S. Pat. No. 2,182,306, Ulrich et al., issued Dec. 5, 1939; U.S. Pat. No.
Boeckh Dieter
Cleary James A.
Ehle Michael
Funhoff Angelika
Gosselink Eugene Paul
BASF - Aktiengesellschaft
Hardee John
Oblon & Spivak, McClelland, Maier & Neustadt P.C.
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