Zwitterionic polyamines and process for their production

Details Zwitterionic polyamines and process for their production Zwitterionic polyamines and process for their production

2002-01-16

2004-01-06

Hampton-Hightower, P. (Department: 1711)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

From ketone or ketene reactant

C528S076000, C528S082000, C528S391000, C528S422000, C528S423000, C525S540000, C564S281000, C564S290000, C564S295000, C558S047000, C558S158000, C510S321000, C510S337000, C510S393000, C510S475000, C510S499000

Reexamination Certificate

active

06673890

ABSTRACT:

This application is a 371 of PCT EP00/06296 filed Jul. 5, 2000.
The present invention relates to zwitterionic polyamines and a process for their production by alkoxylation of polyamines and introduction of anionic groups.
BACKGROUND OF THE INVENTION
EP-A-0,111,976 relates to watersoluble zwitterionic compounds having clay soil removal/anti-redeposition properties. An example of such a compound is a with chlorosulfonic acid sulfated quaternized addition product of ethoxylated tetraethylenepentamine with a total degree of ethoxylation of 21.
EP-A-0,112,592 relates to zwitterionic polymers which are for example obtained by alkoxylation of polyalkyleneamines such as triethylenetetramine or tetraethylenepentamine or of polyethyleneimines, sulfonation of the alkoxylated products and subsequent quaternization. The zwitterionic products disclosed in the above patents have clay-soil removal and anti-redeposition properties when used in detergent compositions, however their effectiveness in dispersing and removing clay embedded in the fabric into the laundry liquor is not sufficient. Furthermore the specifically disclosed compounds of this literature reference are thermally instable.
GB-A-2,220,215 relates to sulfated alkoxylated mono- or polyamines derived from polymethlenediamines with 2-6 methylene groups between the nitrogen atoms or polyalkylenepolyamines in which the alkylene contains 2-4 carbon atoms and containing 3-6 amino groups. They may bear a long chain-alkyl substituent at one of the nitrogen atoms and are quaternized. However it was found that these polymers are not favorable for clay soil removal within laundry operations where anionic surfactants are present.
U.S. Pat. No. 4,739,094 discloses alkoxylated aminopolyethers containing units of ethylene oxide and propylene oxide and having a molecular weight of from 10,000 to 150,000. The alkoxylated aminopolyethers are water-soluble and are used in 5 to 60% strength by weight aqueous solution in the preparation of coal/water slurries. If appropriate, the alkoxylated aminopolyethers can also be reacted with carboxylic acid anhydrides, amidosulfonic acids and urea, acid chlorides of sulfur or of phosphorus or chloroacetic acid esters. The reaction products can be converted into ionic compounds by subsequent neutralization or hydrolysis.
It is therefore an object of the invention to provide new polymers with improved thermal stability.
SUMMARY OF THE INVENTION
The above object is achieved with a zwitterionic polyamine comprising a linear or branched hydrophobic polyamine backbone having 2 to 10 tertiary amino nitrogen atoms and a spacer between two tertiary amino nitrogen atoms wherein the spacer is selected from the group consisting of C
3
-C
15
-alkylene, C
5
-C
15
-cycloalkylene
wherein in formula I, II and III
B is C
2
-C
16
-alkylene, C
5
-C
15
-cycloalkylene
D is C
4
-C
16
-alkylene, C
5
-C
15
-cycloalkylene
O is 1 or 2,
p is 3 to 8
wherein in formula IV
R=C
1
- to C
22
-alkyl or C
7
-C
22
-aralkyl and n=3 to 6,
at least one tertiary amine end group of the polyamine backbone contains two groups having the formula
wherein
A means an ethylene oxide unit, a propylene oxide unit, a unit of butylene oxides and a tetrahydrofuran unit,
n is a number of from 1 to 50,
X is —SO
3
M, —CH
2
—CH
2
—SO
3
M, —CH
2
—CH
2
—CH
2
—SO
3
M,
 with the proviso that in formula VI one X may also be hydrogen and
M is hydrogen, alkali metal or ammonium,
or contains one group of formula V or VI and one group selected from radicals consisting of
C
1
- to C
22
-alkyl and C
7
-C
22
-aralkyl, the meaning of A and n is the same as in formula V or VI,
said zwitterionic polyamine having a molecular weight up to 9,000 optionally containing up to 100% of the nitrogen atoms quaternized.
The object is also achieved with a process for the production of a zwitterionic polyamine which comprises a first step wherein
(i) a linear or branched hydrophobic polyamine having 2to 10 tertiary amino nitrogen atoms and a spacer between two tertiary amino nitrogen atoms wherein the spacer is selected from the group consisting of
C
8
- to C
16
-alkylene, C
5
- to C
15
-cycloalkylene
wherein in formula I, II and III
B is C
2
-C
16
-alkylene, C
5
-C
15
-cycloalkylene
D is C
4
-C
16
-alkylene, C
5
-C
15
-cycloalkylene
o is 1 or 2,
p is 3 to 8
wherein in formula IV
R=C
1
- to C
22
-alkyl or C
7
-C
22
-aralkyl and n=2 to 6,
is reacted with
(ii) at least one C
2
- to C
4
-alkylene oxide or tetrahydro furane at such a ratio that on each NH group of the polyamine 1 to 50 units of the alkylene oxide or of tetrahydrofurane are added,
a second step wherein the alkoxylated polyamine obtained in the first step is reacted with a compound selected from the group consisting of a halogen sulfonic acid, halogen phosphorous acid, vinyl sulfonic acid, propane sultone, halogen acetic acid, acrylic acid, methacrylic acid, vinyl phosphorous acid and the alkali metal or ammonium salts of the said acids, in such a manner that at least one tertiary amine end group of the alkoxylated polyamine contains two groups having the formula
wherein
A means an ethylene oxide unit, a propylene oxide unit, a unit of butylene oxides and a tetrahydrofuran unit,
n is a number of from 1 to 50,
X is —SO
3
M, —CH
2
—CH
2
—SO
3
M, —CH
2
—CH
2
—CH
2
—SO
3
M,
 with the proviso that in formula VI one X may also be hydrogen and
M is hydrogen, alkali metal or ammonium,
or contains one group of formula V or VI and one group selected from radicals consisting of
the meaning of A and n is the same as in formula V or VI,
and optionally
a third step wherein up to 100% of the tertiary nitrogen atoms of the reaction product obtained in the second step are quaternized, said degree of quaternization, may also be obtained by first quaternizing the reaction product obtained in the first step and subsequently carrying out the second step.
Preferred zwitterionic polyamines contain two groups of formula V or VI attached to the tertiary nitrogen atoms of the end groups of the polyamines. Especially preferred zwitterionic polyamines contain the nitrogen atoms of the end groups of the polyamine backbone quaternized and, as substituents, two groups of formula V or VI and one C
1
- to C
22
-alkyl group or a hydroxyalkyl group. In most cases the nitrogen end groups of the polyamine backbone are quaternized and contain as substituents two groups of formula V and a C
1
- to C
22
-alkyl group. Other preferred zwitterionic polyamines contain quaternized amino nitrogen end groups bearing, as substituents, two groups of formula V and a hydroxyethyl or hydroxypropyl group.
The substituent A in formulae V and VI may have the following structures:
Other zwitterionic polyamines are charaterized in that the spacer between two nitrogen atoms of the polyamine backbone is a cyclic C
5
- to C
15
-alkylene group.
Of particular interest are zwitterionic polyamines wherein the polyamine backbone between the nitrogen atoms is derived from an amine selected from the group consisting of bis(hexamethylene)triamine, N,N′-bis(3-aminopropyl)piperazine, N,N′-bis(2-aminoethyl)piperazine and bis(3-aminopropyl)hexamethylenediamine and wherein at least one tertiary amine end group of the polyamine backbone contains two groups having formula V or VI.
The zwitterionic polyamine is derived from a linear or branched hydrophobic polyamine. The backbone of the polyamine contains 2 to 10 tertiary amino nitrogen atoms and has one spacer between two tertiary amino nitrogen atoms. Polyamines containing a C
8
- to C
16
-alkylene group as spacer are for example 1,8-diaminooctane, 1,10-diaminodecane and 1,12-diaminododecane. Examples of suitable polyamines containing the above spacers of formula I-IV are dipropylenetriamine, tripropylenetetramine, bis(hexamethylene)triamine, bis(octamethylene)triamine, aminoethylpropylenediamine, aminoethylbutylenediamine, aminoethylhexamethylenediamine, N,N′-bis(aminoethyl)propylenediamine, N,N′-bis(aminoethyl)butylenediamine, N,N′-bis(aminoethyl)hexamethylenediamine, N,N&prim

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