Zwitterionic polyetherpolyamines and process for their...

Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acids and salts thereof

Reexamination Certificate

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C528S391000, C528S392000, C558S047000, C558S158000

Reexamination Certificate

active

06703523

ABSTRACT:

DESCRIPTION
The present invention relates to zwitterionic polyetherpolyamines and a process for their production by alkoxylation of polyetherpolyamines and introduction of anionic groups.
BACKGROUND OF THE INVENTION
EP-A-0111976 and EP-A-0112592 relate 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. These zwitterionic products 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 it was found, that preferred embodiments of the above mentioned patents show thermal instability.
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.
In the course of optimizing modern laundry detergents there is a need to improve properties of clay soil removal agents for better effectiveness in the wash liquour, improved synergy with the surfactant system and for better thermal stability during processing and storing.
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 polyetherpolyamine comprising a linear or branched polyetherpolyamine backbone having 2 to 10 tertiary amino nitrogen atoms and a molecular weight of from 100 to 800, at least one tertiary amine end group of the polyetherpolyamine backbone contains at least 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,
with the proviso that in formula II one X may also be hydrogen and
M is hydrogen, alkali metal or ammonium,
or contains one group of formula I or II and one group selected from radicals consisting of
C
1
- to C
22
-alkyl and C
7
- to c
22
-aralkyl, the meaning of A and n is the same as in formula I or II,
said zwitterionic polyetherpolyamine having a molecular weight up to 9,000 and optionally containing up to 100% of the nitrogen atoms quaternized.
The object is also achieved with a process for the production of a zwitterionic polyetherpolyamine
which comprises a first step wherein
(i) a linear or branched polyetherpolyamine having a molecular weight of from 100 to 800, 2 to 10 nitrogen atoms and containing at least 2 primary or secondary amino nitrogen end groups or the reaction product of said polyetherpolyamine with up to 1 glycidol per NH group of the polyetherpolyamine is reacted with
(ii) at least one C
2
- to C
4
-alkylene oxide or tetrahydrofuran at such a ratio that on each NH group of the polyetherpolyamine 1 to 50 units of the alkylene oxide are added,
a second step wherein the alkoxylated polyetherpolyamine 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 polyetherpolyamine 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,
with the proviso that in formula II one X may also be hydrogen and
M is hydrogen, alkali metal or ammonium,
or contains one group of formula I or II and one group selected from radicals consisting of
C
1
- to C
22
-alkyl and C
7
- to C
22
-aralkyl, the meaning of A and n is the same as in formula I or II, 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 polyetherpolyamines contain two groups of formula I or II attached to the tertiary nitrogen atoms of the end groups of the polyetherpolyamine backbone. Especially preferred zwitterionic polyetherpolyamines contain the nitrogen atoms of the end groups of the polyetherpolyamine backbone quaternized and, as substituents, two groups of formula I or II and one C1 to C22 alkyl group.
The substituent A in formulae I and II may have the following structures:
Of particular interest are such zwitterionic polyetherpolyamines, wherein the nitrogen atoms of the end groups of the polyetherpolyamine backbone are quaternized and contain, as substituents, two groups of formula I and a C1 to C22 alkyl group. Other zwitterionic polyetherpolyamines which are of particular interest are those wherein the nitrogen atoms of the end groups of the polyetherpolyamine backbone are quaternized and contain, as substituents, two groups of formula I and a hydroxyethyl or a hydroxypropyl group.
The polyetherpolyamine backbone of the zwitterionic polyetherpolyamines can be linear or branched and contains 2 to 10, preferably 2 to 6 and most preferably 2 to 4 tertiary nitrogen atoms and has a molecular weight without pending group of from 100 to 800, preferably 120 to 500. The polyetherpolyamine backbone can be described by the following formulae. The polyetherpolyamine backbone without the nitrogen end groups comprises, for instance, units having the formula
—(B—O)
m
—(D—O)
o
—(B—O)
p
—B—  (III)
wherein
B is a linear or branched C
2
- to C
4
-alkylene
D is a linear, branched or cyclic C
5
- to C
16
-alkylene, C
4
- to C
16
-oxaalkylene or C
5
- to C
16
-azaalkylen,
m is 0-7,
o is 0 or 1,
p is 0-6, with the proviso that m+o+p≧1 up to 9.
The polyetherpolyamine backbone of formula III is derived from diamines having the formula
H
2
N—(B—O)
n
—(D—O)
o
—(B—O)
p
—B—NH
2
  (IIIa),
wherein the symbols have the same meaning as in formula III.
Examples of compounds of the above formula IIIa are hydrogenated cyanomethylated C3- to C12-diols. These compounds are obtained by reacting first a diol with formaldehyde and hydrogencyanide and subsequently hydrogenating the addition product in the presence of ammonia. This method of producing amines is hereinafter referred to as aminoethylation. Compounds so produced are especially 1,9-diamino-3,7-dioxa-nonane, 1,10-diamino-3,8-dioxadecane, 1,12-diamino-3,10-dodecane and 1,14-diamino-3,12-tetradecane.
Other compounds of formula IIIa are &agr;,&ohgr;-diamino polyalkyleneglycols which are obtained by hydrogenation of cyanomethylated polyalkylene glycols (aminoethylation). Suitable polyalkylene glycols contain preferably 2 to 10 repeating units and are derived from polyethylene glycol, polypropylene glycol, polybutylene glycol and polytetrahydrofurane. The polyalkylene glycols may contain the repeating units in statistical distribution or as blocks. Examples of such compounds are 1,5-diamino-3-oxapentane, 1,8-diamino-3,6-dioxa-octane, 1,11-diamino-3,6,9-trioxa-undecane, 1,5-diamino-1,4-dimethyl-3-oxa-heptane, 1,8-diamino-1,4,7-trimethyl-3,6-dioxadecane, 1,9-diamino-5-oxa-nonane and 1,14-diamino-5,10-dioxa-tridecane.
Further compounds of formula IIIa are hydrogenated cyanoethylated C
2
- to C
12
-diols which are obtained by reacting a diol with acrylonitrile in a molar ratio of

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