Drug – bio-affecting and body treating compositions – Preparations characterized by special physical form – Cosmetic – antiperspirant – dentifrice
Reexamination Certificate
1999-05-14
2001-09-11
Jones, Dameron L. (Department: 1619)
Drug, bio-affecting and body treating compositions
Preparations characterized by special physical form
Cosmetic, antiperspirant, dentifrice
Reexamination Certificate
active
06287578
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Technical Field
The present invention describes condensation products of polyether-modified and optionally hydrophobically modified monoesters and/or -amides of &agr;,&bgr;-unsaturated dicarboxylic acids and ammonia, their preparation and use.
2. Prior Art
Polyamino acid derivatives, in particular polyaspartic acid, have recently attracted particular attention because of their properties, in particular their biodegradability and their similarity to naturally occurring structures. Proposed applications are inter alia as biodegradable complexing agents, water softeners and detergent builders. Polyaspartic acid is generally obtained by alkaline hydrolysis of the direct synthesis precursor polysuccinimide (PSI, anhydropolyaspartic acid), the cyclic imide of polyaspartic acid. PSI can be prepared, for example, in accordance with EP 0 578 449 A, WO 92/14753, EP 0 659 875 A or DE 44 20 642 A from aspartic acid, or is obtainable, for example according to DE 36 26 672 A, EP 0 612 784 A, DE 43 00 020 A or U.S. Pat. No. 5, 219, 952 A, from maleic acid derivatives and ammonia. Proposed applications for these customary polyaspartic acids are inter alia as encrustation inhibitors, builders in detergents, fertilizer additive and auxiliary in tanning.
DE 4327494, EP 0578449 and EP 0578450 describe the preparation of polysuccinimide from aspartic acid or maleic acid derivatives in polyethylene glycols as solvents. Here, there is no incorporation of the polyether into the product.
The reaction of polysuccinimide with amines, which has been described by various working groups, leads to polyaspartic amides (Kovacs et al., J. Med. Chem. 1967, 10, 904-7; Neuse, Angew. Makromol. Chem. 1991, 192, 35-50). The ring opening of polysuccinimide using polyamines and the subsequent alkaline hydrolysis for the preparation of polyaspartic acid derivatives for applications as superabsorbers is described, for example, in WO 95/35337. DE 19525365 describes the modification of polysuccinimide with amines and amino-functional polyethers for the preparation of paper auxiliaries.
Kataoka et al. describe, in Macromol. Chem. Phys. 1995, 196, 1899-1905, poly-L-aspartic benzyl ester with terminally linked polyether block for pharmaceutical uses. The preparation of these enantiomerically pure products, however, proceeds via the N-carboxy anhydrides of L-aspartic acid and is very complex and uneconomical.
For applications inter alia as emulsifier, dispersant and surfactant, copolymeric polyaspartic esters partially esterified with long-chain fatty alcohols or their derivatives are of particular interest. Such compounds are readily obtainable on the basis of maleic monoesters and ammonia, as explained in DE 195 45 678 A or EP 96 118 806.7 A.
A disadvantage in the property profile of such polyaspartic acid derivatives having carboxylate side chains as hydrophilic component is, however, the pH dependency of the behavior. Changes in the pH cause undesired changes in the hydrophilicity, e.g. as a result of protonation of carboxylate groups, which is noticeably a disadvantage in their application properties, e.g. as regards the pH, thermal and long-term stability of the preparations, for example in the field of cosmetic W/O and O/W emulsions.
The object of the present invention is therefore to provide copolymeric polyaspartic acid derivatives having improved application properties which also contain nonionic hydrophilic groups.
SUMMARY OF THE INVENTION
The object is achieved according to the present invention by condensation products of polyether-modified and optionally of hydrophobically modified monoesters and/or -amides of &agr;,&bgr;-unsaturated dicarboxylic acids and ammonia.
DETAILED DESCRIPTION OF THE INVENTION
The novel condensation products can be obtained by a preparation process which involves reacting a mixture of monoesters and/or monoamines of monoethylenically unsaturated dicarboxylic acids with ammonia, or thermally converting the ammonium salts of these acids into the polymer. Use can be made, for example, of ester and amide derivatives of maleic acid, fumaric acid, itaconic acid, alkenylsuccinic acid, alkylmaleic acid, citraconic acid or their ammonium salts, preferably derivatives of maleic acid, fumaric acid or itaconic acid, particularly preferably maleic acid derivatives of the general formulae (I) and (II)
where
R
1
can be as defined for R
4
, R
5
and R
6
,
R
2
is indentical or different, straight-chain or branched, saturated or unsaturated alkyl, alkenyl or aryl radicals having from 1 to 30 carbon atoms, is hydroxy- or aminoalkyl having from 2 to 30 carbon atoms, each optionally oxa- or aza-substituted, having from 1 to 6 hydroxyl groups and/or from 1 to 6 amino groups, is their acylation products with C
1
to C
22
carboxylic acid radicals, or is polyoxyalkylene radicals of the type R
12
X(C
n
H
2n−m
R
13
m
O)
o
R
14
, where X is oxygen or NH, R
12
is identical or different divalent alkyl, alkenyl or aryl radicals having from 2 to 30 carbon atoms, R
13
is hydrogen and/or identical or different alkyl, alkenyl or aryl radicals having from 1 to 30 carbon atoms, R
14
is hydrogen, identical or different alkyl, alkenyl, aryl or acyl radicals having from 1 to 30 carbon atoms, n is 2 or 4, m assumes values from 0 to 4 and o assumes values from 1 to 100, or assumes the meaning of R
5
, and
R
3
is hydrogen or a radical R
2
,
R
4
is identical or different, straight-chain or branched, saturated or unsaturated hydroxy-functional alkyl or alkenyl radicals having from 1 to 30 carbon atoms and from 1 to 20 hydroxyl groups or their acylation products with 1 to 22 carboxylic acid radicals, or is polyoxyalkylene radicals of the type R
12
X(C
n
H
2n−m
R
13
m
O)
o
R
14
, where X is oxygen or the radical —NH—, R
12
is identical or different divalent alkyl, alkenyl or aryl radicals having from 2 to 30 carbon atoms, R
13
is hydrogen and/or identical or different alkyl, alkenyl or aryl radicals having from 1 to 30 carbon atoms, R
14
is hydrogen, identical or different alkyl, alkenyl or aryl radicals having from 1 to 30 carbon atoms, n is 2 or 4, m assumes values from 0 to 4 and o assumes values from 1 to 100,
R
5
is identical or different, straight-chain or branched, saturated or unsaturated alkyl or alkenyl radicals R
7
having from 6 to 30 carbon atoms or is radicals of the structure —Y—R
7
, where Y assumes the meaning of polyoxyalkylene radicals of the type (C
n
H
2n−m
R
13
m
O)
o
, where R
13
is hydrogen and/or identical or different alkyl, alkenyl or aryl radicals having from 1 to 30 carbon atoms, n is 2 or 4, m assumes values from 0 to 4, and o assumes values from 1 to 100, and
R
6
is identical or different, straight-chain or branched, saturated or unsaturated alkyl or alkenyl radicals having from 1 to 5 carbon atoms,
Z is one or more radicals from the group of alkali metals, alkaline earth metals, hydrogen or ammonium, [NR
8
R
9
R
10
R
11
]
+
, where R
8
to R
11
are in each case independently of one another hydrogen, identical or different, straight-chain or branched, saturated or unsaturated alkyl radicals, alkenyl radicals or hydroxy-functional alkyl radicals having from 1 to 22 carbon atoms and optionally from 1 to 6 hydroxyl groups, and at least one radical R
2
, R
3
or R
4
contains a polyoxyalkylene chain having from 2 to 100 units, which in the case of R
4
is not like said radicals Y bonded to a radical R
7
.
As usual, all of the data given relating to the composition of the polymeric products refer to the average composition of the polymer chains.
Use is made of mixtures having a total content of from 1 to 100% by weight, preferably from 40 to 100% by weight, of ester components (I) and having a content of from 0 to 99% by weight, preferably from 0 to 60% by weight, of amide components (II). The proportion by weight of the polyoxyalkylene chains in the reaction mixture is from 1 to 95% by weight, preferably from 20 to 80% by weight. The reaction requires the use of from 0.5 to 5 equivalents of ammonia, preferably from 0.8 to 2 eq
Duetsch Michael
Gruning Burghard
Simpelkamp Jorg
Weitemeyer Christian
Jones Dameron L.
Scully Scott Murphy & Presser
Th. Goldschmidt Ag
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