Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From carboxylic acid or derivative thereof
Reexamination Certificate
1999-05-14
2001-11-06
Truong, Duc (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From carboxylic acid or derivative thereof
C528S328000, C528S363000, C525S419000, C525S420000
Reexamination Certificate
active
06313260
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention describes the preparation of high molecular weight copolymeric polyaspartic esters which have been hydrophobically modified with alkyl or alkenyl radicals having from 6 to 30 carbon atoms.
2. Prior Art
Polyamino acid derivatives, in particular polyaspartic acid, have recently attracted particular attention because of their biodegradability and their similarity to naturally occuring 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 an encrustation inhibitor, builders in detergents, fertilizer additive and auxiliary in tanning.
The reaction of polysuccinimide with amines, which has been described by various working groups, leads to polraspartic 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, in WO 96/08523 or in Annu. Tech. Conf. Soc. Plast. Eng. 1995, 53, 1510-13. Neri et al describe, in J. Med. Chem 1973, 16, 893-897 the reaction of polysuccinimide with ethanolamine to give hydroxyethyl polyaspartates for pharmaceutical uses.
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 or EP 96 118 806.7, and generally more usually have low molecular weights.
The object of the invention is to provide copolymeric polyaspartic esters with increased molecular masses.
SUMMARY OF THE INVENTION
The object is achieved according to the invention by copolymeric polyaspartic esters having increased molecular mass, which are prepared from maleic acid derivatives and ammonia with the addition of di- or polyfunctional alcohols or amines.
DETAILED DESCRIPTION OF THE INVENTION
The copolymers used, which are derived from polyaspartic acid, consist, in an amount up to at least 75 mol % of the units present, of structural units of the general formulae (I), (II) and (III)
in which the structural elements A are identical or different trifunctional hydrocarbon radicals having 2 carbon atoms of the type (A1) or (A2), where one copolymer consists of at least three units of the formula (I), where
R
1
is as defined for R
2
, R
3
or R
4
, where
R
2
are one or more radicals from the group of alkali metals, alkaline earth metals, hydrogen or ammonium, [NR
5
R
6
R
7
R
8
]
+
, where R
5
to R
8
independently of one another are hydrogen, alkyl or alkenyl having from 1 to 22 carbon atoms or hydroxyalkyl having from 1 to 22 carbon atoms and from 1 to 6 hydroxyl groups and/or their acylation products containing C
1
- to C
22
-carboxylic acid radicals,
R
3
are identical or different, straight-chain or branched, saturated or unsaturated alkyl or alkenyl radicals R
9
having from 6 to 30 carbon atoms or radicals of the structure -Y-R
9
, where Y is an oligo- or polyoxyalkylene chain having from 1 to 100 oxyalkylene units,
R
4
are identical or different, straight-chain or branched, saturated or unsaturated alkyl or alkenyl radicals having from 1 to 5 carbon atoms, the units of the formula (II) are proteinogenic or nonproteinogenic amino acids and are present in an amount of not more than 20% by weight, based on the copolymeric polyaspartic acid derivatives and
X in the formula (III) is one or more di- or polyfunctional radicals derived from molecular-mass-increasing agents, in particular a di- or polyhydroxy compound, a di- or polyamino compound, or aminoalcohols, having a linear, branched or cyclic, saturated, unsaturated or aromatic hydrocarbon structure, optionally oxo- or aza-substituted with O or N atoms in the chain,
and at least in each case one radical R
1
must assume the meaning of R
2
and at least one radical R
1
that of R
3
and at least one radical R
1
that of X.
All of the data given relating to the composition of the polymeric products refer, as usual, to the average composition of the polymer chain.
The remaining units, which do not have the structure (I) or (II) or (III) (no more than 25 mol % of all units), can inter alia be iminodisuccinate units of the general formula (IV)
and various end groups, on the N-terminus, for example aspartic acid, maleic acid, fumaric acid and malic acid units and their esters or amides, maleimide units or diketopiperazines derived from aspartic acid and/or the amino acid units (II), and esters or amides of the units (II), on the C-terminus, for example aspartic acid or malic acid units, their mono- or diesters, amides or cyclic imides.
Suitable amino acid units (II) from the group of proteinogenic amino acids are, for example, glutamine, asparagine, lysine, alanine, glycine, tyrosine, tryptophan, serine and cysteine and their derivatives; nonproteinogenic amino acids can, for example, be &bgr;-alanine, &ohgr;-amino-1-alkanoic acids, for example 6-aminocaproic acid, etc.
Surprisingly, these derivatives exhibit clear advantages, in terms of their application properties, over the analogous compounds having a relatively low molecular weight, in particular as regards the thermal and long-term stability of the preparations in the field of cosmetic W/O and O/W emulsions and for pigment dispersions for coatings and colorants.
According to the invention, preference is given to compounds in which at least one free carboxylate group (R
1
═H, metal, ammonium) is present, at least one radical R
3
includes identical or different radicals of the structure R
9
-Y-, where R
9
originates from the group of straight-chain or branched, saturated or unsaturated alkyl or alkenyl radicals having from 6 to 30 carbon atoms (for example branched or linear octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl or docosyl radicals, also unsaturated and polyunsaturated species such as, for example, oleyl) and Y is a polyoxyalkylene chain having from 0 to 100 alkylene glycol units, preferably derived from ethylene oxide, propylene oxide or mixtures thereof, and optionally a radical R
4
originates from the group of straight-chain or branched, saturated or unsaturated alkyl or alkenyl radicals having from 1 to 5 carbon atoms (for example methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, n-pentyl) and at least one polyfunctional radical X, preferably derived from a saturated di- or polyhydroxy or a di- or polyamino compound, such as, for example, linear 1, (-alkanediols, glycerol, sorbitol, 1,2-propylene glycol, linear 1, (-diaminoalkanes, lysine, ethanolamine, diethanolamine, triethanolamine, sugar derivatives, oligo- and polysaccharides, and the addition products of said compounds with ethylene oxide and/or propylene oxide. Other suitable polyfunctional compounds are, for example, polyvinyl alcohol, oligo- and polyethylene glycols or ethylene oxide-propylene oxide copolymers.
A preferred form of the copolymers comprises alkyl or alkenyl radicals R
9
having from 10 to 22 carbon atoms without alkylene glycol spacers (alkylene glycol chain length 0), crosslinking groups (III) derived from 1, (-diols and diamines having from 4 to 6 carbon atoms, polyethylene glycols having a molecular mass of from 200 to 2000 or mono-, di- or trie
Gruning Burghard
Simpelkamp Jorg
Weitemeyer Christian
Goldschmidt AG
Scully Scott Murphy & Presser
Truong Duc
LandOfFree
Copolymeric, hydrophobically modified polyaspartic esters... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Copolymeric, hydrophobically modified polyaspartic esters..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Copolymeric, hydrophobically modified polyaspartic esters... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2612251