U.S. patent application number 09/312222 was filed with the patent office on 2001-06-14 for copolymeric, hydrophobically modified polyaspartic esters having increased molecular mass and their use.
Invention is credited to GRUNING, BURGHARD, SIMPELKAMP, JORG, WEITEMEYER, CHRISTIAN.
Application Number | 20010003776 09/312222 |
Document ID | / |
Family ID | 7868384 |
Filed Date | 2001-06-14 |
United States Patent
Application |
20010003776 |
Kind Code |
A1 |
GRUNING, BURGHARD ; et
al. |
June 14, 2001 |
COPOLYMERIC, HYDROPHOBICALLY MODIFIED POLYASPARTIC ESTERS HAVING
INCREASED MOLECULAR MASS AND THEIR USE
Abstract
The invention describes the preparation of high molecular weight
copolymeric polyaspartic esters which have been hydrophobically
modified with alkyl radicals having from 6 to 30 carbon atoms.
Copolymers derived from polyamino acids, in which at least 75 mol %
of the units present consist of structural units of the general
formulae (I), (II) or (III) 1 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.sup.1
is as defined for R.sup.2, R.sup.3 or R.sup.4, where R.sup.2 are
one or more radicals from the group of alkali metals, alkaline
earth metals, hydrogen or ammonium,
[NR.sup.5R.sup.6R.sup.7R.sup.8].sup.+- , where R.sup.5 to R.sup.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.sub.1- to C.sub.22-carboxylic radicals,
R.sup.3 are identical or different, straight-chain or branched,
saturated or unsaturated alkyl or alkenyl radicals R.sup.9 having
from 6 to 30 carbon atoms, or radicals of the structure
--Y--R.sup.9, where Y is an oligo- or polyoxyalkylene chain having
from 1 to 100 oxyalkylene units, R.sup.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, 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.sup.1 must assume the
meaning of R.sup.2 and at least one radical R.sup.1 that of R.sup.3
and at least one radical R.sup.1 that of X.
Inventors: |
GRUNING, BURGHARD; (ESSEN,
DE) ; SIMPELKAMP, JORG; (ESSEN, DE) ;
WEITEMEYER, CHRISTIAN; (ESSEN, DE) |
Correspondence
Address: |
LEOPOLD PRESSER
SCULLY SCOTT MURPHY & PRESSER
400 GARDEN CITY PLAZA
GARDEN CITY
NY
11530
|
Family ID: |
7868384 |
Appl. No.: |
09/312222 |
Filed: |
May 14, 1999 |
Current U.S.
Class: |
528/310 ;
525/419; 525/420; 528/328; 528/363 |
Current CPC
Class: |
C08G 73/16 20130101;
A61Q 19/00 20130101; C08G 73/028 20130101; C08G 73/1092 20130101;
C11D 3/3719 20130101; A61K 8/88 20130101; A61Q 19/10 20130101 |
Class at
Publication: |
528/310 ;
528/328; 528/363; 525/419; 525/420 |
International
Class: |
C08G 069/08; C08G
073/10 |
Foreign Application Data
Date |
Code |
Application Number |
May 20, 1998 |
DE |
198 22 600.4 |
Claims
Patent claims:
1. A copolymer derived from polyamino acids, in which at least 75
mol % of the units present consist of structural units of the
general formulae (I), (II) or (III) 5in 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.sup.1 is as defined for R.sup.2, R.sup.3 or R.sup.4, where
R.sup.2 are one or more radicals from the group of alkali metals,
alkaline earth metals, hydrogen or ammonium,
[NR.sup.5R.sup.6R.sup.7R.sup.8].sup.+, where R.sup.5 to R.sup.8
independently of one another are hydrogen, alkyl or alkylene 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.sub.1- to C.sub.22-carboxylic radicals,
R.sup.3 are identical or different, straight-chain or branched,
saturated or unsaturated alkyl or alkenyl radicals R.sup.9 having
from 6 to 30 carbon atoms, or radicals of the structure
--Y--R.sup.9, where Y is an oligo- or polyoxyalkylene chain having
from 1 to 100 oxyalkylene units, R.sup.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, 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.sup.1 must assume the
meaning of R.sup.2 and at least one radical R.sup.1 that of R.sup.3
and at least one radical R.sup.1 that of X.
2. The copolymer as claimed in claim 1, in which at least one
radical R.sup.1 has the meaning of R.sup.4.
3. The copolymer as claimed in claim 1, in which R.sup.3 are
identical or different, straight-chain or branched, saturated or
unsaturated alkyl or alkenyl radicals having from 8 to 24 carbon
atoms.
4. The copolymer as claimed in claim 1, comprising, as
molecular-mass-increasing agents, di- or polyhydroxy compounds, di-
or polyamino compounds, or aminoalcohols or mixtures, 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.
5. The copolymer as claimed in claim 1, comprising, as
molecular-mass-increasing agents, linear 1,(-alkanediols, glycerol,
sorbitol, 1,2-propylene glycol, linear 1,.omega.-diaminoalkanes,
lysine, ethanolamine, diethanolamine, triethanolamine, sugar
derivatives, oligo- and polysaccharides, the addition products of
ethylene oxide and/or propylene oxide with said compounds,
polyvinyl alcohol, oligo- and polyethylene glycols and/or ethylene
oxide-propylene oxide copolymers.
6. A process for the preparation of the copolymers as claimed in
claim 1, which comprises reacting esters of
.alpha.,.beta.-unsaturated dicarboxylic acids or their ammonium
salts, in particular maleic acid derivatives of the general
formulae (V) and (VI) 6alone or in a mixture with one another, with
ammonia, and converting them into the polymer and then treating
them with molecular-mass-increasing agents, where Z is hydrogen
and/or ammonium, and R.sup.3 and R.sup.4 are the abovementioned
radicals, optionally in the presence of up to 20% by weight of
proteinogenic or nonproteinogenic amino acids or their derivatives
of the general formula (II), and optionally in further stages, by
hydrolysis, producing groups of the structure of the formula (I)
where R.sup.1 has the meaning of R.sup.2, having the abovementioned
definition of R.sup.2.
7. The process as claimed in claim 6, which comprises reacting
esters of .alpha.,.beta.-unsaturated dicarboxylic acids or their
ammonium salts, in particular maleic acid derivatives of the
general formulae (V) and (VI), in the presence of
molecular-mass-increasing agents with ammonia, and converting into
the polymer.
8. A cosmetic emulsion comprising a copolymer as claimed in claim
1, wherein the nonaqueous fraction comprises from 5 to 99% by
weight of oily substances from the group consisting of esters of
linear C.sub.6-C.sub.20-fatty acids with linear
C.sub.6-C.sub.20-fatty alcohols, esters of branched
C.sub.6-C.sub.13-carboxylic acids with linear
C.sub.6-C.sub.20-fatty alcohols, esters of linear
C.sub.6-C.sub.20-fatty acids with branched alcohols, esters of
linear and/or branched C.sub.6-C.sub.20-carboxylic acids with
polyhydric alcohols and/or Guerbet alcohols, triglycerides based on
C.sub.6-C.sub.10-fatty acids, vegetable and animal oils and fats,
branched primary alcohols, substituted cyclohexanes, Guerbet
carbonates, dialkyl ethers and/or aliphatic or naphthenic
hydrocarbons.
9. The cosmetic emulsion as claimed in claim 8, comprising
hydrophilic waxes selected from the group consisting of
C.sub.12-C.sub.30-fatty alcohols, wool wax alcohols,
C.sub.16-C.sub.22-fatty acids, glycerol mono- and diesters and
sorbitan mono- and diesters of saturated fatty acids having from 12
to 22 carbon atoms.
10. The cosmetic emulsion as claimed in claim 8, comprising one or
more coemulsifiers selected from the group consisting of the
addition products of ethylene oxide or ethylene oxide and propylene
oxide with C.sub.12-C.sub.30-fatty alcohols and wool wax alcohols,
the ethylene oxide addition products of glycerol mono- and diesters
and sorbitan mono- and diesters of saturated and unsaturated fatty
acids having from 6 to 22 carbon atoms, of the addition products of
ethylene oxide and/or propylene oxide with fatty acids having from
12 to 22 carbon atoms and with alkylphenols having from 8 to 15
carbon atoms in the alkyl group, of C.sub.12-C.sub.18-fatty acid
mono- and diesters of addition products of ethylene oxide with
glycerol, of addition products of ethylene oxide with fats and
oils, of polyol esters of saturated or unsaturated
C.sub.12-.sub.22-fatty acids, including branched or
hydroxy-substituted ones, of polysiloxane-polyalkyl-polyether
copolymers and their derivatives, of anionic surfactants, cationic
surfactants, nonionic surfactants and zwitterionic or amphoteric
surfactants.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] 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.
[0003] 2. Prior Art
[0004] 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. 5,219,952A, 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.
[0005] 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, 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.
[0006] 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.
[0007] The object of the invention is to provide copolymeric
polyaspartic esters with increased molecular masses.
SUMMARY OF THE INVENTION
[0008] 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
[0009] 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) 2
[0010] 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
[0011] R.sup.1 is as defined for R.sup.2, R.sup.3 or R.sup.4,
where
[0012] R.sup.2 are one or more radicals from the group of alkali
metals, alkaline earth metals, hydrogen or ammonium,
[NR.sup.5R.sup.6R.sup.7R.sup- .8].sup.+, where R.sup.5 to R.sup.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.sub.1- to C.sub.22-carboxylic acid
radicals,
[0013] R.sup.3 are identical or different, straight-chain or
branched, saturated or unsaturated alkyl or alkenyl radicals
R.sup.9 having from 6 to 30 carbon atoms or radicals of the
structure --Y--R.sup.9, where Y is an oligo- or polyoxyalkylene
chain having from 1 to 100 oxyalkylene units,
[0014] R.sup.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
[0015] 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,
[0016] and at least in each case one radical R.sup.1 must assume
the meaning of R.sup.2 and at least one radical R.sup.1 that of
R.sup.3 and at least one radical R.sup.1 that of X.
[0017] All of the data given relating to the composition of the
polymeric products refer, as usual, to the average composition of
the polymer chain.
[0018] 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) 3
[0019] 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.
[0020] 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 .beta.-alanine, .omega.-amino-1-alkanoic acids, for
example 6-aminocaproic acid, etc.
[0021] 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.
[0022] According to the invention, preference is given to compounds
in which at least one free carboxylate group (R.sup.1=H, metal,
ammonium) is present, at least one radical R.sup.3 includes
identical or different radicals of the structure R.sup.9--Y--,
where R.sup.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.sup.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.
[0023] A preferred form of the copolymers comprises alkyl or
alkenyl radicals R.sup.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
triethanolamine, and optionally small amounts of alkyl or alkenyl
radicals R.sup.4 having from 1 to 4 carbon atoms.
[0024] These derivatives are obtainable, for example, by a
preparation process which comprises reacting a mixture of
monoesters of monoethylenically unsaturated dicarboxylic acids with
from 0.1 to 3.0 equivalents of ammonia, preferably with from 0.8 to
1.5 equivalents of ammonia, or thermally converting the ammonium
salts of these acids into the polymer. Use can be made, for
example, of 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 (V) und (VI) 4
[0025] where Z is hydrogen or ammonium, and R.sup.3 and R.sup.4 are
the abovedefined radicals. These maleic acid derivatives can in
each case be used alone or in any desired mixtures with one
another.
[0026] Preferred radicals R.sup.3 are alkyl radicals having from 8
to 30 carbon atoms, for example linear or branched decyl, dodecyl,
tetradecyl, hexadecyl or octadecyl radicals and unsaturated alkenyl
radicals, such as, for example, oleyl. Preferred radicals R.sup.4
are alkyl radicals having from 1 to 4 carbon atoms, preferably
methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or s-butyl.
[0027] The reaction can be carried out with or without the addition
of organic solvents. Examples of suitable solvents are alcohols,
ketones, esters, oligo- and poly(alkylene) glycols and glycol
ethers, dimethyl sulfoxide, dimethylformamide,
N,N-dimethylacetamide or N-methylpyrrolidone and their mixtures,
etc. Preference is given to using alcohols having from 2 to 4
carbon atoms, particularly preferably the short-chain alcohol
R.sup.4OH, and ketones such as, for example, methyl isobutyl ketone
or methyl isoamyl ketone, or alkyl esters of carboxylic acids
having from 1 to 4 carbon atoms, such as, for example, sec-butyl
acetate or pentyl acetate. The reaction can optionally be carried
out in the presence of compatibility-promoting agents. These may be
surface-active compounds, for example addition products of from 1
to 30 mol of ethylene oxide and/or from 0 to 5 mol of propylene
oxide with C.sub.12-C.sub.30-fatty alcohols and wool wax alcohols;
ethylene oxide addition products of glycerol mono- and diesters and
sorbitan mono- and diesters of saturated and unsaturated fatty
acids having from 6 to 22 carbon atoms; addition products of from 2
to 30 mol of ethylene oxide and/or from 0 to 5 mol of propylene
oxide with fatty acids having from 12 to 22 carbon atoms and with
alkylphenols having from 8 to 15 carbon atoms in the alkyl group;
C.sub.12-C.sub.18-fatty acid partial esters of addition products of
from 1 to 30 mol of ethylene oxide with glycerol; addition products
of ethylene oxide with fats and oils, for example castor oil or
hydrogenated castor oil; partial esters of saturated or unsaturated
C.sub.12-C.sub.22-fatty acids, including branched or
hydroxyl-substituted ones, with polyols, for example esters of
glycerol, ethylene glycol, polyalkylene glycols, pentaerythritol,
polyglycerol, sugar alcohols such as sorbitol, and polyglucosides
such as cellulose; polysiloxane-polyalkyl-polyether copolymers and
their derivatives and hydrophobically modified polyaspartic acid
derivatives, for example partially esterified polyaspartic acids,
partially esterified polyaspartic acid-co-glutamic acid or
condensates of maleic monoesters and ammonia, prepared, for
example, by the novel process or as in DE 195 45 678 A, the
preparation process of said polyamino acid derivatives having no
influence on their compatibility-promoting effect. If desired, a
certain fraction of the product mixture may also remain in the
reactor and be used as solubilizer for a subsequent reaction.
[0028] The compatibility- or solubility-promoting agents present
may also be cationic surfactants, for example from the group of
quaternary ammonium compounds, quaternized protein hydrolysates,
alkylamido amines, quaternary ester compounds, quaternary silicone
oils or quaternary sugar and polysaccharide derivatives, anionic
surfactants, for example from the group of sulfates, sulfonates,
carboxylates and mixtures thereof, for example
alkylbenzenesulfonates, .alpha.-olefinsulfonates,
.alpha.-sulfonated fatty acid esters, fatty acid glycerol ester
sulfates, paraffinsulfonates, alkyl sulfates, alkyl polyether
sulfates, alkyl sulfosuccinates, fatty acid salts (soaps), fatty
acid esters of polylactic acid, N-acylamino acid esters,
N-acyltaurates, acylisethionates, ether carboxylates, monoalkyl
phosphates, N-acylamino acid derivatives, such as N-acyl aspartates
or N-acyl glutamates, N-acylsarcosinates, amphoteric or
zwitterionic surfactants, such as, for example, alkylbetaines,
alkylamidoalkylbetaines of the cocoamidopropylbetaine type,
sulfobetaines, phosphobetaines, sultaines and amidosultaines,
imidazolinium derivatives, amphoglycinates, or nonionic
surfactants, such as, for example, oxethylated fatty alcohols,
oxethylated alkylphenols, oxethylated fatty acid esters,
oxethylated mono-, di- or triglycerides or polyalkylene glycol
fatty acid esters, sugar esters, for example fatty acid esters of
sucrose, fructose or of methyl glucoside, sorbitol fatty acid
esters and sorbitan fatty acid esters (optionally oxethylated),
alkyl or alkenyl polyglucosides and their ethoxylates, fatty acid
N-alkylpolyhydroxyalkylamides, polyglycerol esters, fatty acid
alkanolamides, long-chain tertiary amine oxides or phosphine oxides
and dialkyl sulfoxides.
[0029] The compatibility-promoting agents preferably remain in the
product. In a preferred procedure, the reaction to give the
copolymer is carried out with aqueous or gaseous ammonia at
temperatures of from 0 to 150.degree. C., preferably from 50 to
140.degree. C., and subsequent distillation is carried out at from
70 to 240.degree. C., preferably from 110 to 150.degree. C., under
reduced pressure, for example in kneading devices, high-viscosity
reactors, extruders or stirred reactors, optionally using
high-shear-force stirrers such as Mig or Intermig stirrers.
[0030] Under the reaction conditions, some of the ester groups,
preferably those derived from R.sup.4OH, are at the same time
hydrolyzed and the desired carboxylic acid or carboxylate groups
liberated. Subsequent mild partial or complete hydrolysis,
preferably of the ester functions derived from the short-chain
alcohol R.sup.4OH, can, if desired, increase further the amount of
free acid groups, for example by reaction with water, optionally in
the presence of acids or bases, or with alkali metal hydroxides,
optionally in the presence of an organic solvent or cosolvent.
[0031] By adding amino- and carboxy-functional compounds to the
reaction mixture, it is possible to obtain copolymers in which the
offered units are bonded via amide bonds. Suitable units are amino
acids from the group of 20 proteinogenic amino acids which are
present as monomers in all natural proteins, in an enantiomerically
pure or racemic form, such as, for example, glutamine, asparagine,
lysine, alanine, glycine, tyrosine, tryptophan, serine and cysteine
and their derivatives, or nonproteinogenic amino acids having in
each case one or more amino or carboxy functions, such as, for
example .beta.-alanine, .omega.-amino-1-alkanoic acids, for example
6-aminocaproic acid. The units, preferably from 0 to 15% by weight,
are added to the starting mixture of the maleic acid derivatives
or, for modification of the chain ends, are reacted therewith after
synthesis of the polymer has taken place, preferably with the
addition of polar solvents, such as, for example, alcohols or
dimethylformamide.
[0032] The groups (IV) which increase the molecular masses are
introduced by adding the polyfunctional amino or hydroxyl compounds
to the reaction mixture. The addition can take place before, during
or after neutralization of the maleic monoesters using ammonia. In
a preferred embodiment, the crosslinking agents are added after the
neutralization. Furthermore, the crosslinking agents can also be
added at a later point in the reaction after the reaction mixture
has been largely distilled to give the viscous polymer product of
maleic monoesters and ammonia, optionally with the addition of
acidic or Lewis acid catalysts, such as, for example, titanium(IV)
alkoxides. In both embodiments, a further treatment is carried out
by distillation (of water, the short-chain alcohol R.sup.4OH and
optionally other solvents), optionally under reduced pressure, at
from 70 to 220.degree. C., preferably at from 110 to 160.degree. C.
The ratio of dicarboxylic acid monomers to the amino or hydroxyl
groups of the polyfunctional crosslinking agents can be from
99.5:0.5 to 10:90, preferably from 95:5 to 50:50.
[0033] In a further embodiment, the polyfunctional amino or
hydroxyl compounds are reacted in a first stage with from 0.1 to
2.0 equivalents, preferably from 0.5 to 1.2 equivalents, of maleic
anhydride per hydroxyl or amino function. The resulting maleic acid
derivatives are added to the starting material mixture comprising
the maleic monoesters (V) and (VI) before or during neutralization
with ammonia.
[0034] The procedures described for the addition of the
molecular-mass-increasing components can be combined as
desired.
[0035] The resulting polymers can be post-treated, for example by
treatment with ammonia, transesterification catalysts such as, for
example, Lewis acid titanium(IV) compounds, with activated carbon
or other adsorbents, bleaching with oxidizing agents such as
H.sub.2O.sub.2, Cl.sub.2, O.sub.3, sodium chlorite, sodium
hypochlorite etc. or reducing agents such as, for example,
NaBH.sub.4 or H.sub.2 in the presence of catalysts, under customary
conditions.
[0036] Compared with the copolymeric polyaspartic acid derivatives
which are prepared without the addition of
molecular-mass-increasing groups, the novel copolymers exhibit a
significant increase in the resulting molecular masses. They have
excellent properties as sequestering agents, as additives for
colorants and coatings, as foam stabilizers, surfactants and
emulsifiers. In particular, the thermal and long-term stability of
O/W and W/O emulsions is beneficially influenced.
[0037] The novel polymers can be used as emulsifiers for cosmetic
emulsions, for example for lotions having a comparatively low
viscosity or creams and ointments having a high viscosity, for
applications as skin care compositions, such as, for example, day
creams, night creams, care creams, nourishing creams, body lotions,
ointments and the like. Other auxiliaries and additives which may
be present are customary coemulsifiers, bodying agents, oily
substances, superfatting agents, fats, waxes, stabilizers, active
ingredients, glycerol, dyes and fragrances.
[0038] Suitable bodying agents which may be used are hydrophilic
waxes, for example C.sub.12-C.sub.30 fatty alcohols,
C.sub.16-C.sub.22 fatty acids, glycerol mono- and diesters and
sorbitan mono- and diesters of saturated fatty acids having from 12
to 22 carbon atoms.
[0039] Examples of other suitable coemulsifiers are: addition
products of from 2 to 30 mol of ethylene oxide and/or from 0 to 5
mol of propylene oxide with C.sub.12-C.sub.30 fatty alcohols and
wool wax alcohols, preferably linear, saturated C.sub.16-C.sub.22
fatty alcohols; ethylene oxide addition products of glycerol mono-
and diesters and sorbitan mono- and diesters of saturated and
unsaturated fatty acids having from 6 to 22 carbon atoms; addition
products of from 2 to 30 mol of ethylene oxide and/or from 0 to 5
mol of propylene oxide with fatty acids having from 12 to 22 carbon
atoms and with alkylphenols having from 8 to 15 carbon atoms in the
alkyl group; C.sub.12-C.sub.18-fatty acid mono- and diesters of
addition products of from 1 to 30 mol of ethylene oxide with
glycerol; addition products of ethylene oxide with fats and oils;
polyol esters of saturated or unsaturated C.sub.12-C.sub.22 fatty
acids, including branched or hydroxy-substituted ones, for example
esters of pentaerythritol, polyglycerol, sugar alcohols such as
sorbitol and polysaccharides, such as cellulose;
polysiloxane-polyalkyl-polyether copolymers and their derivatives
and hydrophobically modified polyaspartic acid derivatives. The
coemulsifiers may also be anionic, cationic, amphoteric and/or
zwitterionic surfactants and nonionic surfactants, for example from
the groups referred to as compatibility-promoting agents.
[0040] It is possible in each case to use any mixtures of the above
bodying agents and coemulsifiers.
[0041] Examples of suitable oily substances are esters of linear
C.sub.6-C.sub.20 fatty acids with linear C.sub.6-C.sub.20 fatty
alcohols, esters of branched C.sub.6-C.sub.13 carboxylic acids with
linear C.sub.6-C.sub.20 fatty alcohols, esters of linear
C.sub.6-C.sub.20 fatty acids with isopropanol or branched alcohols,
esters of linear and/or branched C.sub.6-C.sub.20 carboxylic acids
with polyhydric alcohols and/or Guerbet alcohols, triglycerides
based on C.sub.6-C.sub.10 fatty acids, vegetable and animal oils
and fats, branched primary alcohols, substituted cyclohexanes,
Guerbet carbonates, dialkyl ethers and/or aliphatic or naphthenic
hydrocarbons.
[0042] Suitable superfatting agents are, for example, lanolin and
lecithin derivatives and their ethoxylates, polyol fatty acid
esters, monoglycerides and fatty acid alkanolamides.
[0043] Silicone compounds such as polydimethylsiloxanes,
cyclodimethicones and amino-, fatty-acid-, alcohol-, epoxy-,
fluorine-, and/or alkyl-modified silicone compounds, and waxes such
as, for example, beeswax, paraffin waxes or microcrystalline waxes
may be present. The emulsions can comprise thickeners, such as
polyacrylic acid derivatives or polysaccharides, such as, for
example, xanthan, carboxymethylcellulose, hydroxyethylcellulose,
cationic cellulose or starch derivatives, cationic chitin or
chitosan derivatives, cationic silicone polymers, copolymers of
diallylammonium salts, for example with acrylamides,
polyethyleneimine. Furthermore, inorganic electrolytes such as
alkali metal and alkaline earth metal or ammonium halides,
sulfates, nitrates or carbonates, or metal salts of fatty acids,
for example magnesium, aluminum or zinc stearate as stabilizers, or
zinc salts of ricinoleic acid may be present as deodorizers.
Customary sunscreen active ingredients, buffer substances,
antioxidants, fragrances, dyes, biogenic active ingredients such as
plant extracts or vitamin complexes, pharmaceutical active
ingredients and customary moisture-regulating substances such as
pyrrolidinedione-2 carboxylate and polyhydroxy compounds such as
glycerol, polyglycerols, propanediol, polyethylene glycols, mono-
and polysaccharides, may be present.
[0044] The emulsions may further comprise lusterizing agents, such
as ethylene glycol distearate, solid inorganic additives such as
metal oxides, silicates, clay minerals etc. and customary
preservatives.
[0045] The emulsification can be carried out in a manner known per
se, i.e. for example by hot, cold, hot-hot/cold or PIT
emulsification.
[0046] Depending on the type of polyaspartic acid derivatives and
coemulsifiers used, emulsions of the O/W or of the W/O type are
obtainable.
[0047] In a preferred embodiment of the invention, the emulsions
comprise, based on the amount of emulsifier, from to 1 to 99% by
weight, preferably from 5 to 50% by weight, of polyaspartic acid
derivatives, from 0 to 99% by weight, in O/W emulsions, preferably
from 15 to 80% by weight of one or more bodying agents, and from 0
to 99% by weight, preferably from 20 to 75% by weight of further
coemulsifiers. The nonaqueous fraction of the emulsions, which is
largely composed of the emulsifier/bodying agent and the oily
subtance content, is usually from 5 to 95% by weight and preferably
from 15 to 75% by weight. This means, in the reverse situation,
that the emulsions can comprise from 5 to 95% by weight and
preferably from 25 to 85% by weight of water, depending on whether
the intention is to prepare lotions with a comparatively low
viscosity or creams and ointments with a high viscosity.
[0048] The novel polyaspartic acid derivatives having a polyamino
acid backbone which is similar to naturally occurring structures
are mild surfactants, which can be used alone or in combination
with anionic, cationic, nonionic, zwitterionic and/or amphoteric
surfactants. Solid, liquid or paste preparations are possible, e.g.
soap bars, washing lotions, shower gels, shampoos.
[0049] The surfactants which can be used in combination with the
novel polyaspartic acid derivatives in emulsions or surface-active
preparations can, for example, be anionic surfactants from the
group of sulfates, sulfonates, carboxylates and mixtures thereof.
The anionic groups can be in neutralized form, containing cationic
counterions from the group of alkali metals, alkaline earth metals,
ammonium or substituted ammonium. Use is made, for example, of
alkylbenzenesulfonates, .alpha.-olefinsulfonates,
.alpha.-sulfonated fatty acid esters, fatty acid glycerol ester
sulfates, paraffinsulfonates, alkyl sulfates, alkyl polyether
sulfates, alkyl sulfosuccinate, fatty acid salts (soaps), fatty
acid esters of polylactic acid, N-acylamino acid esters,
N-acyltaurates, acylisethionates, ether carboxylates, monoalkyl
phosphates, N-acylamino acid derivatives, such as N-acyl aspartates
or N-acylglutamates, N-acyl sarcosinates, polyaspartic acid
derivatives and others.
[0050] The surfactants which can be used in combination with the
novel polyaspartic acid derivatives can, for example, be amphoteric
or zwitterionic surfactants, for example alkylbetaines,
alkylamidoalkylbetaines of the cocoamidopropylbetaine type,
sulfobetaines, phosphobetaines, sultaines and amidosultaines,
imidazolinium derivatives, amphoglycinates and others.
[0051] The surfactants which can be used in combination with the
novel polyaspartic acid derivatives can also be, for example,
nonionic surfactants, for example oxethylated fatty alcohols,
oxethylated alkylphenols, oxethylated fatty acid esters,
oxethylated mono-, di- or triglycerides or polyalkylene glycol
fatty acid esters. Other nonionic surfactants can originate from
the group of alkyl polysaccharides, for example alkyl or alkenyl
polyglucosides and their ethoxylation products, sugar esters, for
example fatty acid esters of glucose, saccharose, fructose or of
methyl glucoside, sorbitol fatty acid esters and sorbitan fatty
acid esters (optionally oxethylated), polyglycerol esters, fatty
acid alkanolamides, N-acylamino sugar derivatives, for example
N-acylglucamines, long-chain tertiary amine oxides or phosphine
oxides and dialkyl sulfoxides.
[0052] The cationic surfactants which are used in combination with
the novel polyaspartic acid derivatives can, for example, be chosen
from the group of quaternary ammonium compounds, quaternized
protein hydrolyzates, alkylamido amines, quaternary ester
compounds, quaternary silicone oils or quaternary sugar and
polysaccharide derivatives.
[0053] The surfactants which are used in combination with the novel
polyaspartic acid derivatives can also be any combination of two or
more surfactants from the abovementioned categories.
[0054] The surfactant preparations according to the invention can
comprise further auxiliaries and additives, such as, for example,
water and solvents, for example from the group of alcohols and
polyols, thickeners, opacifiers, e.g. glycol ester derivatives;
moisturizers, emollients such as animal and vegetable oils,
carboxylic esters, lanolin, beeswax, silicones; polymeric agents
for improving the feel on the skin, conditioning, care or
pharmaceutically active constituents such as, for example, cationic
or amphoteric polymers, proteins and protein derivatives, lanolin
derivatives, pantothenic acid, betaine, polydimethylsiloxanes or
their derivatives, sunscreen active ingredients and solubilizers,
stabilizers, buffer substances, fragrances, preservatives and/or
dyes.
[0055] The surfactant preparations comprising polyaspartic acid
derivatives can advantageously be used in, for example, hair
shampoo, shower preparation, bubble bath preparation, hand, face
and intimate area cleansing lotion, liquid soap, soap bar, shaving
cream, handwashing paste, dishwashing detergents which are gentle
on the skin, cleaner for smooth surfaces and in toothpaste.
[0056] The novel polyaspartic acid derivatives can advantageously
be used as dispersants, for the preparation of aqueous pigment
pastes. To this end, the hydrophobically modified polyaspartic acid
derivatives are neutralized advantageously using prior art
neutralizing agents, in particular amines. Particular preference is
here given to using dimethylethanolamine or
2-amino-2-methylpropanol. For the preparation of aqueous pigment
pastes, from 0.1 to 100% by weight, preferably from 0.5 to 50% by
weight, in particular from 2 to 15% by weight, based on the weight
of the pigments, are used. The hydrophobically modified
polyaspartic acid derivatives can, for the novel use, either be
mixed beforehand with the pigments to be dispersed, or be dissolved
directly in the dispersing medium (water, possible additions of
glycol) prior to or at the same time as the addition of the
pigments and any other solids. Neutralization can take place before
or during the preparation of the pigment pastes. Preference is
given to using polyaspartic acid preparations which have already
been partially or completely neutralized.
[0057] The novel polyaspartic acid derivatives can also be used in
any mixtures with other, prior art dispersion additives, for
example from the group of fatty acid alkoxylates,
poly(meth)acrylates, polyesters, polyethers etc.
[0058] In this connection, examples of pigments which may be
mentioned are inorganic or organic pigments, and carbon blacks.
Examples of inorganic pigments are titanium dioxide and iron
oxides. Suitable organic pigments are, for example, azo pigments,
metal complex pigments, phthalocyanine pigments, anthraquinoid
pigments, polycyclic pigments, in particular those from the
thioindigo, quinacridone, dioxazine, pyrrolopyrrole,
naphthalenetetracarboxylic acid, perylene, isoamidolin(on)e,
flavanthrone, pyranthrone or isoviolanthrone series. The novel
polyaspartic acid derivatives can be used as dispersants, for
example for coatings and colorants.
[0059] Fillers which can, for example, be dispersed in aqueous
coatings are, for example, those based on kaolin, talc, other
silicates, chalk, glass fibers, glass pearls or metal powders.
[0060] Suitable coating systems into which the novel pigment pastes
can be incorporated are any aqueous 1-component or 2-component
coatings. Examples include aqueous 1-component coatings, such as,
for example, those based on alkyd, acrylate, epoxy, polyvinyl
acetate, polyester or polyurethane resins, or aqueous 2-component
coatings, for example those based on hydroxyl-group-containing
polyacrylate or polyester resins with melamine resins or optionally
blocked polyisocyanate resins as crosslinkers. Polyepoxy resin
systems may likewise also be mentioned.
EXAMPLES
Comparative Examples 1 and 2
Poly(aspartic Acid-co-alkyl Aspartate)
[0061] The polyaspartic esters were prepared as described in
accordance with DE 195 45 678 A by reacting the starting materials
(monoethyl maleate, monoalkyl maleate, dissolved in methylisobutyl
ketone) with from 1.0 to 1.5 equivalents of ammonia gas and
distillation of the reaction mixture under reduced pressure at from
110 to 140.degree. C. for from 4 to 6 h.
[0062] The degrees of esterification were determined using NMR
spectroscopy, the average molecular masses were determined by gel
permeation chromatography (column 2.times.SDV100.ANG./microgel
1000.ANG.; tetrahydrofuran/oxalic acid, calibrated against
PMMA)
1 STARTING STARTING PRODUCT: PRODUCT: MATERIAL: MATERIAL: MOL % OF
MOL % OF MOL % EX- ALKYL MOL OF ALKYL MOL OF ETHYL ALKYL ETHYL OF
M.sub.w AMPLE RADICAL MALEATE MALEATE ESTER ESTER ACID (GPC) 1
decyl 1.0 3.0 20 3 77 1200 2 cetyl 1.2 2.8 27 6 67 1800
Example 3
[0063] 300 g of the product from Example 1 were mixed with 70 g of
1,6-diaminohexane at 135.degree. C., and the mixture was stirred at
140.degree. C. for 8 h under distillation conditions.
[0064] GPC: M.sub.w=2500
Example 4
[0065] 400 g of the product from Example 1 were mixed with 86 g of
1,6-hexanediol at 120.degree. C., 4 g of tetrabutyl titanate are
added and the mixture is distilled at 145.degree. C. and 200 mbar
for 8 h.
[0066] GPC: M.sub.w=3900
Example 5
[0067] Following the procedure of Example 3, 400 g of the product
from Ex. 2 were reacted with 140 g of 1,6-diaminohexane.
[0068] GPC: M.sub.w=9800
Example 6
[0069] 340 g (1 mol) of cetyl maleate, 286 g (2 mol) of ethyl
maleate and 79 g (0.25 mol) of the reaction product of maleic
anhydride and 1,6-hexanediol (1:1) were dissolved in
4-methyl-2-pentanone and treated with 4 mol of ammonia gas.
Distillation was carried out at from 110 to 130.degree. C. under
reduced pressure for 5 h.
[0070] GPC: M.sub.w=6200
Examples 7 to 10
[0071] O/W Emulsions containing polyaspartic acid derivatives
2 Cetylpolyaspartate from Example 2, 4, 5 2.0% or 6 (25% in water,
pH 5.5) Glycerol 3.0% Preservative 0.1% Water 70.4% Glycerol
monostearate 4.5% (Tegin .RTM. M, Th. Goldschmidt AG)
Caprylic/capric triglyceride, 20.0% (Tegosoft .RTM.CT, Th.
Goldschmidt AG)
[0072] The aqueous phase and the oily substance/glycerol
monostearate mixture were mixed at 70.degree. C., and vigorously
processed using a rotor-stator homogenizer (SG/220V, 2 min). The
water separation of the O/W emulsions was determined after storage
for 2 d at 20.degree. C. and after storage for a further 7 d at
45.degree. C. The sensory evaluation of the samples showed, in the
case of Ex. 5, no change in the creamy consistency during storage,
and in the case of the comparison, a noticeable deterioration.
3 WATER WATER SEPARATION SEPARATION EMULSIFIER AFTER 2 DAYS/ AFTER
28 DAYS/ FROM 20.degree. C. 45.degree. C. EXAMPLE EXAMPLE (% BY
VOLUME) (% BY VOLUME) 7 2 <0.1% 6 8 4 <0.1% 1 9 5 <0.1%
0.5 10 6 <0.1% 2
[0073] These results show the improvement in the emulsion stability
of the polyaspartic esters modified using polyfunctional
agents.
Example 11
Surfactant Preparations Containing Polyaspartic Acid
Derivatives
[0074]
4 A B FORMULATION (% BY WEIGHT) (% BY WEIGHT) Poly(aspartic
acid-co-decyl 0.0% 1.0% asparate) as in Example 3, (50% strength in
water, pH 5,5) Texapon .RTM. N28 21.4% 21.4% (28% sodium lauryl
ether sulfate (Henkel KGaA)) Tego .RTM. betaine F50 16.0 16.0
(37.5% cocamidopropylbetaine, Th. Goldschmidt AG) Water ad 100%, pH
ad 6.0
[0075] The foaming properties of the surfactant mixture are
determined by frothing up a dilute surfactant solution. (0.5% by
weight of active detergent substance, 8.degree. German hardness,
30.degree. C., Ystral guidebeam mixer, 750 W, 2 min)
5 FOAM WATER VOLUME SEPARATION FOAM DENSITY MIXTURE [ml] 10 MIN
[ml] [g/ml] A 1490 .+-. 17 240 .+-. 2.0 0.208 .+-. 0.002 B 1584
.+-. 11 231 .+-. 2.9 0.193 .+-. 0.003
[0076] This example demonstrates the positive effect of the
polyaspartic acid derivatives on the foaming behavior of surfactant
systems.
Example 12
[0077] Formulation for a shower gel concentrate
6 Poly(aspartic acid-co-decyl aspartate), 9.0% as in Example 3,
(48% strength in water, pH 5,5) Texapon .RTM. N70 (70% sodium
lauryl ether sulfate, 32.0% Henkel KGaA) Tagat .RTM.R40 (PEG-40
ethoxylate of hydrogenated 5.0% castor oil, Th. Goldschmidt AG)
Tego .RTM. glucoside 810 (60% caprylic/capric 9.0% glucoside, Th.
Goldschmidt AG) Citric acid (20%) 0.9% NaCl (25%) 8.5% Water 17.6%
Tego .RTM. betaine F50 (37,5% cocoamidopropyl- 18.0% betaine, Th.
Goldschmidt AG)
Example 13
[0078] O/W-based care cream
7 Poly(aspartic acid-co-cetyl aspartate), 4.5% as in Example 5,
(50% strength in water, pH 5,5) Tego .RTM. care 450 (polyglyceryl-3
methylglucoside 1.0% distearate, Th. Goldschmidt AG) Tegin .RTM. M
(glyceryl stearate, Th. Goldschmidt AG) 0.5% Tego .RTM. alkanol 18
(stearyl alcohol, 0.3% Th. Goldschmidt AG) Avocado oil 12.0%
Tegosoft .RTM. CT (caprylic/capric triglyceride, 9.0% Th.
Goldschmidt AG) Glycerol 3.0% Water 69.7% NaOH (10%) ad pH 5.5
[0079] While the invention has been particularly shown and
described with respect to preferred embodiments thereof, it will be
understood by those skilled in the art that the foregoing and other
changes in form and details may be made therein without departing
from the spirit and scope of the invention.
* * * * *