Carbodiimides with carboxyl or carboxylate groups

Details Carbodiimides with carboxyl or carboxylate groups Carbodiimides with carboxyl or carboxylate groups

2002-03-29

2004-05-04

Shippen, Michael L. (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Carboxylic acids and salts thereof

C528S061000, C562S440000

Reexamination Certificate

active

06730807

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to compounds containing carbodiimide units and carboxyl or carboxylate groups (compounds V), derived from
a) aliphatic or araliphatic C
4
to C
20
polyisocyanates (component a)
b) amino carboxylic acids or amino carboxylic salts (component b) and
c) if desired, further compounds which carry groups able to react with isocyanate groups in an addition reaction (component c)
d) if desired, other isocyanates (component d),
the carbodiimide units deriving essentially exclusively from the isocyanate groups of component (a).
2. Description of the Background
Organic carbodiimides and their use as additives to aqueous polymer dispersions are known. It is also known that these polymer dispersions, for example, are added in order to increase the molecular weight of the polymers. To permit the carbodiimides to be dispersed simply and homogeneously in the dispersion, they are provided with hydrophilic groups.
EP-A-198 343 describes carbodiimides which carry sulfonate groups and, if desired, polyethylene oxide units as well.
EP-A-686 626, furthermore, discloses carbodiimides in which the hydrophilicity is brought about by means of ammonium groups, which are introduced by way of dialkylamino alcohols, by means of sulfonate groups which are introduced by way of salts of hydroxy-functional alkylsulfonic acids, or by means of polyethylene oxide radicals.
The abovementioned products, however, have the following disadvantages:
Cationic products such as carbodiimides hydrophilicized by ammonium groups are not compatible with the anionically stabilized dispersions commonly used.
The carbodiimides hydrophilicized with sulfonate groups are difficult to prepare. Because of the highly lipophobic character of the salts used as starting compounds, the reaction with the hydrophobic isocyanato-containing precursors is extremely difficult, since the mutual solubility is very low.
The dispersions cured with carbodiimides hydrophilicized with polyalkylene oxide radicals possess a permanent hydrophilicity which is unwanted.
DE-A-19821668, unpublished at the priority date of the present specification, discloses carbodiimides based on 1,3-bis(1-methyl-1-isocyanatoethyl)benzene in which the hydrophilicization is brought about with amino sulfonic acids.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide carbodiimides which are compatible with the customary, anionically stabilized polymer dispersions, are easy to prepare, and do not impart any additional, permanent hydrophilicity to the dispersion films cured with them.
The compounds (V) contain preferably from 200 to 2000 mmol/kg, with particular preference from 500 to 1800 mmol/kg, of carboxyl or carboxylate groups, based on the weight of the carbodiimides.
The proportion of carbodiimide groups is generally from 0.05 to 8, preferably from 0.10 to 5, mol/kg based on the weight of the carbodiimides.
The carbodiimide units in the carbodiimides of the invention are formed essentially by the combination of pairs of NCO groups of component (a) with elimination of carbon dioxide, so forming a carbodiimide.
The compounds (V) contain preferably at least one carbodiimide structure, preferably more than one carbodiimide structure; with particular preference, the (number-)average degree of condensation, i.e., the average number of carbodiimide structures in the carbodiimides of the invention, is from 1 to 20, in particular from 2 to 15.
Suitable monomers (a) are the aliphatic or araliphatic isocyanates having 4 to 20 carbon atoms that are commonly used in polyurethane chemistry.
Mention may be made in particular of diisocyanates X(NCO)
2
, where X is an aliphatic hydrocarbon radical having 4 to 12 carbon atoms, a cycloaliphatic hydrocarbon radical having 6 to 15 carbon atoms, or an araliphatic hydrocarbon radical having 7 to 15 carbon atoms. Examples of diisocyanates of this kind are tetramethylenediisocyanate, hexamethylenediisocyanate, dodecamethylenediisocyanate, 1,4-diisocyanatocyclohexane, 1-isocyanato-3,5,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,2-bis(4-isocyanatocyclohexyl)propane, trimethylhexane diisocyanate, 1,4-diisocyanatobenzene, 1,3-bis(1-methyl-1-isocyanatoethyl)benzene (TMXDI), the isomers of bis(4-isocyanatocyclohexyl)methane (HMDI) such as the trans/trans, the cis/cis and the cis/trans isomer, and mixtures of these compounds.
The carbodiimides of the invention therefore preferably comprise units of the formula I
—X—N═C═N—X—[—N═C═N—X—]
n
—  I
where
X is as defined above, and
n is an integer from 0 to 10, preferably 0, 1, 2 or 3.
With particular preference, X is derived from TMXDI or hexamethylenediisocyanate.
Suitable amino carboxylic acids and salts thereof (component B) are, for example, the alpha-amino carboxylic acids specified in Fieser and Fieser, Organische Chemie, 2nd, improved edition, 1982, on p. 1260 ff.; preferably: beta-amino carboxylic acids such as &bgr;-alanine or the Michael adducts of diprimary diamines with &agr;,&bgr;-unsaturated carboxylic acids. Where the amino carboxylic acids are used in the form of their salts, particularly suitable salts are alkali metal, alkaline earth metal, or ammonium salts.
Such compounds conform, for example, to the formula (II)
H
2
N—R
4
—NR—R
5
—X  (II)
where
—R
4
and R
5
, independently of one another, are a C
1
to C
6
alkanediyl unit, preferably ethylene,
and X is COOH or a carboxylate group.
Particularly preferred compounds of the formula (II) are N-(2-aminoethyl)-2-aminoethanecarboxylic acid and the corresponding alkali metal salts, Na being the particularly preferred counterion.
Preferred compounds (V) are those of the formula III
R
1
—CO—NH—X—N═C═N—X—[—N═C═N—X—]
n
—NH—CO—R
2
  III
where n and X are as defined for formula I and R
1
and R
2
are radicals derived from component (b) by abstracting therefrom a hydrogen atom attached to an amino group.
The compounds (V) may, if desired, further comprise, in addition to the structural units derived from components (a) and (b), further structural units which are derived from components (c) and (d) and which comprise primarily urethane units or urea units. These units are formed by reacting the isocyanate groups of the component (d) with the isocyanate-reactive groups of component (c) or with the amino groups of component (b) or by reacting isocyanate-reactive groups of component (c) with the isocyanate groups of component (a). By means of the structural units derived from components (c) and (d), therefore, the structural units of the formula I are interrupted or terminated or are located between a structural unit formed from component (a) and (b). Components (c) and (d) thus serve primarily to regulate the molecular weight, since components (c) and (d) act primarily as chain extenders or chain terminators.
Components (c) carry groups which are able to react with isocyanate groups in an addition reaction. For example, standard substances may be used which by virtue of their reaction with isocyantes produce urethane groups or urea groups. For example, aromatic, aliphatic or araliphatic compounds having 1 to 20 carbon atoms may be used whose isocyanate-reactive groups comprise hydroxyl and/or amino groups. Preferred compounds having at least two isocyanate-reactive groups are organic compounds having at least two hydroxyl groups, having at least two amino groups and/or having at least one hydroxyl group and at least one amino group. Examples which may be used include the following: aromatic, araliphatic and/or aliphatic polyols having 2 to 20 carbon atoms, preferably those having primary hydroxyl groups. Examples that may be mentioned include: 1,2-ethanediol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 2,4-butanediol and/or 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,10-decanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2- and 3-methyl-1,5-pentanediol, polyethylene glycols, polypropylene glycols, preferably h

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