DE102009033638A1 - New formamide compounds useful as reactive amide for preparing oligomers and/or polymers by e.g. polycondensation, and for preparing e.g. adhesives, lacquers, polyurethane-molded bodies or foamed bodies, sealants, elastomers and plastics - Google Patents

Abstract

Formamide compounds (I) are new. Formamide compounds of formula (X-[-N(CHO)] n) (I) are new. X : n-valent aliphatic, cycloaliphatic or aromatic groups (preferably bi- or tri-valent aliphatic or cycloaliphatic groups); and n : not defined. An independent claim is included for the preparation of (I).

Description

The Invention relates to novel formamides based on defined mono-, Di- or triamines and thus formamide-terminated low molecular weight Links.

So far, the synthesis of formamides by the reaction of amines with formic acid has been described ( JP-A 2004 269 375 ).

The implementation of the reaction under the influence of microwaves is in Journal of Chinese Chemical Society, Taipei, Taiwan, 2007, 54 (2), 479-481 described.

Another possibility for the formation of formamides is in DE-A 4 024 466 described. This involves the reaction of amino alcohols in solvents with formic acid or alkyl formate, partly with the aid of a catalyst.

higher molecular weight Polyetheramines can be used with alkyl formates to the corresponding formamide-terminated oligomers to low viscosity Acylharnstoffprepolymeren be implemented.

For numerous applications are the Polyetherstruktureinheiten the oligomeric formamides adversely, since thereby applications with high demands on light fastness are excluded.

It it has now surprisingly been found that it is possible is stable, low-color formamide-terminated low molecular weight compounds without such Polyetherstruktureinheiten and without the use of solvents and produce additional catalysts.

object the invention are formamides of defined mono-, di- or triamines and thus formamide-terminated low molecular weight compounds. she are characterized in that they are liquid at ambient temperature are.

object The invention also formamides based on defined low molecular weight mono-, Di- or triamines, which are solid or crystalline at ambient temperature are.

The Formamides according to the invention based on defined Low molecular weight mono-, di- or triamines are also elevated Temperature stable in storage, color bright and light stable.

Formamidterminierte Low molecular weight compounds are, for example, by reaction of formic acid C1-C4 alkyl esters with suitably defined Amines accessible.

suitable Amines are, for example, mono-, di- and / or triamines with linear and / or branched and / or substituent-carrying and / or heteroatoms, For example, oxygen atoms, containing aliphatic, cycloaliphatic, Heterocyclic and / or aromatic structural units with 2 to 40, preferably 2 to 20 C-atoms. They have a molecular weight from 45 to 700, preferably 60 to 300 g / mol.

The following Monoamines can z. B. be used: ethylamine, propylamine, Isopropylamine, n-butylamine, t-butylamine, n-pentylamine, n-hexylamine, n-octylamine, 2-ethylhexylamine, tridecylamine (mixture of isomers), 3-methoxypropylamine, 2-ethoxyethylamine, 3-ethoxypropylamine, 3- (2-ethylhexyloxy) propylamine, Cyclopentylamine, cyclohexylamine, 1-phenylamine, benzylamine, 2-phenylethylamine, Aniline, o-toluidine, 2,6-xylidine, 2- (diethylamino) ethylamine, 3- (dimethylamino) propylamine.

Suitable di- or triamines may be aliphatic amines z. For example, ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,4-butanediamine, neopentanediamine, 1,5-diamino-2-methylpentane (Dytek ^® A, DuPont), 2-butyl-2-ethyl-1 , 5-pentanediamine, 1,6-hexamethylenediamine, 2,5-diamino-2,5-dimethylhexane, 2,2,4- and / or 2,4,4-trimethyl-1,6-diaminohexane, 1,8- Diaminooctane, 1,11-diaminoundecane, 1,12-diaminododecane, 4-aminomethyl-1,8-octanediamine (triaminononane), diethylenetriamine, triethylenetetramine, cycloaliphatic amines such. For example, 1-amino-3,3,5-timethyl-5-aminomethyl-cyclohexane (isophorone diamine, IPDA), TCD-diamine, 1,4-cyclohexanediamine, 2,4- and / or 2,6-hexahydrotoluylenediamine (H ₆ TDA), isopropyl-2,4-diaminocyclohexane and / or isopropyl-2,6-diaminocyclohexane, tricyclodecanebis (methylamine), 1,3-bis- (aminomethyl) -cyclohexane, 2,4'- and / or 4,4 ' diaminodicyclohexylmethane (PACM 20), 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane (Laromin C 260 ^®, BASF AG, DE), the isomers, a methyl group (as ring substituent having diaminodicyclohexylmethanes = C-monomethyl-diaminodicyclohexyl methanes ), 3 (4) -aminomethyl-1-methylcyclohexylamine (AMCA) and araliphatic di- or triamines, such as. B. 1,3-diaminobenzene, 1,4-diaminobenzene, 2,4- and / or 2,6-diaminotoluene (TDA), 1,3-bis (aminomethyl) benzene, 3,5-diethyltoluene-2, 4-diamine, m-xylylenediamine. 4,6-dimethyl-1,3-benzenedimethanamine, 4,4'- and / or 2,4'- and / or 2,2'-methylenebisbenzolamine (MDA), or heteroatom-containing amines, dimer fatty acid diamine, bis (3-methyl) aminopropyl) -methylamine, 4,9-dioxadodecane-1,12-diamine, 4,7,10-trioxatridecane-1,13-diamine, alkoxysilane-containing diamines used. Also suitable are Michael adducts, z. B. by reaction of bifunctional, primary amines containing unsaturated groups Compounds, such. B hexanediol diacrylate etc. can be obtained. It is also possible to use mixtures of different amines.

Preferred mono-, di- or triamines are ethylamine, propylamine, isopropylamine, n-butalamine, n-pentylamine, n-hexylamine, n-octylamine, 2-ethylhexylamine, 2-ethoxyethylamine, 3-ethoxypropylamine, cyclopentylamine, cyclohexylamine, 1-phenylamine , benzylamine, o-toluidine, 2,6-xylidine, ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,4-butanediamine, neopentanediamine, 1,5-diamino-2-methylpentane (Dytek ^® A, DuPont ), 2-butyl-2-ethyl-1,5-pentanediamine, 1,6-hexamethylenediamine, 2,5-diamino-2,5-dimethylhexane, 2,2,4- and / or 2,4,4-trimethyl -1,6-diaminohexane, 1,8-diaminooctane, 1,11-diaminoundecane, 1,12-diaminododecane, 4-aminomethyl-1,8-octanediamine (triaminononane), diethylenetriamine, triethylenetetramine, 1-amino-3,3, 5-trimethyl-5-aminomethylcyclohexane (isophoronediamine, IPDA), 1,4-cyclohexanediamine, 2,4- and / or 2,6-hexahydrotoluylenediamine (H ₆ TDA), 2,4'- and / or 4,4 'diaminodicyclohexylmethane (PACM 20), 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane (Laromin C 260 ^®, BASF AG, DE), the isomers, a Methyl-containing diaminodicyclohexylmethane (= C-monomethyl-diaminodicyclohexylmethane), 2,4- and / or 2,6-diaminotoluene (TDA), 1,3-bis- (aminomethyl) -benzene, 3,5-diethyltoluene-2, 4-diamine, m-xylylenediamine, 4,6-dimethyl-1,3-benzenedimethanamine, 4,4'- and / or 2,4'- and / or 2,2'-methylenebisbenzeneamine (MDA) and 4,7, 10-trioxatridecane-1,13-diamine.

Particularly preferred mono-, di- or triamines are ethylamine, propylamine, isopropylamine, n-butalamine, n-pentylamine, n-hexylamine, cyclopentylamine, cyclohexylamine, benzylamine, o-toluidine, 2,6-xylidine, ethylenediamine, 1,3- propylenediamine, 1,4-butanediamine, neopentanediamine, 1,5-diamino-2-methylpentane (Dytek ^® A, DuPont), 2-butyl-2-ethyl-1,5-pentanediamine, 1,6-hexamethylenediamine, 2,2 , 4- and / or 2,4,4-trimethyl-1,6-diaminohexane, 1,8-diaminooctane, 1,11-diaminoundecane, 1,12-diaminododecane, 4-aminomethyl-1,8-octanediamine (triaminononane) , Diethylenetriamine, triethylenetetramine, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane (isophoronediamine, IPDA), 2,4- and / or 2,6-hexahydrotoluylenediamine (H ₆ TDA), 2,4 ' and / or 4,4'-diaminodicyclohexylmethane (PACM 20), 2,4- and / or 2,6-diaminotoluene (TDA), m-xylylenediamine, 4,4'- and / or 2,4'- and / or or 2,2'-methylenebisbenzolamine (MDA) and 4,7,10-trioxatridecane-1,13-diamine.

The production of the formamides according to the invention can be carried out in various ways:
The reaction of the mono-, di- and / or triamine can be carried out in an excess of formic acid alkyl ester at the boiling temperature of the formic acid ester, after which reaction of the amino to the formamide group the excess of formic acid alkyl ester and the likewise resulting alcohol is distilled off.

Possible is still the implementation of mono-, di- or triamines to the formamide-terminated low molecular weight compounds with formic acid or other formic acid derivatives, such as carbon monoxide, mixed Formic acid carboxylic anhydrides, low molecular weight Amides or active esters of formic acid or preliminary Reaction products of formic acid with amide coupling reagents, such as carbodiimides or condensed Phosphosäurederivaten.

Prefers the conversion to the formamide takes place in an excess on formic acid C1-C4-alkyl ester. One mole of diamine is added an excess of from 2 to 6 moles of C1-C4 alkyl formate, more preferably 2.5 to 4 mol, preferably methyl formate and / or Ethyl formate and particularly preferably ethyl formate, at the boiling point of the formic acid ester reacted under nitrogen. at For the aliphatic amines, the reaction usually proceeds strongly exothermic. After 2 to 4 hours of reflux is the Reaction of amino to formamide group completed (review by gas chromatography) and the excess of formic acid alkyl ester and the likewise resulting alcohol, preferably methanol or Ethanol, is distilled off under vacuum.

The Use of ethyl formate has the advantage that the products have little discoloration, other alkyl formates lead to slightly stronger discoloration in the case of the formamides according to the invention, the products but are still relatively bright colors.

Likewise possible, the formamide, or the strong base-generated anion of the formamide, with alkylating reagents of the formula (I) X- [A] _n (I) where X is an aliphatic, cycloaliphatic or aromatic radical, n is a natural number from 2 to 3 and A is a leaving group such as chloride, bromide, iodide, mesylate, tosylate or triflate.

The Products of the invention are also distinguished in that they have excellent storage stability exhibit, it does not come to discoloration during storage or precipitates.

The formamides according to the invention are at Room temperature solid or liquid, storage-stable and bright products.

object The invention also provides a process for the preparation of low molecular weight formamides from mono-, di- and / or triamines, characterized in that an excess of formic acid alkyl ester to the pure mono-, di- and / or triamine is added dropwise and after completion of the reaction the excess formic acid alkyl ester and the resulting alcohol is distilled off and after the finished Reaction the resulting products if desired filtered off becomes.

object In the invention, the conversion to the formamide is preferably in excess Formic acid C1-C4 alkyl ester carried out, wherein one mole of diamine with an excess of 2 to 6 moles of C1-C4 alkyl ester, particularly preferably 2.5 to 4 mol, preferably methyl formate or Ethyl formate, at the boiling point of the formic acid ester are reacted, after the reaction of the amino to the formamide group the excess of formic acid alkyl ester and the likewise formed alcohol, preferably methanol or ethanol, be distilled off.

The Formamides of the invention are basically suitable as reactive amides for the preparation of oligomers and / or Polymers by polycondensation, polymerization and / or polyaddition.

The Formamides of the invention are basically suitable as reactive amides for the production of paints, coatings, Sealants, adhesives, inks, printing inks, sizes, foams, Moldings, elastomers, plastics, fibers, fabrics.

Examples:

Used starting materials:

• 2-methyl-1,5-diaminopentane, a difunctional, amino-terminated, branched, aliphatic compound,
• 4,4'-diaminodicyclohexylmethane (PACM 20), a difunctional, amino-terminated, cycloaliphatic compound,
• 3,5-diethyltoluene-2,4-diamine, a difunctional, amino-terminated, aromatic compound,
• 4,7,10-Trioxatridecane-1,13-diamine, a difunctional, amino-terminated one Compound, 4-aminomethyl-1,8-octanediamine, a trifunctional, amino-terminated, aliphatic compound,
• ethyl acetate,
• benzoyl chloride,
• Irganox ^® 1076 (Ciba, CH), a sterically hindered phenol.

example 1

you drips at a maximum of 50 ° C to 612 g of 2-methyl-1,5-diaminopentane within 4 hours 1173 g of ethyl formate and leaves Stir under reflux for 4 h. Then the excess of formic acid ethyl ester and the ethanol formed distilled off.

you receives a formamide-terminated low molecular weight compound with a viscosity of 581 mPas, a calculated molecular weight of 172 g / mol, an equivalent weight of 86 g, which is colorless and storage stable for several weeks at 40 ° C.

Example 2

you drops at a maximum of 50 ° C to 420 g PACM 20 within 3 h 445 g of ethyl formate and allowed 4 h stir under reflux. Then the excess Formic acid ethyl ester and the formed and used Distilled off ethanol.

you receives a formamide-terminated low molecular weight compound with a melting point of 190-195 ° C, a calculated Molecular weight of 266 g / mol, an equivalent weight of 133 g, which is colorless and over several weeks at 40 ° C. storage stable.

Example 3

you drips at a maximum of 50 ° C to 366 g of 3,5-diethyltoluene-2,4-diamine within 1 h 445 g of ethyl formate and leaves Stir under reflux for 4 h. Then the excess of formic acid ethyl ester and the formed and used ethanol distilled off.

you receives a formamide-terminated low molecular weight compound with a viscosity of 196 mPas, a calculated molecular weight of 234 g / mol, an equivalent weight of 113 g, which is nearly colorless and is storage stable for weeks at 40 ° C.

Example 4

you 793 g of 4,7,10-trioxatridecane-1,13-diamine is added dropwise at a maximum of 50 ° C within 3 h 800 g of ethyl formate and leaves Stir under reflux for 4 h. Then the excess Formic acid ethyl ester and the formed and used Distilled off ethanol.

you receives a formamide-terminated low molecular weight compound with a viscosity of 239 mPas, a calculated molecular weight of 276 g / mol, an equivalent weight of 138 g, which is colorless and storage stable for weeks at 40 ° C.

Example 5

you drops at a maximum of 50 ° C to 346 g of 4-aminomethyl-1,8-octanediamine within 3 h 667 g of ethyl formate and let Stir under reflux for 4 h. Then the excess of formic acid ethyl ester and the formed and used ethanol distilled off.

you receives a formamide-terminated low molecular weight compound with a viscosity of 10200 mPas, a calculated Molecular weight of 257 g / mol, an equivalent weight of 86 g, the is colorless and stable for weeks at 40 ° C.

Example 6

you drops at a maximum of 50 ° C to a mixture of 116 g of 2-methyl-1,5-diaminopentane and 186 g of 2-butyl-2-ethylpentane-1,5-diamine within 3 h 445 g of ethyl formate and allowed to reflux for 4 h stirred. Then the excess Formic acid ethyl ester and the formed and used Distilled off ethanol.

you receives a mixed formamide-terminated low molecular weight Compound with a viscosity of 7770 mPas, a medium calculated molecular weight of 207 g / mol, an equivalent weight of 103.5 g, which is colorless and over weeks at 40 ° C storage stable.

In terms of Shelf life is an example number one here singled out. The viscosity increase at 4 weeks storage at 40 ° C is 7.4%.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - JP 2004269375 A [0002]
• - DE 4024466 A [0004]

Cited non-patent literature

• - Journal of Chinese Chemical Society, Taipei, Taiwan, 2007, 54 (2), 479-481 [0003]

Claims (12)

Formamide of the general formula I. X - [- N (CHO)] _n (I) in which X is an n-valent aliphatic, cycloaliphatic or aromatic radical. Formamides according to claim 1, at where X is a dihydric to trihydric aliphatic or cycloaliphatic radical. Process for the preparation of formamides according to claim 1, characterized in that mono-, di- and / or triamines solvent-free and without additional catalyst with alkyl formate formamidterminierten low molecular weight compounds are reacted and the excess of alkyl formate present and the resulting Alcohol are separated by distillation. A method according to claim 3, characterized in that the mono-, di- and / or triamines are linear or branched aliphatic, cycloaliphatic, heterocyclic and / or contain aromatic structural units having 2 to 40 carbon atoms and have a molecular weight of 45 to 700. Use of formamides according to claims 1 to 2 as reactive amides for the preparation of oligomers and / or Polymers by polycondensation, polymerization and / or polyaddition. Use of formamides according to claims 1 to 2 for the preparation of coating compositions. Use of formamides according to claims 1 to 2 for the production of adhesives. Use of formamides according to claims 1 to 2 for the production of paints. Use of formamides according to claims 1 to 2 for the production of PUR molded or foam bodies. Use of formamides according to claims 1 to 2 for the production of sealants. Use of formamides according to claims 1 to 2 for the preparation of elastomers. Use of formamides according to claims 1 to 2 for the production of sizes and plastics.