DE10332152A1 - New perfluoroalkyl-(poly)-uretdiones, used as hardener in (ultra)hydrophobic coating composition, chain extender or chemical modifier, are prepared from functionalized perfluoroalkyl compound and polyisocyanate with uretdione group - Google Patents

Abstract

New (poly)-uretdiones (I) with end and/or side perfluoroalkyl groups are derived from starting components including (A) mono-, di- and/or poly-functionalized perfluoroalkyl compound(s) with trifluoromethyl end group(s) as end and/or side groups and other isocyanate (NCO)-reactive functional group(s) and (B) polyisocyanate(s) with uretdione group(s). (I) contain 0-5 wt.% free NCO groups, melt in the 40-200[deg]C range and have number average molecular weight 500-10000. New (poly)-uretdiones (I) with end and/or side perfluoroalkyl groups are derived from the starting components (A) mono-, di- and/or poly-functionalized perfluoroalkyl compound(s) with trifluoromethyl end group(s) as end and/or side group and other isocyanate (NCO)-reactive functional group(s), (B) polyisocyanate(s) with uretdione group(s) and optionally (C) di- and/or polyols, di- and/or polyamines and/or amino alcohols, (D) di- and/or polyols containing other functional groups, (E) polyisocyanates without uretdione groups and/or (F) NCO-reactive monofunctional compounds. (I) contain 0-5 wt.% free NCO groups and have a melting range between 40 and 200[deg]C and number average molecular weight Mn in the 500-10000 range. An independent claim is also included for the preparation of (I).

Description

The Invention relates to (poly) uretdiones with chemically coupled perfluoroalkyl compounds, for example, together with a resin as a paint with (ultra) hydrophobic surface properties for flat structures such as façade and room elements, traffic control systems and commercial vehicles can be used and a process for their preparation.

functionalized perfluorinated alkanoic acid amides are not yet for Polyaddition reactions for the production of resins, hardeners, additives and chain extender with chemically bound Perfluoralkansäureamiden as end and side groups described.

Substance classes based on a perfluorinated acid amide group have been disclosed in the following documents:
The synthesis of perfluoroalkyl-containing amino acids has been described in US 3,238,235 first described. Such amino acids are used as surface-active substances.

In US 3,944,610 describes the synthesis of N, N'-bis-aminoalkylamide-modified polyoxaperfluoroalkanedioic acids which are used as surface-active substances.

In DD 265 398 A1 there is described a production process of perfluorinated imino-bis (polyoxyalkylenes) in which perfluorinated N, N-bis (2-hydroxyethyl) carboxamide intermediates were used as nonionic surfactants.

In US 5,756,000 Perfluoralkoxycycloalkansäurefluoride were preferably realized by means of an electrochemical fluorination of alkoxybenzoyl derivatives, which then gave by further functionalization of the corresponding acid amides. They are used as surface-active substances in aqueous systems.

In US 6,111,050 describes the use of perfluorinated amides as main chain segments in crosslinkable materials, utilizing perfluoroalkyl-containing trifunctionalized crosslinkers that react with the secondary amino groups of the functionalized perfluorinated amides.

Out the (patent) literature are not yet indications for the production of perfluoroalkyl group-containing (poly) uretdiones, as a hardener in coating agents, as chain extenders and in chemical modification reactions (e.g., polymer analogous reactions) of compounds.

task The invention was therefore (poly) uretdiones with perfluoroalkylgruppenhaltigen End and / or side groups based on chemically bound mono-, di- and / or polyfunctionalized To find perfluoroalkyl compounds by means of polyaddition reactions, which is then preferred for further use in coating compositions Powder coatings, hydrophobic to ultrahydrophobic surface properties exhibit. Furthermore, the (poly) uretdiones as chain extenders and in polymer-analogous reactions to build perfluoroalkylgruppenhaltiger Connections can be used.

The Task is solved according to the claims.

• A) mindestens eine mono-, di- und/oder polyfunktionalisierie Perfluoralkylverbindung mit mindestens einer Trifluormethylendgruppe als End- und/oder Seitengruppe und mindestens einer weiteren gegenüber Isocyanaten reaktiven funktionellen Gruppe, und
• B) mindestens ein Polyisocyanat mit mindestens einer Uretdiongruppe, und gegebenenfalls
• C) Di- und/oder Polyole, und/oder Di- oder Polyamine und/oder Aminoalkohole, und/oder
• D) weitere funktionelle Gruppen enthaltende Di- und/oder Polyole, und/oder
• E) Polyisocyanate ohne Uretdiongruppen und/oder
• F) gegenüber Isocyanaten reaktiven monofunktionellen Verbindungen,

wobei die perfluoralkylgruppenhaltigen (Poly-)Uretdione einen Gehalt an freien NCO-Gruppen von 0 bis 5 Gew.-%, einen Schmelzbereich zwischen 40 und 200 °C und zahlenmittlere Molmassen im Bereich von 500 bis 10000 aufweisen.The invention relates to (poly) uretdiones with terminal and / or pendant perfluoroalkyl groups composed of the starting components

• A) at least one mono-, di- and / or polyfunctionalized perfluoroalkyl compound having at least one trifluoromethylene end group as end and / or side group and at least one further isocyanate-reactive functional group, and
• B) at least one polyisocyanate having at least one uretdione group, and optionally
• C) di- and / or polyols, and / or di- or polyamines and / or amino alcohols, and / or
• D) further functional groups containing di- and / or polyols, and / or
• E) polyisocyanates without uretdione groups and / or
• F) isocyanate-reactive monofunctional compounds,

wherein the perfluoroalkyl-containing (poly) uretdiones have a content of free NCO groups from 0 to 5 wt .-%, a melting range between 40 and 200 ° C and number average molecular weights in the range of 500 to 10,000.

mit m ≥ 1; n = 0 bis 1; o ≥ 1The following components are used for the preparation of the linear or branched (poly) uretdiones:
Component A) is described schematically as follows:

with m ≥ 1; n = 0 to 1; o ≥ 1

The used perfluoroalkyl compounds (component A) in the inventive (poly) uretdiones are functionalized perfluoroalkyl compounds with at least a Trifluormethylendgruppe, which also acid amide and / or sulfonic acid amide groups can have.

typical general representative for functionalized perfluoroalkanoic acid amides, Perfluoralkansulfonsäureamide and perfluoroalkyl compounds are the following compounds: a) functionalized N-spacer chain-bearing perfluoroalkanoic acid amides and perfluoroalkanesulfonic acid amides, b) functionalized N, N-bis-spacer chain-bearing perfluoroalkanoic acid amides and perfluoroalkanesulfonic acid amides and c) functionalized N-spacer chain-bearing and non-functionalized N-alkyl spacer chains bearing perfluoroalkanoic acid amides and perfluoroalkanesulfonic acid amides and d) functionalized spacer chain-bearing perfluoroalkyl compounds. Possess the functionalized spacer chain carrying units at least one functional group necessary for the production of (poly) uretdiones with chemically coupled perfluoroalkanoic acid amides, perfluoroalkanesulfonic acid amides and perfluoroalkyl compounds as end and / or side group is needed. The functionalized spacer chain-carrying units of the functionalized Perfluoralkansäureamide, Perfluoralkansulfonsäureamide and perfluoroalkyl compounds are linear and / or branched units.

The Perfluoroalkyl compounds are preferred as functional groups Hydroxy and / or primary and / or secondary Amino groups or free isocyanate groups on.

The functionalized spacer chain units of the functionalized Perfluoroalkyl compounds are preferably functionalized alkylene chains and / or functionalized arylene chains and / or functionalized Alkylenearylene chains and / or functionalized alkylenearylenealkylene chains and / or functionalized arylenealkylene chains and / or functionalized Arylenalkylenarylenketten. All functionalized spacer chain units can additionally cycloaliphatic and / or heterocyclic units.

The spacer chains have a chain length of C ₁ -C ₆₀ atoms, which may themselves have functional groups which do not react under the given reaction conditions of the polyaddition reactions. As functional groups in the spacer chains can be included: ether, ester, tertiary amino, amide, sulfone, sulfonamide, sulfide, imide, urea and urethane groups and CC double bonds.

The non-functionalized alkyl spacer chains have a chain length of C ₁ -C ₂₀ atoms.

mit m ≥ 1; n = 0 bis 1, o ≥ 1; p = 1 bis 10The perfluoroalkyl radical of the perfluoroalkyl compounds has at least one trifluoromethylene end group and / or side group and a chain length of 2 to 35 carbon atoms. By perfluoroalkyl radical is meant that all carbon atoms are substituted with fluorine. In this case, heteroatoms, preferably oxygen, may be present in the perfluoroalkyl radical. These are, for example, monofunctionalized perfluoroalkyl ethers of the following structure:

with m ≥ 1; n = 0 to 1, o ≥ 1; p = 1 to 10

Typical representatives of component A) are the following N-monosubstituted and N, N-disubstituted perfluoroalkanoic acid amides and / or perfluoroalkanesulfonic acid amides and perfluoroalkanols and / or perfluoroalkanediols: N- (3-hydroxyprop-1-yl) perfluorooctanoic acid amide, N- [3- (methylamino) prop-1-yl] perfluorooctanoic acid amide, N- (11-hydroxyundec-1-yl) perfluorooctane acid amide, N- (5,6-dihydroxyhex-1-yl) perfluorooctanoic acid amide, N-ethyl-N- (5-hydroxy-methyl -6-hydroxyhex-1-yl) perfluorooctanoic acid amide, N- (5-hydroxymethyl-6-hydroxyhex-1-yl) perfluorooctanoic acid amide, N- (3-aminoprop-1-yl) perfluorooctanoic acid amide, N- (4-aminoethyl-6- aminohex-1-yl) perfluorooctanoic acid amide, N, N-bis (4-hydroxybut-1-yl) perfluorooctane acid amide, N- (6,7-dihydroxy-4-oxahept-1-yl) perfluorooctanoic acid amide, N- ( 8,9-dihydroxy-6-oxanon-1-yl) perfluorooctanoic acid amide, N, N-bis (6-hydroxyhex-1-yl) perfluorooctanoic acid amide, N-methyl-N- (4-hydroxybut-1-yl) perfluorohexanoic acid a mid, N- (4-aminoethyl-6-hydroxyhex-1-yl) perfluorooctanoic acid amide, N- (4-hydroxyethyl-6-hydroxyhex-1-yl) perfluorooctanoic acid amide, N- (3- (2-hydroxyethyl) aminoprop-1 yl) perfluorooctanoic acid amide, N- (3-hydroxypent-1-yl) perfluorooctanoic acid amide, N, N, - (bis (2-hydroxyethyl) perfluorooctanoic acid amide, N- (3-hydroxyprop-1-yl) perfluorooctanesulfonic acid amide, N- [3- ( Methylamino) prop-1-yl] perfluorooctanesulfonic acid amide, N- (11-hydroxyundec-1-yl) perfluorohexanesulfonic acid amide, N- (5,6-dihydroxyhex-1-yl) perfluorohexanesulfonic acid amide, N-ethyl-N- (5- Hydroxymethyl-6-hydroxyhex-1-yl) perfluorooctanesulfonic acid amide, N- (5-hydroxymethyl-6-hydroxyhex-1-yl) -perfluorohexanesulfonic acid amide, N- (3-aminoprop-1-yl) perfluorooctanesulfonic acid amide, N- (4- Aminoethyl-6-aminohex-1-yl) perfluorooctanesulfonic acid amide, N, N-bis (4-hydroxybut-1-yl) perfluorooctanesulfonic acid amide, N- (6,7-dihydroxy-4-oxahept-1-yl) perfluorooctanesulfonic acid amide, N- (8,9-Dihydroxy-6-oxanon-1-yl) perfluorooctane sulfonic acid amide, N, N-bis (6-hydroxyhex-1-yl) perfluorooctane sulfone ureamide, N-methyl-N- (4-hydroxybut-1-yl) perfluorohexanesulfonic acid amide, N-methyl-N- (3-hydroxyprop-1-yl) perfluorohexanesulfonic acid amide, N- (4-aminoethyl-6-hydroxyhex-1-yl ) perfluorooctanesulfonic acid amide, N- (4-hydroxyethyl-6-hydroxyhex-1-yl) perfluorooctanesulfonic acid amide, 1H, 1H, 2H, 2H, 3H, 3H, 4H, 4H-perfluorododecan-1-ol, 1H, 1H, 2H, 2H- Perfluorodecan-1-ol, 1H, 1H, 2H, 2H, 3H, 3H, 4H, 4H, 5H, 5H, 6H, 6H, 7H, 7H, 8H, 8H, 9H, 9H, 10H, 10H-perfluoricosan-1 ol, 1H, 1H, 2H, 2H, 3H, 3H-perfluoroundecan-1-ol, 1H, 1H, 2H, 2H, 3H, 3H, 4H, 4H, 5H, 5H-perfluorotridecan-1-ol, 1H, 1H, 2H, 2H, 3H, 3H, 4H, 4H, 5H, 5H, 6H, 6H-perfluorotetradecan-1-ol, 1H, 1H, 2H, 2H, 3H, 3H, 4H, 4H, 5H, 5H, 6H, 6H, 7H, 7H-perfluoropentadecan-1-ol, 1H, 1H, 2H, 2H, 3H, 3H, 4H, 4H-perfluorododecane-1,2-diol, 1H, 1H, 2H, 2H, 3H, 3H, 4H, 4H 5H, 5H, 6H, 6H, 7H, 7H, 8H, 8H, 9H, 9H, 10H, 10H-perfluoricosane-1,2-diol, 1H, 1H, 2H, 2H, 3H, 3H-perfluoroundecane-1,2- diol, 1H, 1H, 2H, 2H, 3H, 3H, 4H, 4H, 5H, 5H-perfluorotridecan-1,2-diol, 1H, 1H, 2H, 2H, 3H, 3H, 4H, 4H, 5H, 5H, 6H, 6H-perfluorotetradecane-1,2-diol, 1H, 1H, 2H, 2H, 3H, 3H, 4H, 4H, 5H, 5H, 6H, 6H, 7H, 7H Perfluoropentadecane-1,2-diol, 1H, 1H, 2H, 2H, 3H, 3H, 4H, 4H-2- (hydroxymethyl) -perfluorododecan-1-ol, 1H, 1H, 2H, 2H, 3H, 3H, 4H , 4H, 5H, 5H, 6H, 6H, 7H, 7H, 8H, 8H, 9H, 9H, 10H, 10H-2- (hydroxymethyl) perfluoricosan-1-ol, 1H, 1H, 2H, 2H, 3H, 3H- 2- (hydroxymethyl) perfluoroundecan-1-ol, 1H, 1H, 2H, 2H, 3H, 3H, 4H, 4H, 5H, 5H-2- (hydroxymethyl) perfluorotridecan-1-ol, 1H, 1H, 2H, 2H , 3H, 3H, 4H, 4H, 5H, 5H, 6H, 6H-2- (hydroxymethyl) perfluorotetradecan-1-ol, 1H, 1H, 2H, 2H, 3H, 3H, 4H, 4H, 5H, 5H, 6H , 6H, 7H, 7H-2- (hydroxymethyl) perfluorpentadecan-1-ol.

The uretdione group-containing polyisocyanates of component B) having an average isocyanate functionality of at least 2.0 are prepared in a conventional manner from any diisocyanates by catalytic dimerization of a portion of the isocyanate groups of simple diisocyanates and preferably subsequent removal of the unreacted diisocyanate excess, for example by thin film distillation , receive. The diisocyanates for the preparation of the polyisocyanates B) are aliphatic, cycloaliphatic, araliphatic and / or aromatic diisocyanates. Preferred examples are 1,4-diisocyanatobutane, 1,6-diisocyanatohexane (HDI), 2-methylpentamethylene diisocyanate-1,5 (MPDI), 2,2,4- / 2,4,4-trimethylhexamethylene diisocyanate (TMDI), 4,4 '-Diisocyanatodicyclohexylmethane (H ₁₂ MDI), 1,3-diisocyanatocyclohexane, 1,4-diisocyanatocyclohexane, isophorone diisocyanate (IPDI), norbornane diisocyanate, diphenylmethane-2,4' and / or -4,4'-diisocyanate, xylylene diisocyanate or 2,4 - And 2,6-toluene diisocyanate and any mixtures of these isomers, these diisocyanates can be used alone or in mixtures for the preparation of the polyisocyanates B). The polyisocyanates containing uretdione groups can also be mixed with one another as desired.

As catalysts for the preparation of component B) from the diisocyanates mentioned, basically all known compounds which catalyze the dimerization of isocyanate groups are suitable. Examples are tertiary organic phosphines ( U.S. Patent 4,614,785 , DE-OSS 1934763, 3900053), tris (dialkylamino) -phosphines (DE-OSS 3030513, 3227779, 3437635), substituted pyridines (DE-OSS 1081895, 3739549) and substituted imidazoles or benzimidazoles ( EP 417603 ).

Preferred components B) are uretdione-containing polyisocyanates which are prepared from diisocyanates having aliphatically and / or cycloaliphatically bonded isocyanate groups. Suitable: 1,4-diisocyanatobutane, 1,6-diisocyanatohexane (HDI), 2-methylpentamethylene diisocyanate-1,5 (MPDI), 2,2,4 (2,4,4) -trimethylhexamethylene diisocyanate (TMDI), 4 , 4'-diisocyanatodicyclohexylmethane (H ₁₂ MDI), 1,3-diisocyanatocyclohexane, 1,4-diisocyanatocyclohexane, isophorone diisocyanate (IPDI), norbornane diisocyanate and any mixtures of these isomers, these diisocyanates used alone or in mixtures as starting component for component B) become.

Particular preference is given to the uretdiones of isophorone diisocyanate (IPDI), 2-methylpentamethylene diisocyanate-1,5 (MPDI), 2,2,4 (2,4,4) -trimethylhexamethylene diisocyanate (TMDI), 4,4'-diisocyanatodicyclohexylmethane ( H ₁₂ MDI), norbornane diisocyanate (NBDI) and / or 1,6-diisocyanatohexane (HDI) used.

Very particular preference is given to the uretdione of isophorone diisocyanate. The use of isophorone diisocyanate allows the preparation of an isocyanurate-free uretdione. This uretdione is highly viscous at room temperature and has a viscosity greater than 10 ⁶ mPa · s, at 60 ° C, the viscosity is 13 · 10 ³ mPa · s and at 80 ° C at 1.4 · 10 ³ mPa · s. The free NCO content is between 16.8 and 18.5 wt .-%, ie that more or less high levels of polyuretdione of IPDI must be present in the reaction product. The monomer content is 1 wt .-%. The total NCO content of the reaction product after heating at 180 to 200 ° C is 37.5 to 37.8 wt .-%.

During the Dimerization of other aliphatic diisocyanates in per se known Processes and catalysts form as by-product isocyanurate in different amounts, so that the NCO functionality of the used isocyanurate-containing polyisocyanate uretdiones between 2 and 2.6.

For the synthesis the inventive (poly) uretdiones are suitable as component C) all in PU chemistry usually used di- and / or polyols, diamines and / or polyamines and / or Amino alcohols.

As aliphatic or cycloaliphatic amines C), all primary or secondary di- or polyamines can be used. Polyamines having primary and secondary amino groups in a compound are also usable, as are mixtures of primary and / or secondary and / or primary / secondary polyamines. Preferred such polyamines are in DE 195 46 750 . DE 196 37 375 . DE 196 37 377 . DE 198 16 547 or DE 198 31 307 described.

example for preferred Compounds of component C) are ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methylpentanediol-1,5, 1,6-hexanediol, 2,2,4 (2,4,4) -trimethylhexanediol-1,6, hydroxypivalate, 1,4-di (hydroxymethyl) cyclohexane, Diethylene glycol, triethylene glycol, neopentyl glycol, trimethylol propane, Trimethylolethane, glycerol or pentaerythritol, ethanolamine, diethanolamine, triethanolamine, Diisopropanolamine, hexamethylenediamine, isophoronediamine, 2-methylpentamethylenediamine, 1,4-cyclohexanediamine, 4,4'-diaminodicyclohexylmethane. They are used individually or in mixtures.

When further functional groups containing di- and / or polyols D) suitable are linear or branched hydroxyl-containing polyesters, Polycaprolactones, polycarbonates, polyethers, polythioethers, polyesteramides, Polyurethanes or polyacetals with number average molecular weights from 134 to 6000. Preference is given to linear hydroxyl-containing Polyester and polycaprolactone used.

Especially advantageous is the use of hydroxyl-containing, linear Polyesters having a molecular weight between 250 and 2,000, preferably 300 to 1 500. They are manufactured z. B. by combination of Diols and dicarboxylic acids. For the preparation of the polyols D) are preferably in addition to the above under C) 2-methylpropanediol, 2,2-dimethylpropanediol, diethylene glycol, Dodecanediol-1,12 and trans- and cis-cyclohexanedimethanol used. To the preferred dicarboxylic acids counting aliphatic, optionally alkyl-branched dicarboxylic acids such as succinic, adipic, Cork, azelaic and sebacic acid and 2,2,4 (2,4,4) -trimethyladipic acid. Continue to be hydroxy like hydroxycaproic acid counted to it.

When Component E) are aliphatic and / or cycloaliphatic and / or used aromatic diisocyanates. Typical representative for component E are the following compounds: tetramethylene diisocyanate, hexamethylene diisocyanate, Decamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 1,3-diisocyanatocyclohexane, 1,2-diisocyanatocyclohexane, Isophorone diisocyanate, 4,4'-di (isocyanatocyclohexyl) methane, 2,4- or 2,6-toluene diisocyanate and 2,4'- or 4,4'-diisocyanatodiphenylmethane.

When Component E) are also isocyanurates o. Isocyanates used. Preferred representatives are trimeric hexamethylene diisocyanate, isophorone diisocyanate, 2,4- or 2,6-toluene diisocyanate, and 1,4- or 1,3-diisocyanatocyclohexane, and / or 4,4'-diisocyanatodicylohexylmethane.

In the preparation of the (poly) uretdiones according to the invention, monofunctional compounds F) which are reactive toward isocyanate groups may optionally be used. They are used for the irreversible capping of free NCO groups. These are, in particular, monoalcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, the isomeric pentanols, hexanols, octanols and nonanols, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, cyclohexanol, the isomeric methylcyclohexanol and hydroxymethylcyclohexane or simple aliphatic or cycloaliphatic monoamines such as methylamine, ethylamine, n-propylamine, isopropylamine, the isomeric butylamines, pentylamines, hexylamines and octylamines, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine, cyclohexylamine, the isomeric methylcyclohexylamines and aminomethylcyclohexane, secondary monoamines, such as dimethylamine, diethylamine, dipropylamine, dibutylamine, bis (2-ethylhexyl) amine, N-methyl and N-ethylcyclohexylamine and dicyclohexylamine, alone or in mixtures.

When further component F) can aliphatic and / or cycloaliphatic and / or aromatic blocking agents be used. For example, the following compounds are suitable: 2-butanone oxime, 3-pentanone oxime, acetaldehyde oxime, phenol, N, N-diisopropylamine, N, N-diisobutylamine, ε-caprolactam, 3,5-dimethylpyrazole, 1,2,4-triazole.

• A) mindestens eine mono-, di- und/oder polyfunktionalisierte Perfluoralkylverbindung mit mindestens einer Trifluormethylendgruppe als End- und/oder Seitengruppe und mindestens einer weiteren gegenüber Isocyanaten reaktiven funktionellen Gruppe, und
• B) mindestens ein Polyisocyanat mit mindestens einer Uretdiongruppe, und gegebenenfalls
• C) Di- und/oder Polyole, und/oder Di- und/oder Polyamine und/oder Aminoalkohole, und/oder
• D) weitere funktionelle Gruppen enthaltende Di- und/oder Polyole, und/oder
• E) Polyisocyanate ohne Uretdiongruppen und/oder
• F) gegenüber Isocyanaten reaktiven monofunktionellen Verbindungen,

wobei die perfluoralkylgruppenhaltigen (Poly-)Uretdione einen Gehalt an freien NCO-Gruppen von 0 bis 5 Gew.-%, einen Schmelzbereich zwischen 40 und 200 °C und zahlenmittlere Molmassen im Bereich von 500 bis 10000 aufweisen, bei Temperaturen von 40 bis 200 °C.The invention also provides a process for the preparation of the (poly) uretdiones having terminal and / or pendant perfluoroalkyl groups, synthesized from the starting components

• A) at least one mono-, di- and / or polyfunctionalized perfluoroalkyl compound having at least one trifluoromethylene end group as end and / or side group and at least one further isocyanate-reactive functional group, and
• B) at least one polyisocyanate having at least one uretdione group, and optionally
• C) di- and / or polyols, and / or di- and / or polyamines and / or amino alcohols, and / or
• D) further functional groups containing di- and / or polyols, and / or
• E) polyisocyanates without uretdione groups and / or
• F) isocyanate-reactive monofunctional compounds,

wherein the perfluoroalkyl-containing (poly) uretdiones have a content of free NCO groups from 0 to 5 wt .-%, a melting range between 40 and 200 ° C and number average molecular weights in the range of 500 to 10,000, at temperatures of 40 to 200 ° C.

The Production of the (poly) uretdiones according to the invention can be discontinuous both in solvent and in substance, So solvents free, done.

The Preparation of the compound of the invention occurs by polyaddition reaction.

The following polyaddition reactions are preferably carried out in order to obtain reactive linear and / or branched (poly) uretdiones having chemically coupled perfluoroalkyl compounds having at least one trifluoromethylene end group as end and / or side groups:
Reaction of component A) (monofunctionalized perfluoroalkyl compound) with component B) (dimeric diisocyanates as uretdione compound with two free isocyanate groups) - with the components are linear uretdione with chemically coupled perfluoroalkyl having at least one trifluoromethylene end groups as end groups for use as coupling reagent in polymer-analogous reactions representable.

implementation of component A) (mono- and / or difunctionalized perfluoroalkyl compound) with component B) (dimeric diisocyanates as Uretdionverbindung with two free isocyanate groups), component C) (di- or polyols) and optionally component F) (blocking agent for isocyanate group) - with the Components are linear or branched polyuretdiones with possibly irreversibly or reversibly blocked isocyanato-functionalized End groups and chemically coupled perfluoroalkyl compounds with at least one trifluoromethylene end group as end and / or side groups for the Use as hardener in various coating agents, chain extenders and Modification of polymers representable.

implementation of component A) (mono-, di- and / or polyfunctionalized perfluoroalkyl compound) Component B) (dimeric diisocyanates as Uretdionverbindung with two free isocyanate groups), component C) (di- or polyols), component D) (further functional groups containing di- or polyols such as Polyester polyols), optionally component F) (blocking agent for isocyanate group) and / or optionally component E) (diisocyanates or isocyanurates) - with the Components are linear or branched, more flexible polyuretdiones with optionally irreversibly or reversibly blocked isocyanato-functionalized End and / or side groups and chemically coupled perfluoroalkyl compounds with at least one trifluoromethylene end group as end and / or side groups for the Use as hardener in various coating agents, chain extenders and Modification of polymers representable.

The reaction in the solvent is generally carried out at temperatures of 40 to 100 ° C, vorzugswei between 60 and 90 ° C. The components A) and C) and / or D) and / or E) are initially charged and the polyisocyanate with uretdione groups B) added as quickly as possible, without the reaction temperature exceeds the above limits. The reaction is complete after 30 to 150 minutes. Component F) may be present during the reaction and may be added after the reaction has ended. Subsequently, the solvent is removed. Suitable for this are z. B. Abdampfschnecken, Filmtruder or spray dryer.

suitable solvent are benzene, toluene or other aromatic or aliphatic hydrocarbons, Ethyl acetate or butyl acetate, also ketones such as acetone, Methyl ethyl ketone, methyl isobutyl ketone or chlorinated aromatic and aliphatic hydrocarbons and any mixtures of these or opposite the reactive groups of the composition according to the invention inert Solvents.

The solvent free reaction takes place discontinuously in a boiler at temperatures up to 200 ° C.

to Acceleration of the polyaddition reaction can also be used in PUR chemistry Catalysts are used. Proved to be particularly suitable Tin II and IV compounds. Dibutyltin dilaurate (DBTL) is mentioned here in particular. The catalysts are in a concentration of 0.01 to 1 mass%, preferably from 0.03 to 0.5% by weight, based on the reaction components used used.

The Component A) is for the polyaddition reactions in amounts of 1 to 70% by mass, and preferably from 1 to 50% by mass. For this purpose, known catalysts for the polyaddition reactions in the usual Range of ≤ 1 Mass%, based on the total amount of functionalized monomers and functionalized perfluoroalkyl used.

Advantageous for this Invention is that the perfluoroalkylgruppenhaltigen (Poly) uretdiones in coating agents simultaneously as hardeners, phase segregating Compound and in situ modification of resins with and without Perfluoroalkylgruppenhaltigen substituents for the production of (ultra) hydrophobic surface properties different layer systems can be used. Also It is advantageous to use low molecular weight uretdione compounds containing perfluoroalkyl groups End groups in polymer-analogous reactions or chemical modification reactions to use compounds that the accessibility of new polymers with Permit perfluoroalkyl-containing substituents.

The The invention is further illustrated by the following examples.

Examples

example 1

In to a 1 liter reactor, 52.63% by weight of N- (5-hydroxymethyl-6-hydroxyhex-1-yl) perfluorooctanoic acid amide, 47.37% by mass of IPDI uretdione and 0.1% by mass of catalyst dibutyltin dilaurate, based on the two monomers used, in 500 ml of anhydrous Acetone under inert gas atmosphere solved. The reaction solution is 18 h at 60 ° C touched. Thereafter, the reaction solution cooled to room temperature and an appropriate amount of pentylamine to block the excess isocyanate groups added and stirred for 4 h.

Example 2

In 17.4% by weight of N- (5-hydroxymethyl-6-hydroxyhex-1-yl) perfluorooctanoic acid amide in a 1 liter reactor, 71.3 mass% of IPDI uretdione, 11.27 mass% of 1,4-butanediol and 0.1 mass% of catalyst dibutyltin dilaurate, based on the monomers used, dissolved in 450 ml of anhydrous acetone under an inert gas atmosphere. The reaction solution is 6 h at 60 ° C touched and then the addition of 1-pentanol and some catalyst Dibutyltin dilaurate for blocking excess isocyanate groups. The reaction solution is another 4 h at 60 ° C stirred.

Example 3

In a 1 l reactor, 21.31% by mass of N- (5-hydroxymethyl-6-hydroxyhex-1-yl) perfluorooctanoic acid amide, 34.87% by mass of IPDI uretdione, 14.14% by mass of 1,4-dibutyl Butanediol, 29.68% by weight of hexame thylene diisocyanate and 0.1% by mass of catalyst dibutyltin dilaurate, based on the monomers used, dissolved in 350 ml of anhydrous acetone under an inert gas atmosphere. The reaction solution is stirred for 8 h at 60 ° C and then followed by the addition of 1-pentanol and some catalyst dibutyltin dilaurate for quenching excess isocyanate groups. The reaction solution is stirred for a further 4 hours at 60.degree.

Example 4

In 11.22% by weight of N- (5-hydroxymethyl-6-hydroxyhex-1-yl) perfluorooctanoic acid amide in a 1 l reactor, 36.73% by mass of IPDI uretdione, 15.65% by mass of 1,4-butanediol, 34.74 Mass% of hexamethylene diisocyanate, 1.66 mass% of 1,1,1-trishydroxymethylpropane and 0.1% by mass of catalyst dibutyltin dilaurate, based on the monomers used, dissolved in 450 ml of anhydrous acetone under an inert gas atmosphere. The reaction solution is 4 h at 60 ° C touched. Thereafter, the reaction solution cooled to room temperature and an appropriate amount of N, N-dibutylamine to block the excess isocyanate groups added and stirred for 4 h.

Example 5

In 11.61% by weight of 1H, 1H, 2H, 2H, 3H, 3H, 4H, 4H, 5H, 5H, 6H, 6H, 7H, 7H-2- (hydroxymethyl) perfluoropentadecane-1 are added to a 1 liter reactor -ol, 36.58% by mass IPDI uretdione, 15.57 mass% 1,4-butanediamine, 34.59 mass% hexamethylene diisocyanate, 1.65% by weight of 1,1,1-trishydroxymethylpropane and 0.1% by mass of catalyst dibutyltin dilaurate, based on the monomers used, dissolved in 450 ml of anhydrous acetone under an inert gas atmosphere. The reaction solution is 6 h at 60 ° C touched and then adding 1-pentanol and some catalyst dibutyltin dilaurate for quenching excess isocyanate groups. The reaction solution is left for a further 4 h at 60 ° C stirred.

Example 6

In a 1 l reactor, 17.29% by mass of 1H, 1H, 2H, 2H, 3H, 3H, 4H, 4H, 5H, 5H, 6H, 6H, 7H, 7H-perfluoropentadecan-1-ol, 71.92% by mass of IPDI uretdione, 10.79% by mass of 1,4-butanediol and 0.1 mass% of catalyst dibutyltin dilaurate, based on the monomers used, dissolved in 450 ml of anhydrous acetone under an inert gas atmosphere. The reaction solution is 7 h at 60 ° C touched and then the addition of 1-pentanol and some catalyst Dibutyltin dilaurate for blocking excess isocyanate groups. The reaction solution is left for a further 4 h at 60 ° C stirred.

Claims (25)

(Poly) uretdiones having terminal and / or pendant perfluoroalkyl groups constructed from the output components A) at least one mono-, di- and / or polyfunctionalized perfluoroalkyl compound having at least a trifluoromethylene end group as end and / or side group and at least one more opposite Isocyanate-reactive functional group, and B) at least a polyisocyanate having at least one uretdione group, and optionally C) Di- and / or polyols and / or di- and / or polyamines and / or amino alcohols, and or D) further di- and / or functional groups containing Polyols, and / or E) polyisocyanates without uretdione groups and / or F) across from Isocyanate-reactive monofunctional compounds, in which the perfluoroalkyl-containing (poly) uretdiones a content of free NCO groups from 0 to 5 wt .-%, a melting range between 40 and 200 ° C and number average Have molecular weights in the range of 500 to 10,000. Perfluoroalkyl-containing (poly) uretdiones according to Claim 1, characterized in that compounds of the following formula are used as component A):

with m ≥ 1; n = 0 to 1; o ≥ 1 Perfluoroalkyl-containing (poly) uretdiones according to claim 2, characterized in that compounds of the following formula are used as component A):

with m ≥ 1; n = 0 to 1, o ≥ 1; p = 1 to 10 Perfluoralkylgruppenhaltige (poly) uretdiones after one of the preceding claims, characterized in that as component A) Perfluoralkansäureamide and / or perfluoroalkanesulfonic acid amides be used. Perfluoralkylgruppenhaltige (poly) uretdiones after at least one of the preceding claims, characterized that the component A) is in the form that the perfluoroalkyl segments via a linear or branched spacer chain bound with a chain length of 1 to 60 carbon atoms are. Perfluoralkylgruppenhaltige (poly) uretdiones after Claim 5, characterized in that the spacer chains at least have a functional group. Perfluoralkylgruppenhaltige (poly) uretdiones after Claim 6, wherein the functional group (s) of the spacer chain (s) selected are made from carboxylic ester, carboxamide, sulfonamide, Imide, urethane, urea, amino, keto, sulfide, sulfone groups and / or C-C double bonds. Perfluoralkylgruppenhaltige (poly) uretdiones after at least one of the preceding claims, characterized in that as component A) Perfluoralkansäureamide and / or perfluoroalkanesulfonic acid amides with non-functionalized N-alkyl spacer chains and a chain length of 1 to 20 carbon atoms are used. Perfluoroalkyl-containing (poly) uretdiones according to at least one of the preceding claims, characterized in that component A) has a chain length of 2 to 35 carbon atoms having at least one CF ₃ group for the perfluoroalkyl chain segment, and substituting all carbon atoms of the chain with fluorine are. Perfluoralkylgruppenhaltige (poly) uretdiones after Claim 9, characterized in that the perfluoroalkyl chain segment Contains heteroatoms. Perfluoralkylgruppenhaltige (poly) uretdiones after at least one of the preceding claims, characterized that the component A) over a urethane group and / or urea group in the (poly) uretdione chemically is bound. Perfluoroalkyl-containing (poly) uretdiones according to at least one of the preceding claims, characterized in that 1,4-diisocyanatobutane, 1,6-diisocyanatohexane (HDI), 2-methylpentamethylene diisocyanate-1,5 (MPDI), 2,2,4 (2,4,4) -trimethylhexamethylene diisocyanate (TMDI), 4,4'-diisocyanatodicyclohexylmethane (H ₁₂ MDI), 1,3-diisocyanatocyclohexane, 1,4-diisocyanatocyclohexane, isophorone diisocyanate (IPDI), norbornane diisocyanate, diphenylmethane-2,4 ' and / or -4,4'-diisocyanate, xylylene diisocyanate or 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate and any mixtures of these isomers, these diisocyanates are used alone or in mixtures as the starting component for the component B). Perfluoroalkyl-containing (poly) uretdiones according to at least one of the preceding claims, characterized in that as component B) isophorone diisocyanate (IPDI), 2-methylpentamethylene diisocyanate-1,5 (MPDI), 2,2,4- / 2,4, 4-trimethylhexamethylene diisocyanate (TMDI), 4,4'-diisocyanatodicyclohexylmethane (H ₁₂ MDI), norbornane diisocyanate (NBDI) and / or 1,6-diisocyanatohexane (HDI) can be used. Perfluoralkylgruppenhaltige (poly) uretdiones after at least one of the preceding claims, characterized that as component C) ethylene glycol, 1,3-propanediol, 1,4-butanediol, Pentanediol-1,5, 3-methylpentanediol-1,5, 1,6-hexanediol, 2,2,4- / 2,4,4-trimethylhexanediol-1,6, hydroxypivalic acid neopentyl glycol ester, 1,4-di (hydroxymethyl) cyclohexane, diethylene glycol, triethylene glycol, Neopentylglycol, trimethylolpropane, trimethylolethane, glycerol or Pentaerythritol, ethanolamine, diethanolamine, triethanolamine, diisopropanolamine, Hexamethylenediamine, isophoronediamine, 2-methylpentamethylenediamine, 1,4-cyclohexanediamine, 4,4'-diaminodicyclohexylmethane be used. Perfluoralkylgruppenhaltige (poly) uretdiones after at least one of the preceding claims, characterized that as component D) linear or branched hydroxyl-containing Polyesters, polycaprolactones, polycarbonates, polyethers, polythioethers, Polyesteramides, polyurethanes and / or polyacetals with number average Molecular weights of 134 to 6000 are used. Perfluoralkylgruppenhaltige (poly) uretdiones after at least one of the preceding claims, characterized in that component E) is tetramethylene diisocyanate, hexamethylene diisocyanate, Decamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 1,3-diisocyanatocyclohexane, 1,2-diisocyanatocyclohexane, isophorone diisocyanate, 4,4'-diisocyanatocyclohexylmethane, 2,4- and / or 2,6-toluene diisocyanate and 2,4'- and / or 4,4'-diisocyanatodiphenylmethane be used. Perfluoralkylgruppenhaltige (poly) uretdiones after at least one of the preceding claims, characterized in that component E) is preferably hexamethylene diisocyanate, isophorone diisocyanate, tolylene 2,4-diisocyanate, 2,6-tolylene diisocyanate, 1,4-diisocyanatocyclohexane, 1,3-diisocyanatocyclohexane and / or 4,4'-diisocyanatocyclohexylmethane, be used. Perfluoralkylgruppenhaltige (poly) uretdiones after at least one of the preceding claims, characterized that as component F) monoalcohols, monoamines, oximes, pyrazoles, Triazoles and / or lactams are used. Perfluoralkylgruppenhaltige (poly) uretdiones after at least one of the preceding claims, characterized that as component F) compounds selected from methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, den isomeric pentanols, hexanols, octanols, nonanols, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, cyclohexanol, methylcyclohexanol, Hydroxymethylcyclohexane, methylamine, ethylamine, n-propylamine, isopropylamine, the isomeric butylamines, pentylamines, hexylamines, octylamines, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine, cyclohexylamine, Methylcyclohexylamines, aminomethylcyclohexane, dimethylamine, diethylamine, Dipropylamine, dibutylamine, bis (2-ethylhexyl) amine, N-methyl- and N-ethylcyclohexylamine, Dicyclohexylamine, 2-butanone oxime, 3-pentanone oxime, acetaldehyde oxime, phenol, N, N-diisopropylamine, N, N-diisobutylamine, 3,5-dimethylpyrazole, 1,2,4-triazole and / or ε-caprolactam be used. Process for the preparation of (poly) uretdiones with end and / or side Perfluoroalkyl groups, composed of the starting components A) at least one mono-, di- and / or polyfunctionalized perfluoroalkyl compound with at least one trifluoromethylene end group as end and / or side group and at least one further isocyanate-reactive functional Group, and B) at least one polyisocyanate with at least a uretdione group, and optionally C) di- and / or polyols, and / or di- and / or polyamines and / or amino alcohols, and / or D) further functional groups containing di- and / or polyols, and / or e) Polyisocyanates without uretdione groups and / or F) against isocyanates reactive monofunctional compounds, wherein the perfluoroalkylgruppenhaltigen (Poly) uretdione a content of free NCO groups from 0 to 5 wt .-%, a melting range between 40 and 200 ° C and number average molecular weights in the range of 500 to 10,000, at temperatures of 40 to 200 ° C. The method of claim 20, wherein the polyaddition reactions catalyzed performed become. A method according to claim 20 or 21, wherein the Polyaddition reactions in solution carried out become. Use of (poly) uretdiones after at least one of the claims 1 to 19, with a resin and optionally with catalysts and other additives as coating agents. Use according to claim 23 for the preparation of (ultra) hydrophobic surface properties. Use according to claim 23 or 24 for façade and room elements, traffic control equipment and commercial vehicles.