EP3380538A1 - Amine pour compositions polymères durcissables à sécurité de process élevée - Google Patents

Amine pour compositions polymères durcissables à sécurité de process élevée

Info

Publication number
EP3380538A1
EP3380538A1 EP16805746.1A EP16805746A EP3380538A1 EP 3380538 A1 EP3380538 A1 EP 3380538A1 EP 16805746 A EP16805746 A EP 16805746A EP 3380538 A1 EP3380538 A1 EP 3380538A1
Authority
EP
European Patent Office
Prior art keywords
amine
formula
meth
acrylate
groups
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP16805746.1A
Other languages
German (de)
English (en)
Inventor
Edis Kasemi
Andreas Kramer
Ursula Stadelmann
Urs Burckhardt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sika Technology AG
Original Assignee
Sika Technology AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sika Technology AG filed Critical Sika Technology AG
Publication of EP3380538A1 publication Critical patent/EP3380538A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3234—Polyamines cycloaliphatic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/26—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring
    • C07C211/27—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring having amino groups linked to the six-membered aromatic ring by saturated carbon chains
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3237—Polyamines aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3237—Polyamines aromatic
    • C08G18/324—Polyamines aromatic containing only one aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3246—Polyamines heterocyclic, the heteroatom being oxygen or nitrogen in the form of an amino group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/325—Polyamines containing secondary or tertiary amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3253—Polyamines being in latent form
    • C08G18/3256—Reaction products of polyamines with aldehydes or ketones

Definitions

  • the invention relates to the field of amines, curable polymer compositions and applications thereof.
  • Amines containing two or more primary and / or secondary amino groups are used in many polymer compositions as a hardener, or as a reactive constituent of the hardener component. You have a good one
  • solvents can be used to control the blushing susceptibility of amines.
  • this causes emissions problems.
  • Another possibility is to previously react the amines with reactants contained in the polymer composition, thereby reducing their tendency to carbamate.
  • this leads to a strong increase in viscosity, which complicates the processing of the composition or in turn requires the use of solvents.
  • special amines with electronically or sterically hindered amino groups such as polyetheramines or secondary amines, can be used. Such amines show less blushing, but are significantly less reactive and result in slow cure, often associated with sacrifices in mechanical strength or durability.
  • the object of the present invention is therefore to provide a low molecular weight low-odor amine for use in curable polymer compositions which has a high reactivity, is very stable in storage even in contact with ambient air and thus products with low emission and high process reliability in the Storage, application and curing possible.
  • amines of the formula (I) as described in claim 1 solves this problem.
  • Amines of the For- mel (I) show surprisingly little carbamation when exposed to air, even after several days and at high humidity.
  • formulated polymer compositions can thus be used even in unfavorable climatic conditions such as low temperature and high humidity or in slow-curing, so-called long-open time systems, without increasing blushing-typical errors such as precipitation, turbidity, staining, roughness or Stickiness occur, and thus have a very high process reliability.
  • the amine of formula (I) despite the low susceptibility to blushing effects, has a high reactivity towards amine-crosslinkable compounds, thus without appreciable losses in cure rate as a replacement for conventional low molecular weight amines such as MXDA, IPDA or TETA is usable. Its low viscosity, low odor and low vapor pressure also make it possible to formulate easy to process and low-emission products even without solvents. Finally, the unequal reactivity of the primary and secondary amino groups present in the amine of the formula (I) produces a favorable curing profile, in particular a long open time with rapid curing. Further aspects of the invention are the subject of further independent claims. Particularly preferred embodiments of the invention are the subject of the dependent claims.
  • the invention relates to the use of an amine of the formula (I) in which
  • X is 1, 2-propylene
  • R is a hydrogen radical or a hydrocarbon radical having 1 to 6 C atoms
  • A represents a five, six or seven membered, optionally in the ring an oxygen, sulfur or nitrogen atom having cycloalkyl or aryl radical having 4 to 7 carbon atoms,
  • Y is identical or different radicals selected from the group consisting of alkyl, alkoxy and dialkylamino having 1 to 18 C atoms, m is 1 or 2 or 3, and
  • n 0 or 1 or 2 or 3
  • curable composition comprising at least one amine-crosslinkable compound which is free of epoxide groups.
  • curable is meant a composition capable of curing by crosslinking reactions of reactive groups contained therein or obtaining a state of increased mechanical strength.
  • amine-crosslinkable compound is meant a compound having a reactive group (s) whose reactive group (s) can or may react with amines to crosslink or cure.
  • a dashed line in the formulas in each case represents the bond between a substituent and the associated molecular residue.
  • primary amino group denotes an NH 2 group which is bonded to an organic radical and "secondary amino group” denotes an NH group which is bonded to two organic radicals which may also together be part of a ring. is bound.
  • viscosity denotes the dynamic viscosity or shear viscosity, which is defined by the ratio between the shear stress and the shear rate (velocity gradient) and determined as described in DIN EN ISO 3219.
  • molecular weight is meant the molar mass (in grams per mole) of a molecule or molecular residue.
  • Average molecular weight is the number average molecular weight (M n ) of an oligomeric or polymeric mixture of molecules or molecular residues designated. It is usually It was determined by gel permeation chromatography (GPC) against polystyrene as standard.
  • a substance or composition is defined as “storage stable” or “storable” if it can be stored at room temperature in a suitable dressing for a prolonged period of time, typically at least 3 months to 6 months or more, without being absorbed their application or service properties, in particular the viscosity and the rate of crosslinking, changed by the storage in a relevant for their use to the extent.
  • room temperature refers to a temperature of 23 ° C.
  • R is preferably a hydrogen radical or methyl or phenyl, in particular a hydrogen radical or methyl.
  • R is a hydrogen radical.
  • A preferably represents a five- or six-membered, optionally in the ring having an oxygen atom containing cycloalkyl or aryl radical having 4 to 6 C-atoms, in particular an optionally substituted cyclopentyl or cyclohexyl or tetrahydrofurfuryl or phenyl or furfuryl -Rest.
  • A is an optionally substituted phenyl radical.
  • A is an unsubstituted phenyl radical.
  • n is preferably 0 or 1 or 2, in particular 0 or 1.
  • n is 0.
  • m is preferably 1 or 2, in particular 1.
  • Y is preferably in the para position.
  • Y preferably represents identical or different radicals selected from the group consisting of alkyl, alkoxy and dialkylamino having in each case 1 to 12, in particular 1 to 4, C atoms.
  • Y is particularly preferably methyl or methoxy or dimethylamino, in particular methoxy or dimethylamino.
  • n is 1
  • m is 1
  • Y is methoxy or dimethylamino in the para position.
  • n is 0, m is 1 and A is cyclopentyl or cyclohexyl.
  • R here preferably stands for a hydrogen radical.
  • n is 0, m is 1 and A is phenyl.
  • R here preferably stands for a hydrogen radical.
  • Amine is the most preferred amine of formula (I). It is particularly accessible, very easy to prepare, particularly low viscosity, very reactive and has a particularly low tendency to carbamate.
  • n is 0, m is 2 and A is 1, 2- or 1, 3 or 1, 4-phenylene.
  • R is preferably a hydrogen radical and A is preferably 1,4-phenylene.
  • the amine of the formula (I) is preferably selected from the group consisting of N 1 -cyclopentylmethyl-1,2-propanediamine and N 2 -cyclopentylmethyl-1,2-propanediamine and a mixture of these isomers, N 1 -cyclohexylmethyl-1,2 propanediamine and N 2 -cyclohexylmethyl-1,2-propanediamine and a mixture of these isomers, N 1 - (2-tetrahydrofuryl) methyl-1,2-propanediamine and N 2 - (2-tetrahydrofuryl) trahydrofuryl) nnethyl-1, 2-propane diamine and a mixture of these isomers, N 1 - (3-tetrahydrofuryl) methyl-1, 2-propanediamine and N 2 - (3-tetrahydrofuryl) methyl-1, 2-propanediamine and Mixture of these isomers, N 1 -benzyl-1,2-propanediamine and N 2
  • N 1 -cyclopentylmethyl-1,2-propanediamine or N 2 -cyclopentylmethyl-1,2-propanediamine or a mixture of these isomers preference is given to N 1 -cyclopentylmethyl-1,2-propanediamine or N 2 -cyclopentylmethyl-1,2-propanediamine or a mixture of these isomers, N 1 -cyclohexylmethyl-1,2-propanediamine or N 2 -cyclohexylmethyl- 1, 2-propanediamine or a mixture of these isomers, N 1 -benzyl-1,2-propanediamine or N 2 -benzyl-1,2-propanediamine or a mixture of these isomers, N 1 - (4-methoxybenzyl) -1, 2-propanediamine or N 2 - (4-methoxybenzyl) -1,2-propanediamine or a mixture of these isomers, N 1 - (4- (dimethylamino) benzyl) -1,
  • N 1 -benzyl-1, 2-propanediamine or N 2 -benzyl-1, 2-propanediamine or a mixture of these isomers is particularly preferred.
  • an isomeric mixture consisting of N 1 -benzyl-1,2-propanediamine and N 2 -benzyl-1,2-propanediamine.
  • Such an isomer mixture is also referred to below as N-benzyl-1,2-propanediamine.
  • the preferred amines of the formula (I) are particularly readily available and are particularly easy to prepare.
  • the amine of the formula (I) is used in particular in the form of a mixture of isomers in which each X, which is 1, 2-propylene, is substituted in each case in both possible ways.
  • the amine of formula (I) is preferably obtained from the simple alkylation of 1,2-propylenediamine with a suitable alkylating agent, for example an organic halide or a carbonyl compound.
  • a suitable alkylating agent for example an organic halide or a carbonyl compound.
  • the amine of the formula (I) is preferably prepared by reductive alkylation of 1, 2-propylenediamine with at least one carbonyl compound of the formula (II) and hydrogen,
  • A is an aryl radical
  • it can either not be hydrogenated in the reductive alkylation or can be hydrogenated in a targeted manner to the corresponding cycloalkyl radical.
  • the amine of formula (I) is thus preferably used in the form of a reaction product of the reductive alkylation of 1, 2-propylenediamine with at least one carbonyl compound of formula (II) and hydrogen.
  • Such a reaction product is particularly pure even without expensive purification steps, i. it contains a high content of amine of formula (I) and is therefore particularly low viscosity.
  • Suitable carbonyl compounds of the formula (II) are, in particular, cyclopentanecarbaldehyde, cyclohexanecarbaldehyde, 2-tetrahydrofurancarbaldehyde, 3-tetrahydrofurancarbaldehyde, benzaldehyde, 4-methoxybenzaldehyde (anisaldehyde), 4-dimethylaminobenzaldehyde, acetophenone, 4'-methoxyacetophenone, 2-furancarbaldehyde, ortho Phthalaldehyde (1,2-benzenedicarbaldehyde), isophthalaldehyde (1,3-benzenedicarbaldehyde) or terephthalaldehyde (1,4-benzenedicarbaldehyde).
  • benzaldehyde is particularly preferred.
  • the reductive alkylation can be done directly with molecular hydrogen or indirectly by hydrogen transfer from other reagents, such as formic acid.
  • molecular hydrogen is used.
  • the conditions are advantageously selected such that, above all, an amino group of 1,2-propylenediamine is simply alkylated with good selectivity.
  • an amine of formula (I) is to be prepared in which the radical A is a cycloaliphatic radical
  • a carbonyl compound of the formula (II) with a corresponding aromatic radical A and the reaction conditions in the reductive alkylation be chosen so that the aromatic ring in the radical A is also hydrogenated.
  • the reaction is preferably carried out at a temperature of 40 to 120 ° C, in particular 60 to 100 ° C, and in the presence of a suitable catalyst.
  • Preferred as catalyst are palladium on carbon (Pd / C), platinum on carbon (Pt / C), Adams catalyst or Raney nickel, in particular palladium on carbon or Raney nickel.
  • molecular hydrogen When using molecular hydrogen is preferably in a pressure apparatus at a hydrogen pressure of 5 to 250 bar, in particular 10 to 150 bar, worked.
  • an amine of the formula (I) is to be prepared with an aromatic radical A
  • the reaction product of the described reductive alkylation may contain, in addition to at least one amine of the formula (I), further amines as by-products.
  • By-products are mainly higher alkylated products, as exemplified in the following formulas.
  • the presence of higher alkylated by-products increases the viscosity and lowers the reactivity of the reaction product.
  • the reaction is therefore preferably carried out so that the formation of higher alkylated by-products is suppressed as possible.
  • the reductive alkylation is preferably carried out with stoichiometric excess of 1,2-propylenediamine over the carbonyl groups.
  • the ratio between the number of 1,2-propylenediamine molecules and the number of carbonyl groups is preferably at least 1 .5 / 1, in particular at least 2/1, particularly preferably at least 2.5 / 1.
  • Excess 1,2-propylenediamine is removed before or preferably after the reduction, in particular by distillation, for example by means of thin-layer, short-path or downflow. In this way, the formation of higher alkylated by-products is suppressed, whereby a particularly low-viscosity and reactive reaction product is obtained.
  • the amine of the formula (I) is thus preferably used in the form of a reaction product from the reductive alkylation of 1,2-propylenediamine with at least one carbonyl compound of the formula (II) and hydrogen, 1,2-propylenediamine being present in a stoichiometric amount over the carbonyl groups. used and the excess is removed by distillation after reduction.
  • the reaction product is substantially free of 1, 2-propylenediamine. It contains in particular less than 1% by weight, preferably less than 0.5% by weight, more preferably less than 0.1% by weight, of 1,2-propylenediamine.
  • the reaction product is preferably purified by distillation.
  • the reaction product is distilled and the distillate obtained is used.
  • Such a purified by distillation reaction product contains a particularly high proportion of amine of formula (I) and thus allows a particularly attractive combination of high reactivity and low tendency to carbamation.
  • Very particular preference is given to a purified by distillation reaction product of the reductive alkylation of 1, 2-propylenediamine and benzaldehyde.
  • Such a reaction product consists mainly of an isomeric mixture of N 1 -benzyl-1, 2-propanediamine and N 2 -benzyl-1, 2-propanediamine, hereinafter also referred to as N-benzyl-1, 2-propanediamine.
  • the amine of formula (I) is used as part of a curable composition comprising at least one amine-crosslinkable compound which is free of epoxide groups.
  • the amine of formula (I) acts in the inventive use in particular as a curing agent for the amine-crosslinkable compound.
  • the amine-crosslinkable compound in the reaction with the amine of the formula (I), can also be in dissolved or emulsified or dispersed form, either in an organic medium or solvent or in water.
  • the amine of formula (I) can also be used in blocked, hydrolytically activatable form, in particular as aldimine, cycloaminoal, ketimine, enamine or oxazolidine.
  • blocked, hydrolytically activatable form in particular as aldimine, cycloaminoal, ketimine, enamine or oxazolidine.
  • primary amino groups and, depending on the type of blocking if appropriate also secondary amino groups are blocked in their reactivity with, for example, isocyanate groups in such a way that they react with them much more slowly and / or only under the action of moisture.
  • Such a blocked amine is particularly useful as a component of two-part long-processing time polyurethane compositions.
  • R 1 is a hydrogen radical or a hydrocarbon radical having 1 to 8 C atoms, in particular a hydrogen radical or methyl
  • R 2 is a hydrogen radical or a hydrocarbon radical which may have heteroatoms 1 to 30 carbon atoms
  • R 2 and R 3 together represent 1, 4-butylene or 1, 5-pentylene, and Y, n, A, R and X have the meanings already mentioned.
  • R 1 is a hydrogen radical and R 2 is phenyl, methyl, ethyl, 2-propyl, n-pentyl, n-heptyl, n-nonyl, n-undecyl or a radical of
  • Radical having 1 to 20 carbon atoms in particular methyl or n-undecyl.
  • R 1 is preferably methyl and R 2 is methyl, ethyl, isopropyl, isobutyl or isoamyl.
  • the amine of formula (I) may also affect other properties of the curable composition.
  • it can influence the rheological properties of the composition, in particular by causing an increased flow limit of the composition during processing. This is advantageous in that such compositions have good stability during processing in the liquid state, ie they drain or slip off less when applied to inclined surfaces.
  • the amines crosslinkable compound preferably has one or more identical or different reactive groups selected from isocyanate, isothiocyanate, cyanate, thiocyanate, thioepoxide, aziridine, (meth) acrylate, (meth) acrylamide, maleate, maleamide , Maleimide, fumarate, fumaramide, itaconate, itaconamide, crotonate, crotonamide, carboxylic anhydride, carbonate, carboxylic acid, carboxylic ester, lactone, carboxylic acid chloride, ketone, aldehyde, acetoacetate and acetoacetamide groups.
  • Preferred reactive groups are isocyanate or (meth) acrylate or cyclic carboxylic acid anhydride or cyclic carbonate or acetoacetate groups.
  • isocyanate or (meth) acrylate groups are particularly inexpensive and widely used.
  • the entirety of the compounds which are crosslinkable with amines in the composition are polyfunctional with respect to the reactive groups contained.
  • the average functionality is in the range from 1 .1 to 20, preferably 1 .2 to 10, in particular 1 .3 to 5.
  • the compound which can be crosslinked with amines can contain, in addition to the reactive groups mentioned, further reactive groups capable of crosslinking reactions, in particular hydroxyl groups or alkoxysilyl groups ("SN groups").
  • crosslinkable compound with amines are particularly suitable polyisocyanates.
  • Their isocyanate groups can be present in free and / or blocked form.
  • the amine of formula (I) reacts with isocyanate groups to form urea groups. This reaction proceeds rapidly in the case of free isocyanate groups even at room temperature, while blocked isocyanate groups typically react slowly at room temperature or only after activation in the heat.
  • Suitable polyisocyanates are in particular
  • aliphatic or cycloaliphatic di- or triisocyanates preferably 1,4-tetramethylene diisocyanate, 2-methylpentamethylene-1,5-diisocyanate, 1,6-hexamethylene diisocyanate (HDI), 2,2,4- and / or 2,4,4- Trimethyl-1,6-hexamethylene diisocyanate (TMDI), 1,10-decamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, lysine or lysine ester diisocyanate, cyclohexane 1, 3 or -1, 4-diisocyanate, 1-methyl- 2,4- and / or 2,6-diisocyanatocyclohexane (H 6 TDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), perhydro-2,4'- and / or -4,4'-diphenylmethane
  • MDI 2,4- or 2,6-toluene diisocyanate or mixtures of these isomers
  • TDI 2,4- or 2,6-toluene diisocyanate or mixtures of these isomers
  • PMDI polymeric MDI or PMDI
  • 1, 3 or 1 4-phenylene diisocyanate 2, 3,5,6-tetramethyl-1,4-diisocyanatobenzene, naphthalene-1,5-diisocyanate (NDI), 3,3'-dimethyl-4,4'-diisocyanato-diphenyl (TODI), dianisidine diisocyanate (DADI) Tris (4-isocyanatophenyl) methane or tris (4-isocyanatophenyl) thiophosphate; in particular MDI or TDI;
  • di- or triisocyanates in particular derived from HDI, IPDI, MDI or TDI, in particular oligomers containing uretdione or isocyanurate or iminooxadiazinedione groups; or di- or polyvalent derivatives containing ester or urea or urethane or biuret or allophanate or carbodiimide or uretonimine or oxadiazinetrione groups.
  • polyisocyanates are usually mixtures of substances with different degrees of oligomerization and / or chemical structures. In particular, they have an average NCO functionality of 2.1 to 4.0.
  • Isocyanate group-containing polyurethane polymers from the reaction of polyols with polyisocyanates, as described below.
  • a suitable isocyanate group-containing polyurethane polymer is obtained, in particular, from the reaction of at least one polyol with a more than stoichiometric amount of at least one polyisocyanate, in particular a diisocyanate.
  • the reaction is preferably carried out with exposure to moisture. conclusion carried out at a temperature in the range of 50 to 160 ° C, optionally in the presence of suitable catalysts.
  • the excess of polyisocyanate is preferably selected such that in the polyurethane polymer after the reaction of all hydroxyl groups, a content of free isocyanate groups in the range of 1 to 30% by weight, preferably 1 .5 to 25% by weight, particularly preferably 2 to 20% by weight. , based on the total polymer remains.
  • the polyurethane polymer may be prepared using plasticizers or solvents, with the plasticizers or solvents used containing no isocyanate-reactive groups.
  • the isocyanate group-containing polyurethane polymer preferably has an average molecular weight in the range of 350 to 6 ⁇ 00 g / mol.
  • Preferred polyisocyanates for the preparation of an isocyanate group-containing polyurethane polymer are the polyisocyanates already mentioned, in particular the diisocyanates, in particular MDI, TDI, IPDI, HDI or Hi 2 MDI.
  • Suitable polyols are, in particular, polyether polyols, preferably polyoxyalkylene polyols, which are polymerization products of ethylene oxide or 1,2-propylene oxide or 1,2- or 2,3-butylene oxide or oxetane or tetrahydrofuran or mixtures thereof, possibly polymerized with the aid of a starter molecule two or more active hydrogen atoms; Polyester polyols, preferably products from the polycondensation of diols or triols with lactones or dicarboxylic acids or their esters or anhydrides; Polycarbonate polyols, OH-terminated block copolymers having at least two different blocks with polyether, polyester or polycarbonate units; Polyacrylate or polymethacrylate polyols; Polyhydroxy-functional fats or oils, especially natural fats or oils; or polyhydrocarbyl polyols such as polyhydroxy-functional polyolefins.
  • polyether polyols preferably polyoxyalkylene polyol
  • diols or triols or mixtures thereof are particularly suitable.
  • at least one difunctional or polyfunctional alcohol may also be used, such as, in particular, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1 , 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 3-pentanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, neopentyl glycol, dibromoneopentyl glycol, 1, 2-hexanediol, 1 , 6-hexanediol, 1, 7-heptanediol, 1, 2-octanediol, 1, 8-octanediol, 2-ethyl
  • a form of MDI which is liquid at room temperature represents liquefied 4,4'-MDI either by partial chemical modification-in particular carbodiimidization or uretonimine formation or adduct formation with polyols-or it is a deliberately brought about by mixing or conditioned by the preparation process Mixture of 4,4'-MDI with other MDI isomers (2,4'-MDI and / or 2,2'-MDI), MDI oligomers or MDI homologs (PMDI).
  • 4,4'-MDI either by partial chemical modification-in particular carbodiimidization or uretonimine formation or adduct formation with polyols-or it is a deliberately brought about by mixing or conditioned by the preparation process Mixture of 4,4'-MDI with other MDI isomers (2,4'-MDI and / or 2,2'-MDI), MDI oligomers or MDI homologs (PMDI).
  • the polyisocyanate is in blocked form.
  • a blocked polyisocyanate is a surface-deactivated polyisocyanate solid at room temperature.
  • One such is based on a solid polyisocyanate at room temperature, the melting point is well above room temperature, in particular the commercially available, finely divided uretdione of 2,4-toluene diisocyanate, for example as Addolink ® TT (by Rhein Chemie).
  • the solid at room temperature polyisocyanate is on the surface is additionally deactivated by reacting with a substance which has at least one isocyanate-reactive group, for example with a primary polyamine.
  • a protective layer which is stable at room temperature or slightly elevated temperature, ie impermeable and largely insoluble, is formed on the surface of the polyisocyanate particles.
  • the surface-deactivated polyisocyanate is heated to a temperature of in particular at least 80 ° C., the layer on the polyisocyanate particles is damaged to such an extent that the isocyanate groups in the particle interior become accessible to chemical reactants, ie they are "activated".
  • blocked polyisocyanate is a blocked by the prior implementation of the free isocyanate groups with a known from the prior art blocking agent, for example, a phenol, ketoxime, pyrazole, lactam or malonic acid, blocked polyisocyanate.
  • a known from the prior art blocking agent for example, a phenol, ketoxime, pyrazole, lactam or malonic acid, blocked polyisocyanate.
  • Blocking reduces the reactivity of the polyisocyanate to nucleophiles such that it is storage stable at room temperature with suitable curing agents and does not react with these curing agents under the action of heat and / or moisture, the blocking agent being released depending on the type or not releasedC.
  • suitable curing agents such as Trixene ® BL-7641, BL-7642, BL-7770, BL-7771, BL-7772 , Bl 7774 or Bl 7779 (all from Baxenden)
  • Tolonate ® D2 (of Vencorex) or they may be prepared by reaction of polyisocyanates with suitable blocking agents according to Need to be made.
  • the polyisocyanate is in the form of an aqueous emulsion which is crosslinked with the amine of formula (I) to form a polyurethane dispersion.
  • the polyisocyanate contains polyoxyethylene chains and / or ionic groups, in particular carboxylate or sulfonate or ammonium groups.
  • the polyisocyanate is preferably an isocyanate group-containing polyurethane polymer which is mixed with fractions of hydro- xyfunktionellen carboxylic acids such as in particular dimethylolpropionic acid or with proportions of diolsulfonates or with portions of, for example, methyldiethanolamine and / or with portions of hydroxy-functional polyethylene oxides are present and present carboxylic acid groups or sulfonic acid groups or amino groups in the emulsion in neutralized form.
  • such an aqueous emulsion contains a water content in the range of 30 to 80% by weight.
  • Particularly suitable for this use is an amine of the formula (I) in which m is 1.
  • Such an amine reacts rapidly with crosslinking with the polyisocyanate emulsified in water, the two differently reactive amino groups favoring a controlled reaction. From this use, a polyurethane dispersion is formed, which is particularly suitable as a binder for aqueous adhesives, sealants or coatings. When used, existing water evaporates, resulting in a solid film having particularly elastic properties.
  • poly (meth) acrylates are furthermore particularly suitable.
  • the amine of formula (I) reacts with (meth) acrylate groups mainly in a Michael-type addition reaction with alkylation of the amino groups.
  • Suitable poly (meth) acrylates are in particular
  • Adducts of di- or polyvalent epoxides with acrylic acid or methacrylic acid Adducts of di- or polyvalent epoxides with acrylic acid or methacrylic acid
  • polyurethane polymers having two or more acrylate or methacrylate groups, in particular having an average molecular weight in the range from 500 to 20,000 g / mol, in particular from the reaction of hydroxy-functional (meth) acrylates, in particular 2-hydroxyethyl acrylate (HEA), 2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl acrylate (HPA) or 2-hydroxypropyl methacrylate (HPMA), with isocyanate group-containing polyurethane polymers.
  • HEA 2-hydroxyethyl acrylate
  • HEMA 2-hydroxyethyl methacrylate
  • HPMA 2-hydroxypropyl methacrylate
  • Preferred poly (meth) acrylates are urethane (meth) acrylates of 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentylglycol di (meth) acrylate, bisphenol A ethoxylate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pent
  • monofunctional (meth) acrylates in particular methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, can be used in addition to the abovementioned poly (meth) acrylates.
  • substances with cydic carboxylic anhydride groups are furthermore particularly suitable.
  • the amine of formula (I) reacts with cyclic carboxylic acid anhydride groups to give carboxylic acid amide and carboxylic acid groups.
  • the latter can react under suitable conditions with further amine of the formula (I) to give carboxylic acid amide groups.
  • Preferred as substances having carboxylic anhydride groups are copolymers of unsaturated anhydrides with one or more olefinically unsaturated monomers, in particular copolymers of maleic anhydride or itaconic anhydride with olefins, dienes, vinyl-functional hydrocarbons, vinyl ethers, vinyl esters, vinylnitriles, acrylates or methacrylates; Addition products of unsaturated anhydrides with polyunsaturated oligomers or polymers, especially of maleic anhydride or itaconic anhydride with polybutadienes, polychloroprenes, natural rubbers or synthetic rubbers, in particular copolymers of butadiene or isoprene with styrene, acrylonitrile or 1-olefins, or with unsaturated aliphatic esters, in particular based on natural Fats and oils; Graft polymers obtained by free-radically induced grafting of unsaturated anhydrides, especially maleic anhydride, on
  • cyclic anhydrides for controlling the crosslinking density and / or as reactive diluents, cyclic anhydrides, in particular succinic anhydride, methylsuccinic anhydride or other alkylsuccinic anhydrides, dodecenylsuccinic anhydrides or other alkenylsuccinic anhydrides, maleic anhydride, itaconic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetra, may be used in addition to the cydic carboxylic anhydride - Hydrophthalic anhydride, methyltetrahydrophthalic anhydride, phthalic anhydride, methylphthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, Benzoltetracarbonklahydrid, Benzophenontetracarbonklahydride or 4,4 '- [(isopropylidene) bis (p-phenyleneoxy)
  • substances with cydic carbonate groups are furthermore particularly suitable.
  • the amine of formula (I) reacts with cyclic carbonic groups to open ring to carboxylic acid amide and hydroxyl groups.
  • the latter can, under suitable conditions, react with further cydic carbonate groups to form noncyclic carbonate groups.
  • Preferred substances having cyclic carbonate groups are substances having terminal 2-oxo-1,3-dioxolane groups, in particular reaction products of 4- (hydroxymethyl) -1,3-dioxolan-2-ones (glycerol carbonate) with polyisocyanates, in particular isocyanate group-containing polyurethane polymers; polyfunctional ethers or esters of glycerol carbonate; or reaction products of polyepoxides, in particular epoxy resins, preferably bisphenol A, F or A / F liquid resins or epoxy-terminated polyethers, with carbon dioxide (CO 2 ), wherein the carbon dioxide under the action of pressure, temperature and suitable Catalysts are converted by insertion of part or all of the epoxide groups
  • low molecular weight cyclic carbonates in particular ethylene carbonate, propylene carbonate or glycerol carbonate, can be used in addition to the substances mentioned with cyclic carbonate groups.
  • substances with acetoacetate groups are furthermore particularly suitable.
  • the amine of formula (I) reacts with acetoacetate groups to release water to acetoacetylimine groups.
  • Preferred substances with acetoacetate groups are reaction products of diols, triols or polyols with acetoacetic acid esters or diketene, in particular ethylene glycol bis (acetoacetate), diethylene glycol bis (acetoacetate), triethylene glycol bis (acetoacetate), tetraethylene glycol bis (acetoacetate), poly ethylene glycol bis (acetoacetate), dipropylene glycol bis (acetoacetate), tripropylene glycol bis (acetoacetate), polypropylene glycol bis (acetoacetate), 1, 3-propanediol bis (acetoacetate), 1, 4-butanediol bis ( acetoacetate), 1,5-pentanediol bis (acetoacetate), 3-methyl-1,5-pentanediol bis (acetoacetate), 1,6-hexanediol bis (acetoacetate), 2,2 (4), 4 Trimethyl-1,6-hexanediol bis (
  • acetoacetates in addition to the abovementioned substances with acetoacetate groups, it is possible, in addition to the abovementioned substances with acetoacetate groups, to use low molecular weight acetoacetates, in particular methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate, n-butyl acetoacetate, isobutyl acetoacetate or tert-butyl acetoacetate.
  • the amine-crosslinkable compound is particularly preferably an optionally blocked polyisocyanate or a poly (meth) acrylate, in particular an optionally blocked polyisocyanate.
  • Such compounds are particularly well available commercially and inexpensively and give after curing products with particularly valuable mechanical properties and particularly good resistance.
  • the amine of the formula (I) is preferably used in such an amount that the amino groups are present in a stoichiometric excess relative to the reactive groups of the amine-crosslinkable compound.
  • Another object of the invention is a curable composition comprising at least one amine of formula (I) and at least one amine-crosslinkable compound which is free of epoxide groups.
  • Such a composition allows easy-to-process, low-emission products which can be used even at high air humidity and / or slow curing with high process reliability without defects due to carbamatization and thereby have a long open time with rapid curing.
  • Suitable compounds which can be crosslinked with amines are those described above. Preference is given to optionally blocked polyisocyanates or poly (meth) acrylates. Particularly preferred are optionally blocked polyisocyanates.
  • the curable composition may contain, in addition to the amine of the formula (I) and the amine-crosslinkable compound, further ingredients, in particular those mentioned below.
  • the curable composition optionally additionally contains further amines which do not correspond to the formula (I), in particular
  • - Amino alcohols such as in particular 2-aminoethanol, 2- (2-aminoethoxy) ethanol or 3-aminomethyl-3,5,5-trimethylcyclohexanol or ether, ester or urethane groups having derivatives thereof;
  • Amines having primary and secondary amino groups in particular N-methylethanediamine, N-ethylethanediamine, N-hexylethanediamine, N-butyl-1,3-propanediamine, N-cyclohexyl-1,3-propanediamine, N-benzyl-1 , 5-diamino-2-methylpentane, N-benzyl-1,3-bis (aminomethyl) benzene, N- (2-ethylhexyl) -1,3-bis (aminomethyl) benzene, 4-aminomethylpiperidine, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), dipropylenetriamine (DPTA), N- (2-aminoethyl) -1, 3-propanediamine (N3-amine), bis-hexamethylenetriamine (BHMT ), N3- (3-aminopentyl)
  • - Primary di- or triamines such as in particular ethylenediamine, 1, 2- and 1, 3-propanediamine, 2-methyl-1, 2-propanediamine, 2, 2-dimethyl-1, 3-propanediamine, 1, 3-butanediamine , 1, 4-butanediamine, 1, 3-pentanediamine (DAMP), 1, 5-pentanediamine, 1, 5-diamino-2-methylpentane (MPMD), 2-butyl-2-ethyl-1, 5-pentanedi - amine (C1 1 -Neodiamin), 1, 6-hexanediamine, 2,5-dimethyl-1, 6-hexanediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine (TMD), 1, 7-heptanediamine , 1, 8-octanediamine, 1, 9-nonanediamine, 1, 10-decanediamine, 1, 1 1-undecanediamine, 1, 12-dodecanediamine, 1, 2, 1, 3 and 1, 4-diaminocyclohexan
  • Such amines may be present in free or blocked form. In blocked form, they are present in particular as so-called latent hardeners which are activatable with moisture, in particular in the form of aldimines, ketimines, enamines, oxazolidines, imidazolidines or hexahydropyrimidines. Such latent hardeners are particularly suitable as a component of isocyanate group-containing compositions.
  • N secondary aliphatic polyamines
  • secondary aliphatic polyamines such as in particular N, N'-dibutylethylenediamine; N, N'-di-tert-butylethylenediamine, N, N'-diethyl-1,6-hexanediamine, 1- (1-methylethylamino) -3- (1-methylethylaminomethyl) -3,5,5-trimethylcyclohexane (Jeff Link ® 754 from Huntsman), N4-cyclohexyl-2-methyl-N2- (2-methylpropyl) - 2,4-pentanediamine, N, N'-dibenzyl-1, 3-bis (aminonnethyl) benzene, N, N '-bis (2-ethylhexyl) -1, 3-bis (aminonnethyl) benzene, bis (4- (N-alkylamino) cyclohexyl) - methane, N-al
  • N, N'-dialkyl-p-phenylene lendiamine such as in particular Unilink ® 4100 (from Dorf Ketal) or N, N'-dialkyl-4,4'-diaminodiphenylmethanes such as in particular Unilink 4200 ® (from village Ketal); or
  • aromatic polyamines in particular 4,4'-diaminodiphenylsulfone (DDS), 2,6-diaminopyridine, 4-amino-N- (4-aminophenyl) benzenesulfonamide, 5,5'-methylenedianthranilic acid, dimethyl ( 5,5'-methylenedithethranilate), 1,3-propylene bis (4-aminobenzoate), 1,4-butylene bis (4-aminobenzoate), tetramethylene oxide bis (4-aminobenzoate), in particular the Versalink ® - Tylen P-250, P-650 or P-1000 (all ex Air Products), 1, 2-bis (2-amino- phenylthio) ethane.
  • DDS 4,4'-diaminodiphenylsulfone
  • 2,6-diaminopyridine 2,6-diaminopyridine
  • the curable composition optionally contains additionally hydroxyl- or mercapto-containing compounds, in particular glycols or polyols or polyphenols or polythiols.
  • 1, 2-ethanediol, 1, 2-propanediol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol are particularly suitable , 1, 3-pentanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, neopentyl glycol, Dibromneopentylgly- kol, 1, 2-hexanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 2 -Octandiol, 1, 8-octanediol, 2-ethyl-1, 3-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tri-propylene glycol, 1, 3-cyclohexanedimethanol, 1, 4-cycl
  • Polyetherpolyols in particular polyoxyalkylenediols and / or polyoxyalkylenetriols, in particular polymerization products of ethylene oxide or 1,2-propylene oxide or 1,2- or 2,3-butylene oxide or oxetane or tetrahydrofuran or mixtures thereof, these with the aid of a starter molecule with two or more active hydrogen atoms may be polymerized, in particular a starter molecule such as water, ammonia or a compound having several OH or NH groups such as 1, 2-ethanediol, 1, 2- or 1, 3-propanediol, neopentyl glycol, diethylene glycol, Triethylene glycol, the isomeric dipropylene glycols or tripropylene glycols, the isomeric butanediols, pentanediols, hexanediols, heptanediols, octanediols
  • polyether polyols having polymer particles dispersed therein, in particular those of acrylonitrile, styrene, ⁇ -methylstyrene, methyl (meth) acrylate or hydroxyethyl (meth) acrylate, or of polyurea or polyhydrazodicarbonamide (PHD) or of polyurethane, the two being Phases form a stable, storable dispersion and the polymer may be partially grafted onto the polyether polyol or covalently bound to the polyether polyol.
  • PLD polyhydrazodicarbonamide
  • Preferred polyether polyols are polyoxypropylene diols or polyoxypropylene triols, or so-called ethylene oxide-terminated (EO-endcapped) polyoxypropylene diols or triols.
  • the latter are polyoxyethylene-polyoxypropylene mixed polyols, which are obtained, in particular, in that polyoxypropylene diols or triols are further alkoxylated after completion of the polypropoxylation reaction with ethylene oxide and thus ultimately have primary hydroxyl groups.
  • Preferred polyether polyols have a degree of unsaturation of less than 0.02 meq / g, especially less than 0.01 meq / g.
  • Polyesterpolyols in particular from the polycondensation of hydroxycarboxylic acids or in particular those which are prepared from dihydric to trihydric, in particular dihydric, alcohols, for example ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1, 5-pentanediol, 3-methyl-1, 5-hexanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 10-decanediol, 1, 12-dodecanediol, 1, 12-hydroxystearyl alcohol, 1, 4- Cyclohexanedimethanol, dimer fatty acid diol (dimerdiol), hydroxypivalic acid neopen
  • Polycarbonate polyols as they are accessible by reaction of dihydric or polyhydric alcohols with dialkyl carbonates, diaryl carbonates or phosgene.
  • At least two hydroxyl-bearing block copolymers which have at least two different blocks having a polyether, polyester and / or polycarbonate structure of the type described above, in particular polyetherpolyesterpolyols.
  • Polyhydroxy-functional fats and oils for example natural fats and oils, especially castor oil; or by chemical modification of natural fats and oils-so-called oleochemical-polyols, for example the epoxypolyesters or epoxypolyethers obtained by epoxidation of unsaturated oils and subsequent ring opening with carboxylic acids or alcohols, or by hydroformylation and hydrogenation.
  • saturated oils obtained polyols; or from natural fats and oils by degradation processes such as alcoholysis or ozonolysis and subsequent chemical linkage, for example by transesterification or dimerization, the resulting degradation products or derivatives thereof obtained polyols.
  • Suitable degradation products of natural fats and oils are, in particular, fatty acids and fatty alcohols and also fatty acid esters, in particular the methyl esters (FAME), which can be derivatized, for example by hydroformylation and hydrogenation, to form hydroxy fatty acid esters.
  • FAME methyl esters
  • Polyhydrocarbyl polyols also called oligohydrocarbonols, such as, for example, polyhydroxy-functional polyolefins, polyisobutylenes, polyisoprenes; polyhydroxy-functional ethylene-propylene, ethylene-butylene or ethylene-propylene-diene copolymers, such as those produced by Kraton Polymers; polyhydroxy-functional polymers of dienes, in particular of 1, 3-butadiene, which may in particular also be prepared from anionic polymerization; polyhydroxy-functional copolymers of dienes such as 1, 3-butadiene or diene mixtures and vinyl monomers such as styrene, acrylonitrile, vinyl chloride, vinyl acetate, vinyl alcohol, isobutylene and isoprene, for example polyhydroxy-functional acrylonitrile / butadiene copolymers, such as those from epoxides or amino alcohols and carboxyl-terminated acrylonitrile / butadiene copo
  • polyether polyols Preference is given to polyether polyols, polyester polyols, polycarbonate polyols, poly (meth) acrylate polyols or polybutadiene polyols.
  • the composition preferably comprises a mixture of at least one glycol and at least one polyol, preference being given as glycol 1, 4-butanediol and as polyol to an ethylene oxide-terminated polyoxypropylene polyol.
  • the amine of the formula (I) has, in particular, the function of directly changing the flow properties of the composition when mixing the two components in such a way that a pseudoplastic, less flowing or slipping material is formed. This is also called "in situ thixotropy".
  • the composition preferably contains at least one polyoxyalkylene diamine or triamine having an average molecular weight in the range of 1 to ⁇ 00 6 ⁇ 00 g / mol, in particular the Jeffamine ® grades D-2000, D-4000, T-3000 and / or T-5000 (from Huntsman) and optionally at least one aromatic polyamine, in particular 3,5-diethyl-2,4- or -2,6-toluenediamine or mixtures thereof
  • the amine of the formula (I) effects rapid curing and enables compositions having high strength and extensibility and a particularly low modulus of elasticity, which is advantageous in particular for crack-bridging properties, for example when used as a coating or when sealing expansion joints.
  • the curable composition additionally contains other auxiliaries and additives customarily used in curable compositions, in particular accelerators or catalysts, solvents, thinners, plasticizers, film-forming aids or extenders, polymers, inorganic or organic fillers, fibers, pigments, rheology modifiers , in particular thickeners or anti-settling agents, adhesion promoters, stabilizers against hydrolysis, oxidation, heat, light or UV radiation, flame retardants, surface-active substances, in particular wetting agents, leveling agents, deaerating agents or defoamers, biocides, in particular algicides, fungicides or fungal growth inhibiting substances.
  • the curable composition is a two-part composition wherein the amine of formula (I) is contained in the first component and the amine-crosslinkable compound in the second component.
  • the second component preferably contains at least one polyisocyanate, in particular HDI, IPDI, H 2 MDI, TDI, MDI, PMDI or oligomers or isocyanate-group-containing polyurethane polymers of these isocyanates or mixtures thereof.
  • the second component contains at least one isocyanate group-containing polyurethane polymer based on HDI or IPDI or TDI or MDI.
  • the second component contains at least one liquid form of MDI or PMDI which is liquid at room temperature.
  • the second component contains a combination of at least one room temperature liquid form of MDI or PMDI and at least one isocyanate group-containing polyurethane polymer based on HDI or IPDI or TDI or MDI, in particular based on MDI.
  • the first component preferably contains at least one further compound selected from amines, glycols and polyols which do not correspond to the formula (I).
  • the two components are typically stored in the absence of moisture. They are stored separately from each other.
  • the two components are mixed together with a suitable method, which is influenced by the viscosity and the reaction rate of the two components, shortly before or during the application and brought to harden.
  • a suitable method which is influenced by the viscosity and the reaction rate of the two components, shortly before or during the application and brought to harden.
  • the mixing and / or the curing at ambient temperature in particular in the range of 0 to 50 ° C or at elevated temperature, in particular dere in the range of 60 to 180 ° C, take place.
  • the curing can be carried out in part by moisture, in particular by moisture from the environment, in particular atmospheric moisture.
  • the composition may be heated or heated before, during or after mixing the components. Heating or heating may be expedient for the two components to have a consistency suitable for mixing or for the curing to take place more quickly or to become possible for the first time, for example in the case of blocked isocyanate groups.
  • the mixing can be continuous or batchwise. When mixing, make sure that the two components are mixed as homogeneously as possible. In case of insufficient mixing, local deviations from the advantageous mixing ratio occur, which may result in a deterioration of the mechanical properties and / or blistering. If mixed before application, care must be taken that there is not too much time between blending and the application, so that it does not lead to disturbances such as a poor course or a slow or incomplete build up of adhesion. In particular, the open time of the composition during the application should not be exceeded.
  • open time or "pot life” is used to denote the time span between the mixing of the components and the end of a state of the composition suitable for processing.
  • a measure of the pot life for example, the time to doubling the initial viscosity or the time to tack-free time (tack-free time).
  • the mixing ratio is preferably selected so that the reactive groups of the first component are in a suitable ratio to the reactive groups of the second component.
  • the mixing ratio between the first and second components is typically in the range of about 1: 100 to 100: 1, more preferably 1:20 to 20: 1.
  • the curing of the curable composition is carried out by chemical reaction of the amino groups of the amine of formula (I) and optionally present other nucleophilic reactive groups with the reactive groups of the amine-crosslinkable compounds, optionally with the additional action of moisture or heat. This results in a cured composition.
  • curable compositions are adhesives, sealants, coatings, coatings, paints, elastomers, casting resins, foams, resins for molded parts such as in particular RIM or fiber composites for construction or industrial applications.
  • the curable composition is an adhesive or a sealant or a coating.
  • Suitable substrates to which the curable composition can be applied are, in particular
  • PCC polymer-modified cement mortar
  • ECC epoxy resin-modified cement mortar
  • metals or alloys such as aluminum, copper, iron, steel, non-ferrous metals, including surface-refined metals or alloys such as galvanized or chromium-plated metals;
  • plastics such as hard and soft PVC, polycarbonate, polyester, polyamide, PMMA, ABS, SAN, epoxy resins, phenolic resins, PUR, POM, TPO, PE, PP,
  • EPM or EPDM either untreated or surface treated, for example by means of plasma, corona or flames; - Fiber reinforced plastics such as Carbon Fiber Reinforced Plastics (CFRP), Glass Fiber Reinforced Plastics (GRP) and Sheet Molding Compounds (SMC);
  • CFRP Carbon Fiber Reinforced Plastics
  • GRP Glass Fiber Reinforced Plastics
  • SMC Sheet Molding Compounds
  • insulating foams in particular of EPS, XPS, PUR, PIR, rock wool, glass wool or foamed glass (foam glass);
  • coated or painted substrates in particular painted tiles, painted concrete, powder-coated metals or alloys or painted sheets;
  • the substrates can be pretreated prior to application, in particular by physical and / or chemical cleaning methods or the application of an activator or a primer.
  • Two similar or two different substrates can be bonded and / or sealed.
  • This article is obtained which is glued or sealed or coated with the composition.
  • This article may be a building or a part thereof, in particular a building of civil engineering, a bridge, a roof, a staircase or a facade, or it may be an industrial good or a consumer good, in particular a window Pipe, a rotor blade of a wind turbine, a household machine or a means of transport such as, in particular, an automobile, a bus, a truck
  • Rail vehicle a ship, an airplane or a helicopter, or an attachment thereof.
  • the amine of the formula (I) has the function of directly changing the flow properties of the composition during mixing of the two components in such a way that a pseudoplastic, less flowing or slipping material is formed. This is also called "in situ thixotropy".
  • the curable composition is an aqueous polyurethane dispersion.
  • the amine of formula (I) is used in particular in the preparation of the polyurethane dispersion as Kettenverlteil- erer, wherein during or immediately after emulsifying an isocyanate group-containing emulsifiable polyurethane polymer in water, the amine of formula (I), optionally dissolved in water and optionally together with another chain extender, in particular ethylenediamine, 1, 3-pentanediamine (DAMP) or 1, 5-diamino-2-methylpentane (MPMD) is added.
  • DAMP 1, 3-pentanediamine
  • MPMD 5-diamino-2-methylpentane
  • the amine of the formula (I) is preferably used in a sub-stoichiometric or stoichiometric amount; preferably in such an amount that the ratio between the amino groups of the amine of the formula (I) and the isocyanate groups in the range of 0.1 to 1 .0.
  • the amine of the formula (I) allows a high strength and extensibility of the cured polyurethane dispersion, with a particularly low modulus of elasticity, which is particularly advantageous for crack-bridging properties.
  • NK stands for standard climate
  • standard climate refers to a temperature of 23 + 1 ° C and a relative humidity of 50 + 5%.
  • the viscosity of low-viscosity samples (below 150 mPa-s) was measured on a thermostated cone-plate Rheometer Anton Paar Physica MCR 300 (cone diameter 25 mm, cone angle 2 °, cone tip-plate distance 0.05 mm, shear rate 100 s -1 )
  • the viscosity of higher-viscosity samples (above 150 rnPa-s) was measured on a thermostated Rheotec RC30 cone-plate viscometer (cone diameter 50 mm, cone angle 1 °, cone tip-to-plate distance 0.05 mm, shear rate 10 s -1 ).
  • the amine number was determined by titration (with 0.1 N HClO 4 in acetic acid against crystal violet).
  • FT-IR Infrared
  • GC Gas chromatograms
  • the reaction was checked by IR spectroscopy to see if the imine band had disappeared at about 1665 cm -1 and then the hydrogenated solution was concentrated on a rotary evaporator at 65 ° C., removing unreacted 1,2-propanediamine and isopropanol of which 300 g were distilled under reduced pressure at 80 ° C., collecting 237.5 g of distillate at a vapor temperature of 60 to 63 ° C.
  • FT-IR 3361, 3229, 3025, 2956, 2817, 1601, 1494, 1452, 1372, 1115, 1027, 824, 732.
  • the purified by distillation quality was used as N-benzyl-1, 2-propanediamine.
  • compositions Z1 and Z2 and Ref1 to Ref4 are Compositions Z1 and Z2 and Ref1 to Ref4:
  • compositions are particularly suitable as two-component adhesives with in-situ thixotropy.
  • a first component K1 was prepared by
  • Voranol CP ® 4755 EO-endcapped polyoxypropylene lentriol, an OH number of 35.0 mg KOH / g, from Dow
  • the polymer 1 was prepared by mixing 1300 g Acclaim ® 4200 (polyoxypropylene pylene-diol, OH number 28.5 mg KOH / g, of Covestro) 2600 g Voranol CP ® 4755 (EO-endcapped polyoxypropylene triol, OH number 35.0 mg KOH / g, from Dow), 600 g Desmodur ® 44 MC L (4,4'-diphenylmethane diisocyanate, from Covestro) and 500 g of diisodecyl phthalate according to a known method at 80 ° C to a Isocyanate group-containing polyurethane polymer having a content of free isocyanate groups of 2.1% by weight were reacted.
  • a film of 2 mm thickness was prepared, cured for 7 days in standard atmosphere and on aspect and the mechanical properties of tensile strength, elongation at break and modulus 5% (at 0.5-5% elongation) according to DIN EN 53504 at a pulling speed of 200 mm / min tested.
  • beautiful a bubble-free, non-sticky film was called a homogeneous surface.
  • the time to tack-free time was determined by applying a few grams of the freshly mixed composition in a layer thickness of about 2 mm to cardboard and determining the time in the standard atmosphere until for the first time, no residue remained on the pipette when lightly tapping the surface of the composition by means of a pipette made of LDPE.
  • each composition was determined. For this purpose, 8 ml of the freshly mixed mass were applied from a front-cut commercial 10 ml plastic syringe from above onto a piece of horizontally lying cardboard boxes and this tilted immediately in a vertical position, so that the applied composition came to rest horizontally. Subsequently, the extent of the decay was measured from the horizontal position down during curing in standard atmosphere.
  • compositions Z1 and Z2 are examples according to the invention.
  • compositions Ref1 to Ref3 are comparative examples.
  • Table 2 :
  • compositions Z3 and Z4 and Ref4 are Compositions Z3 and Z4 and Ref4:
  • compositions are particularly suitable as two-component, hand-processable coatings having crack-bridging properties.
  • a first component K1 was prepared by processing and storing the amines shown in Table 3 in the amount indicated in a vacuum dissolver with exclusion of moisture.
  • composition Z1 For each composition, a film of 2 mm thickness was cast, cured for 14 days under standard conditions and tested for aspect, tensile strength, elongation at break and modulus of elasticity 5% as described for composition Z1. Furthermore, the tear propagation resistance was determined according to DIN ISO 34 at a tensile speed of 500 mm / min.
  • compositions Z3 and Z4 are examples according to the invention.
  • the composition Ref4 is a comparative example.
  • polyether amines T 5000 polyoxypropylene triamine having an average molecular weight of about 5000 g / mol, from BASF
  • Ethacure ® 100 (mixture containing 3,5-diethyl-2,4- and -2,6-toluylendi- amine, from Albemarle)
  • composition Z5 is a composition of Composition Z5:
  • This composition is particularly suitable as a two-component, hand processable elastic coating with a long open time.
  • a first component K1 was prepared by
  • Voranol CP ® 4755 EO-endcapped polyoxypropylene lentriol, an OH number of 35.0 mg KOH / g, from Dow
  • GT zeolite paste molecular sieve powder 3A, 50% by weight in castor oil, from Zeochem
  • 2.0 GT salicylic acid solution 5% by weight in dioctyl adipate
  • K2 Desmodur ® VH 20 N 24.5% by weight NCO content; modified 4,4'-di-phenylmethane diisocyanate comprising MDI carbodiimide adduct reacted with little polyol, liquid at room temperature of Covestro was used.
  • the pot life was determined by moving 20 grams of the blended composition at regular intervals using a spatula. If the composition was emotionally thickened for sensible processing for the first time, the pot life was read off.
  • composition Z3 Tensile strength, elongation at break, modulus of elasticity 5%, tear propagation resistance and aspect were tested as described for composition Z3.
  • the resulting polymer was then cooled to 30 ° C and treated with 4.4 g of triethylamine. Then, with good stirring, 203.5 g of cold water (1 ° C.) were stirred in, followed by a solution of 100 g of cold water and the chain extender indicated in Table 4 in the stated amount. The resulting dispersion was stirred for 10 minutes, followed by 10 minutes of gentle vacuum and gentle stirring.
  • particle size Zetasizer Nano ZS from Malvern, average particle diameter
  • solids content Halogen Moisture Analyzer HR73 from Mettler Toledo
  • a film of thickness 1 .5 mm was prepared from each dispersion by placing an appropriate amount of the dispersion in a Teflon mold and keeping it dry for 14 days under standard climatic conditions.
  • an elastic, clear, non-sticky film of which tensile strength, elongation at break, modulus of elasticity 5% (at 0.5-5% elongation) and modulus of elasticity 10% (at 0-100% elongation) according to DIN EN 53504 at a Tensile speed of 200 mm / min and the water absorption were checked.
  • Dispersion D1 is an example according to the invention.
  • the dispersions Ref5 and Ref6 are comparative examples.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne l'utilisation d'une amine représentée par la formule (I) pour des compositions polymères durcissables. L'amine représentée par la formule (I) présente des propriétés avantageuses en termes d'odeur et d'émission ainsi qu'en termes de réactivité, ce qui confère notamment aux compositions une sécurité de process remarquable pendant les opérations de stockage, d'application et de durcissement.
EP16805746.1A 2015-11-24 2016-11-24 Amine pour compositions polymères durcissables à sécurité de process élevée Withdrawn EP3380538A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP15195975 2015-11-24
PCT/EP2016/078700 WO2017089472A1 (fr) 2015-11-24 2016-11-24 Amine pour compositions polymères durcissables à sécurité de process élevée

Publications (1)

Publication Number Publication Date
EP3380538A1 true EP3380538A1 (fr) 2018-10-03

Family

ID=54780070

Family Applications (1)

Application Number Title Priority Date Filing Date
EP16805746.1A Withdrawn EP3380538A1 (fr) 2015-11-24 2016-11-24 Amine pour compositions polymères durcissables à sécurité de process élevée

Country Status (2)

Country Link
EP (1) EP3380538A1 (fr)
WO (1) WO2017089472A1 (fr)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2465843A1 (fr) * 2010-12-17 2012-06-20 Sika Technology AG Polyamines dotées de groupes aminés aliphatiques secondaires
EP2706075A1 (fr) * 2012-09-11 2014-03-12 Sika Technology AG Colle de polyuréthane structurelle avec une température de transition vitreuse basse
US10287388B2 (en) * 2014-08-13 2019-05-14 Sika Technology Agh Amine for low-emission epoxy resin compositions

Also Published As

Publication number Publication date
WO2017089472A1 (fr) 2017-06-01

Similar Documents

Publication Publication Date Title
EP2200973B1 (fr) Aldimines comprenant des groupes hydroxyle et compositions contenant des aldimines
EP2132245B1 (fr) Composition munie de groupes d'isocyanat et d'aldimine contenant une teneur en isocyanat monomère moindre
EP1934172B1 (fr) Composes contenant des aldimines
EP2038323B1 (fr) Couche de polyuréthane sans cov ou pauvre en cov
EP2220034B1 (fr) Aldimines aromatiques et compositions de polyuréthane contenant de l'aldimine
EP2414418B1 (fr) Composition à double durcissement contenant un polyisocyanate désactivé en surface
EP3116928B1 (fr) Film liquide en polyuréthane sans solvant
EP3394136B1 (fr) Polyaldimine et composition de polyurethane durcissable
EP1770107A1 (fr) Composition de polyuréthanne durcissant par l'humidité
EP2137137B1 (fr) Dialdimine, emulsion contenant une dialdimine, et composition de polyurethane a deux composants et utilisations correspondantes
EP1834971A1 (fr) Composition de polyuréthane durcissable par l'humidite ayant une bonne caractéristique a basse température
EP2072550A1 (fr) Compositions durcissables à dégazage réduit
WO2010063739A1 (fr) Compositon de polyuréthanne contenant de l'hydroxyaldimine
EP2132248A1 (fr) Aldimines comportant des groupements réactifs munis d'hydrogène actif
EP1975187A1 (fr) Procédé de fabrication de composition de polyuréthane ayant une teneur en isocyanat monomère moindre
WO2017108834A1 (fr) Compositions de polyuréthane présentant une migration des plastifiants réduite
EP3642252A1 (fr) Durcisseur latent et composition polyuréthane durcissable
WO2020030607A1 (fr) Composition de polyuréthane ayant une faible teneur en diisocyanates monomères
EP2200970B1 (fr) Aldéhydes présentant des groupes hydroxyle
EP3394132A1 (fr) Composition de polyuréthane bicomposant
EP3380538A1 (fr) Amine pour compositions polymères durcissables à sécurité de process élevée

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20180625

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20190116