EP2132246A1 - Procédé de production de compositions de polyuréthane à faible teneur en monomère isocyanate - Google Patents

Procédé de production de compositions de polyuréthane à faible teneur en monomère isocyanate

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Publication number
EP2132246A1
EP2132246A1 EP08735551A EP08735551A EP2132246A1 EP 2132246 A1 EP2132246 A1 EP 2132246A1 EP 08735551 A EP08735551 A EP 08735551A EP 08735551 A EP08735551 A EP 08735551A EP 2132246 A1 EP2132246 A1 EP 2132246A1
Authority
EP
European Patent Office
Prior art keywords
atoms
formula
hydrocarbon radical
group
optionally
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.)
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Application number
EP08735551A
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German (de)
English (en)
Inventor
Urs Burckhardt
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Sika Technology AG
Original Assignee
Sika Technology AG
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Publication date
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Priority to EP08735551A priority Critical patent/EP2132246A1/fr
Publication of EP2132246A1 publication Critical patent/EP2132246A1/fr
Withdrawn legal-status Critical Current

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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
    • C08G18/3271—Hydroxyamines
    • C08G18/3296—Hydroxyamines being in latent form
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C08G2170/00—Compositions for adhesives
    • C08G2170/20—Compositions for hot melt adhesives

Definitions

  • Polyurethane compositions in particular the isocyanate-containing polyurethane compositions with a low content of monomeric diisocyanates.
  • the monomeric diisocyanates can be partially or completely removed from the polyurethane polymer containing isocyanate groups, for example by extraction or distillation, as disclosed, for example, in WO 01/014443 A1, which, however, is costly and therefore costly.
  • a low NCO / OH ratio in the preparation of isocyanate group-containing polyurethane polymers leads directly to a lower isocyanate monomer content;
  • polymers prepared in this way have increased because of Oligomehs mecanicsrecisionen ("chain extension”) Viscosity and are thus generally less difficult to process and less stable.
  • the object of the present invention is therefore to provide a process for the preparation of isocyanate group-containing polyurethane polymers with a low content of monomeric diisocyanates, which is able to overcome the disadvantages of the prior art. Surprisingly, it has been found that a method according to
  • Claim 1 can solve this problem. This process is extremely efficient, cost-effective and also has the advantage that the dual functionality of the monomers is not lost, so that they are usefully incorporated into the navalmole- cular plastic resulting from the crosslinking of the polyurethane polymers.
  • compositions can be formed which have an advantageous viscosity, are storage-stable and have no slower curing.
  • Such compositions are the subject of claim 19. They are particularly suitable for applications in which a high isocyanate monomer content is disadvantageous, such as in spray applications or in hot-to-process compositions such as hot-melt adhesives.
  • the invention relates to a process for the preparation of a polyurethane composition with a low content of monomeric diisocyanates.
  • a) at least one polyurethane polymer PUP containing isocyanate groups is reacted with b) at least one compound VB, wherein the compound VB is characterized in that it contains both i) an active hydrogen-bearing group, a hydroxyl group or a mercapto group or a secondary group And ii) has at least one blocked amino group which is selected from the group consisting of aldimino groups of the formula (Ia) or (Ib), ketimino groups, enamino groups and oxazolidino groups,
  • Z 1 and Z 2 either independently of one another each represent a hydrogen atom or a monovalent hydrocarbon radical having 1 to 12 C atoms, or together represent a bivalent hydrocarbon radical having 4 to 20 C atoms, the part of an optionally substituted, carbocyclic Rings with 5 to 8, preferably 6, C atoms, are; and Z 3 is either a hydrogen atom or is a branched or unbranched alkyl, cycloalkyl, alkylene or cycloalkylene group, or represents a substituted or unsubstituted aryl or arylalkyl group,
  • Il II or represents a radical of the formula OR or OCR 2 or COR 2 or ff CR 2 , where R 2 represents an aryl, arylalkyl or alkyl group and is in each case substituted or unsubstituted, or represents a radical of the formula (II) stands,
  • R 3 is a hydrogen atom or an alkyl or arylalkyl group, in particular having 1 to 12 C atoms, preferably a
  • Hydrogen atom, and R 4 either is a hydrocarbon radical having 1 to 30 carbon atoms, optionally containing ether oxygen atoms,
  • Z 4 is either a substituted or unsubstituted aryl or heteroaryl group which has a ring size of 5 to 8, preferably 6, atoms,
  • R is a hydrogen atom or an alkoxy group, or a substituted or unsubstituted alkenyl or
  • Arylalkenyl group having at least 6 C atoms having at least 6 C atoms.
  • the proviso here is that the ratio between the isocyanate groups of the polyurethane polymer PUP and the sum of the blocked amino groups and the active hydrogen-bearing group of the compound VB has a value of> 1.
  • the term also encompasses derivatives of such a collective of macromolecules from polyreactions, compounds which have been obtained by reactions, such as additions or substitutions, of functional groups on given macromolecules and which may be chemically uniform or chemically nonuniform.
  • the term also includes so-called prepolymers, ie reactive oligomeric pre-adducts whose functional groups are involved in the construction of macromolecules.
  • polyurethane polymer encompasses all polymers which are prepared by the so-called diisocyanate-polyaddition process, including those polymers which are almost or completely free of urethane groups
  • polyurethane polymers are polyether polyurethanes, polyester polyurethanes, polyethers Polyureas, polyureas, polyester-polyureas, polyisocyanurates and polycarbodiimides.
  • active hydrogen refers to a deprotonatable hydrogen atom attached to a nitrogen, oxygen or sulfur atom.
  • a “blocked amino group” or a “latent amine” is understood in the present text indiscriminately a derivative of an amine having aliphatic primary and / or secondary amino groups, which does not have free, but contains exclusively blocked amino groups and thereby does not undergo direct reaction with isocyanates for at least a certain time. By contact with water, the blocked amino groups of the latent amine hydrolyze wholly or partially, whereupon this begins to react with isocyanates. These reactions lead to crosslinking in polyurethane polymers containing isocyanate groups.
  • primary amino group in the present document denotes an NH 2 group which is bonded to an organic radical
  • secondary amino group denotes an NH group which is attached to two organic radicals which also together form part of a ring may be bonded
  • tertiary amino group or tertiary amine nitrogen denotes a nitrogen atom which is bonded to three organic radicals, wherein two of these radicals may also together be part of a ring.
  • aliphatic amino group refers to an amino group attached to an aliphatic, cycloaliphatic or arylaliphatic radical and thus differs from an "aromatic amino group” attached directly to an aromatic or heteroaromatic radical, such as aniline or 2 -Aminopyhdin.
  • At least one isocyanate group-containing polyurethane polymer PUP is used.
  • a suitable isocyanate group-containing polyurethane polymer PUP is obtainable by the reaction of at least one polyol with at least one polyisocyanate.
  • polyether polyols also called polyoxyalkylene polyols or oligoetherols, which are polymerization products of ethylene oxide, 1,2-propylene oxide, 1,2- or 2,3-butylene oxide , Oxetan, tetrahydrofuran or mixtures thereof, possibly polymerized by means of a starter molecule with two or a plurality of active hydrogen atoms such as water, ammonia or compounds having several OH or NH groups such as 1, 2-ethanediol, 1, 2- and 1, 3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols and tripropylene glycols, the isomeric butanediols, pentanediols, hexanediols, hept
  • Both polyoxyalkylene polyols having a low degree of unsaturation (measured according to ASTM D-2849-69 and expressed in milliequivalents of unsaturation per gram of polyol (mEq / g)) prepared, for example, by means of so-called double metal cyanide complex catalysts (DMC) can be used.
  • DMC double metal cyanide complex catalysts
  • Catalysts), as well as polyoxyalkylene polyols having a higher degree of unsaturation prepared for example with the aid of anionic catalysts such as NaOH, KOH, CsOH or alkali metal alkoxides.
  • Particularly suitable polyether polyols are polyoxyalkylene diols and triols, in particular polyoxyalkylene diols.
  • Particularly suitable polyoxyalkylene di- and triols are polyoxyethylene di- and triols as well as polyoxypropylenedi- and triols.
  • polyoxypropylene diols and triols having a degree of unsaturation lower than 0.02 meq / g and a molecular weight in the range from 1000 to 30,000 g / mol, and also polyoxypropylene diols and triols having a molecular weight of from 400 to 8,000 g / mol.
  • molecular weight or “molar weight” is meant in the present document always the molecular weight average M n .
  • polyoxypropylene diols having a degree of unsaturation lower than 0.02 meq / g and a molecular weight in the range of 1000 to 12O00, in particular between 1000 and 8000 g / mol.
  • Such polyether polyols are sold, for example, under the trade name Acclaim® by Bayer.
  • EO-endcapped ethylene oxide-endcapped polyoxypropylene diols and triols
  • polyoxypropylene-polyoxyethylene polyols which are, for example, characterized to obtain pure polyoxypropylene polyols are alkoxylated with ethylene oxide after completion of the polypropoxylation and thereby have primary hydroxyl groups.
  • Polyester polyols also called oligoesterols, prepared by known methods, in particular the polycondensation of hydroxycarboxylic acids or the polycondensation of aliphatic and / or aromatic polycarboxylic acids with dihydric or polyhydric alcohols.
  • polyester polyols which are prepared from dihydric to trihydric, especially dihydric, alcohols, such as, 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 neopentyl glycol ester, glycerol, 1, 1, 1 - trimethylolpropane or mixtures of the abovementioned alcohols, with organic di- or tricarboxylic acids, especially dicarboxylic acids,
  • polyester polyols are polyester diols.
  • Particularly suitable polyesterdiols are those prepared from adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, dimer fatty acid, phthalic acid, isophthalic acid and terephthalic acid as dicarboxylic acid and from ethylene glycol, diethylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, dimer fatty acid diol and 1,4. Cyclohexanedimethanol as a dihydric alcohol.
  • polyester diols prepared from ⁇ -caprolactone and one of the aforementioned divalent
  • liquid at room temperature amorphous, partially crystalline and crystalline polyester di- and triols, in particular polyester diols.
  • Suitable at room temperature liquid polyester polyols are not far below room temperature, for example, at
  • polyester polyols Combination with at least one amorphous, partially crystalline or crystalline polyester polyol used.
  • Polycarbonate polyols as obtained by reacting, for example, the abovementioned alcohols used to form the polyesterpolyols
  • Dialkyl carbonates such as dimethyl carbonate, diaryl carbonates, such as diphenyl carbonate, or phosgene are accessible.
  • polycarbonate diols in particular amorphous polycarbonate diols.
  • polystyrene resin Suitable as polyols are block copolymers bearing at least two hydroxyl groups which have at least two different blocks having a polyether, polyester and / or polycarbonate structure of the type described above.
  • Polyacrylate and polymethacrylate polyols are also suitable as polyols.
  • Polyhydroxy-functional fats and oils for example natural fats and oils, in particular castor oil; or obtained by chemical modification of natural fats and oils - so-called oleochemical - polyols, for example, obtained by epoxidation of unsaturated oils and subsequent ring opening with carboxylic acids or alcohols epoxy polyesters or epoxy polyethers, or obtained by hydroformylation and hydrogenation of unsaturated oils polyols; or from natural fats and oils by degradation processes such as alcoholysis or ozonolysis and subsequent chemical linkage, for example by transesterification or dimehization, of the resulting degradation products or derivatives thereof obtained polyols.
  • oleochemical - polyols for example, obtained by epoxidation of unsaturated oils and subsequent ring opening with carboxylic acids or alcohols epoxy polyesters or epoxy polyethers, or obtained by hydroformylation and hydrogenation of unsaturated oils polyols
  • degradation processes such as alcoholysis or ozonolysis and subsequent chemical linkage
  • Suitable degradation products of natural fats and oils are in particular fatty acids and fatty alcohols and fatty acid esters, in particular the methyl esters (FAME), which For example, by hydroformylation and hydrogenation to hydroxy fatty acid esters can be derivatized.
  • FAME methyl esters
  • Polyhydrocarbyl polyols also called oligohydrocarbonols, such as, for example, polyhydroxy-functional ethylene-propylene, ethylene-butylene or ethylene-propylene-diene copolymers, for example produced by Kraton Polymers, or polyhydroxy-functional copolymers of dienes, such as 1,3-butanediene or diene mixtures and vinyl monomers such as styrene, acrylonitrile or isobutylene, or polyhydroxy-functional polybutadiene polyols such as those prepared by copolymerization of 1,3-butadiene and allyl alcohol and which may also be hydrogenated.
  • oligohydrocarbonols such as, for example, polyhydroxy-functional ethylene-propylene, ethylene-butylene or ethylene-propylene-diene copolymers, for example produced by Kraton Polymers, or polyhydroxy-functional copolymers of dienes, such as 1,3-butanediene or dien
  • Polyhydroxy-functional acrylonitrile / butadiene copolymers as they can be prepared, for example, from epoxides or aminoalcohols and carboxyl Acrylo- nithl / butadiene copolymers (commercially available under the name of Hycar ® CTBN from Hanse Chemie).
  • These stated polyols preferably have an average molecular weight of from 250 to 30,000 g / mol, in particular from 400 to 20,000 g / mol, and preferably have an average OH functionality in the range from 1.6 to 3.
  • small amounts of low molecular weight di- or polyhydric alcohols such as 1, 2-ethanediol, 1, 2- and 1, 3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols and tripropylene glycols, the isomeric Butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, 1, 3- and 1, 4-cyclohexanedimethanol, hydrogenated bisphenol A, dimeric fatty alcohols, 1, 1, 1-trimethylolethane, 1, 1, 1 -Th- methylolpropane, glycehn, pentaerythritol, low molecular weight alkoxylation products
  • polyisocyanates for the preparation of a polyurethane polymer PUP can be commercially available aliphatic, cycloaliphatic or aromatic Polyisocyanates, in particular diisocyanates, are used, for example the following:
  • HDI 1, 6-hexamethylene diisocyanate
  • TMDI 2-methylpentamethylene-1,5-diisocyanate, 2,2,4- and 2,4,4-trimethyl-1,6-hexamethylene diisocyanate
  • HMDI 1, 10-decamethylene diisocyanate
  • TMDI 2-methylpentamethylene-1,5-diisocyanate
  • TMDI 2,2,4- and 2,4,4-trimethyl-1,6-hexamethylene diisocyanate
  • 10-decamethylene diisocyanate 1, 12-dodecamethylene diisocyanate, lysine and lysine diisocyanate, cyclohexane-1, 3- and -1, 4-diisocyanate and any mixtures of these isomers, 1-methyl-2,4- and -2,6-diisocyanatocyclohexane and any Mixtures of these isomers (HTDI or H 6 TDI), 1-isocyanato-3,3,5-thmethyl-5-
  • the preparation of the polyurethane polymer PUP is carried out in a known manner directly from the polyisocyanates and the polyols, or by stepwise adduction, as they are also known as chain extension reactions.
  • the polyurethane polymer PUP is prepared via a reaction of at least one polyisocyanate and at least one polyol, wherein the isocyanate groups are present in a stoichiometric excess over the hydroxyl groups.
  • the ratio between isocyanate and hydroxyl groups is 1.3 to 5, in particular 1.5 to 3.
  • the reaction is carried out at a temperature at which the polyols, polyisocyanates and polyurethane polymer used are present in liquid form.
  • the polyurethane polymer PUP has a molecular weight of preferably more than 500 g / mol, in particular such between 1000 and 50O00 g / mol, preferably between 2000 and 30,000 g / mol.
  • the polyurethane polymer PUP preferably has an average functionality in the range of 1.8 to 3.
  • the polyurethane polymer PUP is a room temperature solid polyurethane polymer PUP1.
  • a room temperature solid polyurethane polymer PUP1 is advantageously obtainable from polyether polyols, polyester polyols and polycarbonate polyols. Particularly suitable are liquid at room temperature, amorphous, partially crystalline and crystalline polyester and Polycarbonatdi- and triols, especially polyester diols and polycarbonatediols, wherein liquid at room temperature polyester and Polycarbonatdi- and triols are not far below room temperature, for example at temperatures between 0 0 C and 25 0 C, and are preferably used in combination with at least one amorphous, partially crystalline or crystalline polyol.
  • polyester and polycarbonate diols and triols advantageously have a molecular weight of 500 to 5,000 g / mol.
  • a room temperature solid polyurethane polymer PUP1 may be crystalline, semi-crystalline or amorphous.
  • a semi-crystalline or amorphous For a semi-crystalline or amorphous
  • Polyurethane polymer PUP1 is true that it is not or only slightly flowable at room temperature, that is, in particular, that it at 20 0 C a
  • Viscosity of more than 5'0OO Pa-s has.
  • the polyurethane polymer PUP1 preferably has a mean molecular weight of from 1 000 to 10 000 g / mol, in particular from 2 000 to 5 000 g / mol.
  • at least one compound VB is furthermore used, the compound VB being characterized in that it comprises both i) an active hydrogen-bearing group which represents a hydroxyl group or a mercapto group or a secondary amino group, and ii) at least a blocked amino group which is selected from the group consisting of aldimino groups of the formula (I a) or (I b), keto groups, enamino groups and oxazolidino groups.
  • Suitable compounds VB in one embodiment are compounds which have both an active hydrogen-bearing group and at least one aldimino group of the formula (Ia) or (Ib). Such compounds VB are especially aldimino-containing compounds VB1 of the formula (III a) or (III b)
  • a 1 is either a divalent, optionally heteroatom-containing, hydrocarbon radical having 2 to 20 C atoms, or together with R 8 is a trivalent hydrocarbon radical having 3 to 20 C atoms, which optionally at least one heteroatom, in particular in the form of ether Oxygen or tertiary annine nitrogen, contains;
  • X 1 is O or S or NR 7 or NR 8 , wherein R 7 is either a monovalent hydrocarbon radical having 1 to 20 C atoms, which optionally at least one carboxylic acid ester, nitrile, nitro, phosphonic ester, sulfonic or sulfonic acid Group has, stands, or is a substituent of the formula (IV a) or (IV b),
  • B 1 is a bivalent, optionally having hetero atoms, hydrocarbon radical having 2 to 20 carbon atoms, and R 8, together with A 1 is a trivalent hydrocarbon radical having 3 to 20 C Atoms which optionally contains at least one heteroatom, in particular in the form of ether oxygen or tertiary amine nitrogen, is; and
  • Z 1 , Z 2 , Z 3 and Z 4 have the meanings already mentioned.
  • X 1 is O or NR 7 or NR 8 .
  • a 1 and / or B 1 are preferably each an alkylene or oxyalkylene radical having a chain length of 5 atoms, in particular when X 1 is O or S.
  • Preferred compounds VB1 of the formula (III a) are compounds
  • Y 1 and Y 2 either independently of one another each represent a monovalent hydrocarbon radical having 1 to 12 C atoms, or together represent a divalent hydrocarbon radical having 4 to 12
  • Y 3 is either a branched or unbranched alkyl, cycloalkyl, alkylene or
  • Cycloalkylene group is, or Y 3 is a substituted or unsubstituted aryl or arylalkyl group,
  • Il II represents Il or a radical of the formula OR or OCR 2 or COR 2 or CR 2 , where R 2 has the already mentioned meaning, or represents a radical of the formula (II);
  • X 1 ' is O or S or NR 7' or NR 8 , where R 7 is either a monovalent hydrocarbon radical having 1 to 20 C atoms, which optionally contains at least one carboxylic acid ester, nitrile, nitro, phosphonic acid ester, Having sulfonic or sulfonic acid ester group, is, or is a substituent of formula (VI);
  • Y 1 and Y 2 each preferably represent a methyl group.
  • Y 3 is preferably a radical of the formula (II), in particular a radical of the formula (II) in which R 3 is a radical
  • a compound VB1 of the formula (IIIa) or (IIIb) is obtainable, for example, from the reaction of at least one amine B1 of the formula (VII) with at least one aldehyde ALD of the formula (VIIIa) or (VIIIb)
  • X 1a is O or S or NR 9 or NR 8 , where R 9 is either a monovalent hydrocarbon radical having 1 to 20 C atoms, which optionally contains at least one carboxylic acid ester, nitrile, nitro, phosphonic ester, sulfone or sulfonic acid ester group, is, or represents a substituent of the formula (VII a),
  • the reaction between at least one amine B 1 of the formula (VII) and at least one aldehyde ALD of the formula (VIII a) or (VIII b) takes place in a condensation reaction with elimination of water.
  • condensation reactions are well known and described, for example, in Houben-Weyl, "Methods of Organic Chemistry", Vol. XI / 2, page 73ff.,
  • the aldehyde ALD is here stoichiometric or in stoichiometric with respect to the primary amino groups of the amine B1
  • condensation reactions are carried out in the presence of a solvent, by means of which the water formed in the reaction is removed azeotropically.
  • Suitable aldehyde ALD are on the one hand aldehydes of the formula
  • VIII a such as, for example, propanal, 2-methylpropanal, butanal, 2-methylbutanal, 2-ethylbutanal, pentanal, 2-methylpentanal, 3-methylpentanal,
  • Suitable aldehyde ALD are, on the other hand, aldehydes of the formula (VIII b), for example aromatic aldehydes, such as benzaldehyde, 2- and 3- and 4-tolualdehyde, 4-ethyl- and 4-propyl- and 4-isopropyl and 4-butyl benzaldehyde, 2,4-dimethylbenzaldehyde, 2,4,5-thymethylbenzaldehyde, 4-acetoxybenzaldehyde, 4-anisaldehyde, 4-ethoxybenzaldehyde, the isomeric di- and trialkoxybenzaldehydes, 2-, 3- and 4-nitrobenzaldehyde, 2- and 3- and 4-formylpyridine, 2-furfuraldehyde, 2-thiophenecarbaldehyde, 1- and 2-naphthyl-aldehyde, 3- and 4-phenyloxy-benzaldehyde; Quinoline-2-carbaldeh
  • aldehyde ALD are particularly suitable aldehydes which are not enolisable, in particular those which have no hydrogen atom in the ⁇ -position to the carbonyl group.
  • aldehydes ALD examples include the aldehydes of the formula (VIII b) mentioned.
  • aldehydes ALD are furthermore the so-called tertiary aldehydes, that is to say aldehydes ALD of the formula (VIII a) which have no hydrogen atom in the ⁇ -position to the carbonyl group.
  • Tertiary aldehydes ALD of the formula (VIII a) represent aldehydes ALD of the formula (IX).
  • Ethers of 2-hydroxy-2-methylpropanal and alcohols such as propanol, isopropanol, butanol and 2-ethylhexanol; Esters of 2-formyl-2-methylpropionic acid or 3-formyl-3-methylbutyric acid and alcohols such as propanol, isopropanol, Butanol and 2-ethylhexanol; Esters of 2-hydroxy-2-methylpropanal and carboxylic acids such as butyric, isobutyric and 2-ethylhexanoic acid; and the ethers and esters of 2,2-disubstituted 3-hydroxypropanals, butanals or analogous higher aldehydes, especially of 2,2-dimethyl-3-hydroxypropanal, which are described below as being particularly suitable.
  • aldehydes ALD of the formula (IX) are aldehydes ALD of the formula (X).
  • Y 1 , Y 2 , R 3 and R 4 have the meanings already mentioned.
  • Y 1 and Y 2 each represent a methyl group and
  • R 3 is a hydrogen atom.
  • a suitable aldehyde ALD of the formula (X) is in one embodiment an aldehyde ALDI of the formula (X a)
  • R 4a is a hydrocarbon radical having 1 to 30 C atoms, in particular 11 to 30 C atoms, which optionally contains ether oxygen atoms.
  • the aldehydes ALDI of the formula (X a) are ethers of aliphatic, cycloaliphatic or arylaliphatic 2,2-disubstituted 3-hydroxy aldehydes with alcohols or phenols of the formula R 4a -OH, for example fatty alcohols or phenols.
  • Suitable 2,2-disubstituted 3-hydroxy aldehydes are themselves obtainable from aldol reactions, in particular crossed aldol reactions, between primary or secondary aliphatic aldehydes, in particular formaldehyde, and secondary aliphatic, secondary cycloaliphatic or secondary arylaliphatic aldehydes, such as, for example Isobutyraldehyde, 2-methylbutyraldehyde, 2-ethyl butyraldehyde, 2-methylvaleraldehyde, 2-ethylcaproic aldehyde, cyclopentanecarboxaldehyde, cyclohexanecarboxaldehyde, 1, 2,3,6-tetrahydrobenzaldehyde, 2-methyl-3-phenylpropionaldehyde, 2-phenylpropionaldehyde (hydratropaldehyde) or diphenylacetaldehyde.
  • aldol reactions in particular crossed aldo
  • Examples of suitable 2,2-disubstituted 3-hydroxyaldehydes are 2,2-dimethyl-3-hydroxypropanal, 2-hydroxymethyl-2-methylbutanal, 2-hydroxymethyl-2-ethyl-butanal, 2-hydroxymethyl-2-methyl pentanal, 2-hydroxymethyl-2-ethyl-hexanal, 1-hydroxymethyl-cyclopentanecarboxaldehyde, 1-hydroxymethylcyclohexanecarboxaldehyde 1-hydroxymethylcyclohex-3-en-carboxaldehyde, 2-hydroxymethyl-2-methyl-3-phenylpropanal, 3-hydroxy-2-methyl-2-phenylpropanal and 3-hydroxy-2,2-diphenylpropanal.
  • aldehydes ALDI of the formula (X a) are 2,2-dimethyl-3-phenoxy-propanal, 3-cyclohexyloxy-2,2-dimethyl-propanal, 2,2-dimethyl-3- (2-ethylhexyloxy) Propanal, 2,2-dimethyl-3-lauroxy-propanal and 2,2-dimethyl-3-stearoxy-propanal.
  • a suitable aldehyde ALD of the formula (X) is in another embodiment an aldehyde ALD2 of the formula (Xb),
  • aldehydes ALD2 of the formula (Xb) are esters of 2,2-disubstituted 3-hydroxy aldehydes already described, such as 2,2-dimethyl-3-hydroxypropanal, 2-hydroxymethyl-2-methyl-butanal, 2-hydroxy methyl 2-ethyl-butanal, 2-hydroxymethyl-2-methyl-pentanal, 2-hydroxymethyl-2-ethyl-hexanal, 1-hydroxymethyl-cyclopentanecarboxaldehyde, 1-hydroxy-methyl-cyclohexanecarboxaldehyde 1-hydroxymethyl-cyclohex-3-encarboxaldehyde hyd, 2-hydroxymethyl-2-methyl-3-phenyl-propanal, 3-hydroxy-2-methyl-2-phenyl-propanal and 3-hydroxy-2,2-diphenyl-propanal, with carboxylic acids such as formic acid, acetic acid, propionic acid , But
  • aldehydes ALD are the aldehydes ALD of the formula (VIII b) and the formula (IX). Particularly preferred are the aldehydes ALD of the formula (X).
  • an aldimino-containing compound VB1 of the formula (III a) or (III b) it is also possible, in addition to at least one aldehyde ALD of the formula (VIII a) or (VIII b), to use, for example, at least one amine B 1 of the formula (VII).
  • An amine B1 of the formula (VII) contains one or two aliphatic primary amino groups and at least one reactive group which has an active hydrogen.
  • compounds having one or two primary aliphatic and one secondary amino group such as N-methyl-1,2-ethanediamine, N-ethyl-1,2-ethanediamine, N-butyl, are suitable -1, 2-ethanediamine, N-hexyl-1,2-ethanediamine, N- (2-ethylhexyl) -1, 2-ethanediamine, N-cyclohexyl-1,2-ethanediamine, 4-amino-methyl-piperidine, 3 - (4-aminobutyl) piperidine, N- (2-aminoethyl) piperazine, diethylenetriamine (DETA), bis-hexamethylenetriamine (BHMT), 3- (2-aminoethyl) aminopropylamine; Di- and triamines from the cyanoethylation or cyanobutylation of primary mono- and diamines, for example N-methyl-1,3-propanediamine, N
  • aliphatic hydroxyamines having a primary amino group such as, for example, 2-aminoethanol, 2-methylaminoethanol, 1-amino-2-propanol, 3-amino-1-propanol, 4 are suitable as amine B1 of the formula (VII) Amino-1-butanol, 4-amino-2-butanol, 2-amino-2-methyl-propanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 7-amino-1-heptanol, 8 Amino-1-octanol, 10-amino-1-decanol, 12-amino-1-dodecanol, 4- (2-aminoethyl) -2-hydroxyethylbenzene, 3-aminomethyl-3,5,5-trimethylcyclohexanol ; a primary amino-bearing derivatives of glycols such as diethylene glycol, dipropylene glycol,
  • aliphatic mercaptoamines having a primary amino group such as, for example, 2-aminoethanethiol (cysteamine), 3-aminopropanethiol, 4-amino-1-butanethiol, 6-amino-1-hexanethiol, are suitable as amine B1 of the formula (VII), 8-amino-1-octanethiol, 10-amino-1 decanethiol, 12-amino-i-dodecanethiol and aminothio sugars such as 2-amino-2-d eoxy-6-thoglucose.
  • 2-aminoethanethiol cysteamine
  • 3-aminopropanethiol 4-amino-1-butanethiol
  • 6-amino-1-hexanethiol 6-amino-1-hexanethiol
  • Preferred amines B1 of the formula (VII) are amines which are selected from the group consisting of N-methyl-1,2-ethanediamine, N-ethyl-1,2-ethanediamine, N-cyclohexyl-1,2-ethanediamine, N-methyl-1,3-propanediamine, N-ethyl-1,3-propanediamine, N-butyl-1,3-propanediamine, N-cyclohexyl-1,3-propanediamine, 4-aminomethylpiperidine, 3- (4 Aminobutyl) piperidine, DETA, DPTA, BHMT and fatty diamines such as N-cocoalkyl-1,3-propanediamine, N-oleyl-1,3-propanediamine, N-soyaalkyl-1,3-propanediamine and N-tallowalkylamine.
  • X 1 is NR 7 .
  • Such compounds VB1 of the formula (III a) or (III b) can optionally be prepared by a slightly different route than that described so far.
  • This synthetic route consists of reacting an aldehyde ALD of the formula (VIII a) or (VIII b) with a divalent aliphatic primary amine C of the formula H 2 N-A'-NH 2 - where A 'is a bivalent, optionally heteroatom, Hydrocarbon radical having 2 to 20 carbon atoms is - is reacted in a first step to form an intermediate which, in addition to an aldimino group still contains a primary amino group.
  • This intermediate is then reacted in a second step to an aldimino-containing compound VB1 of the formula (III a) or (III b) by simply alkylating the primary amino group.
  • VB1 of the formula (III a) or (III b)
  • the reaction of an aldehyde ALD with an amine C to a primary amino group-containing intermediate is carried out in a condensation reaction with elimination of water, as described above for the reaction of at least one aldehyde ALD with at least one amine B1 of the formula (VII).
  • the stoichiometry between the aldehyde ALD and the amine C is chosen so that 1 mol of aldehyde ALD is used for 1 mol of amine C, which contains two primary amino groups.
  • a solvent-free preparation process is preferred in which the water formed during the condensation is removed from the reaction mixture by applying a vacuum.
  • the reaction of the primary amino group-containing intermediate with the Michael acceptor takes place, for example, by mixing the intermediate with a stoichiometric or slightly more than stoichiometric amount of the Michael acceptor and mixing the mixture at temperatures of from 20.degree. C. to 110.degree complete sales of the Intermediate to the compound VB1 of the formula (III a) or (III b) is heated.
  • the reaction is preferably carried out without the use of solvents.
  • Suitable amines C for this reaction are aliphatic diamines such as ethylenediamine, 1, 2- and 1, 3-propanediamine, 2-methyl-1, 2-propanediamine, 2,2-dimethyl-1, 3-propanediamine, 1 , 3- and 1,4-butanediamine, 1, 3- and 1,5-pentanediamine, 2-butyl-2-ethyl-1, 5-pentanediamine, 1,6-hexamethylenediamine (HMDA), 2,2,4- and 2,4,4-trimethylhexamethylenediamine and mixtures thereof (TMD), 1,7-heptanediamine, 1,8-octanediamine, 2,4-dimethyl-1,8-octanediamine, 4-aminomethyl-1,8-octanediamine , 1, 9-nonanediamine, 2-methyl-1, 9-nonanediamine, 5-methyl-1, 9-nonanediamine, 1, 10-decanediamine, isodecanediamine, 1,11-undecanediamine, 1,12-d
  • polyoxyalkylene diols typically products from the amination of polyoxyalkylene diols, and are available, for example under the name Jeffamine ® (from Huntsman Chemicals), under the name polyetheramine (from BASF) or under the name PC Amine ® (from Nitroil).
  • Particularly suitable polyoxyalkylene diamines are Jeffamine ® D-230, Jeffamine ® D-400, Jeffamine ® XTJ-511, Jeffamine ® XTJ-568 and Jeffamine ® XTJ-569; Polyetheramine D 230 and polyetheramine D 400; PC Amine® DA 250 and PC Amine® DA 400.
  • Preferred amine C are diamines in which the primary amino groups are separated by a chain of at least 5 atoms, or by a ring, in particular 1, 5-diamino-2-methylpentane, 1,6-hexamethylenediamine, 2 , 2,4- and 2,4,4-trimethylhexamethylenediamine and mixtures thereof, 1, 10-decanediamine, 1, 12-dodecanediamine, 1, 3- and 1, 4-diaminocyclohexane, bis (4-aminocyclohexyl) -methane, Bis (4-amino-3-methylcyclohexyl) methane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 1, 3 and 1, 4-bis (aminomethyl) cyclohexane, 2, 5 (2,6) bis (aminomethyl) bicyclo [2.2.1] heptane, 3 (4), 8 (9) - bis (aminomethyl) tricyclo [5.2.1.0 26
  • Michael acceptors for this reaction are maleic or fumaric diesters, such as dimethyl maleate, diethyl maleate, di-butyl maleate, diethyl fumarate; Citraconic diesters such as dimethyl citraconate; Acrylic or methacrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofuryl (meth) acrylate, isobornyl (meth) acrylate; Itaconic diesters such as dimethyl itaconate; Cinnamic acid esters such as methyl cinnamate; Vinylphosphonklarediester such as dimethyl vinylphosphonate; Vinylsulfonic acid esters, in particular vinylsulfonic acid aryl esters; vinyl sulfones; Vinyl nitriles such as acrylonit
  • suitable compounds VB are compounds which have both an active hydrogen-bearing group and at least one ketimino group.
  • Such compounds VB are especially keto-containing compounds VB2 of the formula (XI),
  • X 2 is O or S or NR 10 or NR 8 , where R 10 is either a monovalent hydrocarbon radical having 1 to 20 C atoms which optionally contains at least one carboxylic acid ester, nitrile, nitro, phosphonic ester, sulfone or sulfonic acid ester group, is, or is a substituent of the formula (XII);
  • Z 5 and Z 6 either independently of one another each represent a monovalent hydrocarbon radical having 1 to 12 C atoms, or together represent a bivalent hydrocarbon radical having 4 to 20 C atoms, which forms part of an optionally substituted, carbo-cyclic ring with 5 to 8, preferably 6, carbon atoms; and
  • a 1 , B 1 and R 8 have the meanings already mentioned.
  • Z 5 and Z 6 are preferably either independently of one another in each case an unbranched or especially branched alkyl radical having 1 to 6 C atoms, or together represent an alkyl radical having 4 to 10 C atoms, the part an optionally substituted carbocyclic ring having 5 to 6, in particular 6, C atoms, and / or X 2 is preferably O or NR 10 or NR 8 .
  • a ketimino group-containing compound VB2 of the formula (XI) is obtainable, for example, from the reaction of at least one amine B1 of the formula (VII) with at least one ketone of the formula (XIII) with elimination of water, wherein the keto groups are stoichiometric relative to the primary amino groups or in stoichiometric excess.
  • Suitable ketones of the formula (XIII) for this reaction are, for example, acetone, methylethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl pentyl ketone, methyl isopentyl ketone, diethyl ketone, dipropyl ketone, diisopropyl ketone, dibutyl ketone, diisobutyl ketone, cyclopentanone, Cyclohexanone and actetophenone.
  • X 2 is NR 10 .
  • Such compounds VB2 of the formula (XI) can optionally be prepared by a slightly different route than previously described by reacting at least one ketone of the formula (XIII) with at least one divalent aliphatic primary amine C of the formula H 2 N-A'-NH 2 wherein A 'is a divalent, optionally heteroatom-containing, hydrocarbon radical having 2 to 20 carbon atoms - is reacted in a first step to form an intermediate, which in addition to a keto group still contains a primary amino group.
  • This intermediate is then reacted in a second step in an addition reaction with a double bond Michael acceptor, wherein the double bonds with respect to the primary Amino groups of the intermediate are used stoichiometrically.
  • the reaction of a ketone of the formula (XIII) with an amine C to the primary amino group-containing intermediate is carried out in the same manner as already described for the reaction of an aldehyde ALD with an amine C, as well as the reaction of the intermediate with the Michael acceptor.
  • Such compounds VB are in particular compounds VB3 having enamine groups
  • a 3 is either a divalent, optionally heteroatom-containing, hydrocarbon radical having 2 to 20 C atoms, or together with D 1 or together with R 12 is a trivalent hydrocarbon radical having 3 to 20 C atoms, which optionally at least one heteroatom, in particular in the form of ether oxygen or tertiary amine nitrogen,
  • X 3 is O or S or NR 11 or NR 12 , where R 11 is either a monovalent hydrocarbon radical having 1 to 20 C atoms which optionally contains at least one carboxylic acid ester, nitrile, Has nitro, phosphonic ester, sulfonic or sulfonic acid ester group, is, or represents a substituent of the formula (XV),
  • D 2 stands for a monovalent hydrocarbon radical having 1 to 12 C atoms, and R 12 either together with A 3 or together with D 1 for a trivalent hydrocarbon radical having 3 to 20 C atoms, which optionally at least one heteroatom, in particular in Form of ether oxygen or tertiary amine nitrogen;
  • Z 7 and Z 8 either independently of one another represent a hydrogen atom or a monovalent hydrocarbon radical having 1 to 12 C atoms, or together represent a bivalent hydrocarbon radical having 3 to 20 C atoms, the part of an optionally substituted, carbocyclic ring 5 to 8, preferably 6, C atoms are;
  • Z 9 represents a hydrogen atom or a monovalent hydrocarbon radical having 1 to 12 C atoms
  • D 1 is either a monovalent hydrocarbon radical having 1 to 12 C atoms, or together with R 12 , or together with A 3 , for a trivalent hydrocarbon radical having 4 to 20 C atoms, which optionally at least one heteroatom, in particular in Form of ether oxygen or tertiary amine nitrogen
  • B 1 has the meaning already mentioned.
  • Z 7 , Z 8 and Z 9 are each independently of one another either a hydrogen atom or an alkyl radical having 1 to 4 C atoms. Furthermore, Z 7 and Z 8 together are preferably a divalent hydrocarbon radical having 3 to 10 C atoms, which is part of an optionally substituted carbocyclic ring having 5 to 8, preferably 6, C atoms. Further preferably, D 1 and D 2 are each independently a monovalent hydrocarbon radical having 1 to 6 carbon atoms.
  • D 1 together with R 12 is preferably an optionally substituted, ethylene radical.
  • D 1 together with A 3 preferably represents a trivalent hydrocarbon radical having 4 to 10 C atoms, which optionally contains at least one heteroatom, in particular in the form of ether oxygen or tertiary amine nitrogen.
  • An enamino group-containing compound VB3 of the formula (XIV) is obtainable, for example, from the reaction of at least one amine B3 of the formula (XVI) with at least one aliphatic or cycloaliphatic aldehyde or ketone of the formula (XVII) which is in the ⁇ -position to the carbonyl group has at least one CH group, with elimination of water.
  • X 3a represents O or NR 13 or NR 12 , wherein R 13 is either a monovalent hydrocarbon radical having 1 to 20 C atoms, which optionally has at least one carboxylic acid ester, nitrile, nitro, phosphonic ester, sulfonic or sulfonic acid ester group , is, or represents a substituent of the formula (XVIII), 1 H
  • a 3 , D 1 , Z 7 , Z 8 and Z 9 , R 12 , B 1 and D 2 have the meanings already mentioned.
  • polyamines having two secondary amino groups such as, for example, piperazine, 4,4'-dipiperidylpropane, N, N'-dimethyl-hexamethylenediamine and homologues having higher alkyl or cycloalkyl groups in place of the methyl groups
  • polyamines having three secondary amino groups such as N 1 N'-dimethyl-diethylenetriamine, and such amines are reacted so B3 with an aldimine or ketimine of the formula (XVII), that one of the secondary amino groups will not be implemented, so that an active hydrogen as group HX 3 is preserved.
  • amines B3 of the formula (XVI) which are suitable as amine B3 of the formula (XVI) are hydroxyls and a secondary amino group such as N- (2-hydroxyethyl) piperazine, 4-hydroxypiperidine and monoalkoxylated primary monoamines, ie reaction products of primary Monoamines such as methylamine, ethylamine, propylamine, propylamine, butylamine, hexylamine, 2-ethylhexylamine, benzylamine and fatty amines such as laurylamine or stearylamine, with epoxides such as ethylene oxide, propylene oxide or butylene oxide in a stoichiometric ratio of 1: 1, for example N-methyl-ethanolamine, N Ethyl ethanolamine, N-butyl ethanolamine and N-butyl isopropanolamine.
  • primary Monoamines such as methylamine, ethylamine, propylamine, propy
  • amines B3 of the formula (XVI) which are suitable are amines having a mercapto group and a secondary amino group, for example N- (2-mercaptoethyl) -piperazine, 4-mercapto-piperidine and 2-mercaptoethyl-butylamine.
  • Suitable aldehydes or ketones of the formula (XVII) are aldehydes, for example propanal, 2-methylpropanal, butanal, 2-methylbutanal, 2-ethylbutanal, pentanal, 2-methylpentanal, 3-methylpentanal, 4-methylpentanal, 2,3-dimethylpentanal, hexanal, 2-ethylhexanal, heptanal, octanal, nonanal, decanal, undecanal, 2-methyl-undecanal, dodecanal, methoxyacetaldehyde, cyclopropanecarboxaldehyde, cyclopentanecarboxaldehyde, cyclohexanecarboxaldehyde and diphenylacetaldehyde; and ketones, especially cyclic ketones such as cyclopentanone and cyclohexanone.
  • Such compounds VB are, in particular, compounds VB4 of the formula (XIX) which have oxazolidino groups,
  • a 4 is a bivalent, optionally heteroatom-containing, hydrocarbon radical having 2 to 20 C atoms;
  • Z 10 and Z 11 each independently represent a hydrogen atom or a monovalent hydrocarbon radical having 1 to 12 C atoms,
  • D 3 represents an optionally substituted, alkylene radical having 2 or 3 C atoms, and
  • X 4 is O or S or NR 14 , where R 14 is either a monovalent hydrocarbon radical having 1 to 20 C atoms, which optionally has at least one carboxylic acid ester, nitrile, nitro, phosphonic ester, sulfonic or sulfonic acid ester group , is, or represents a substituent of the formula (XX),
  • Z 10 is preferably a hydrogen atom and Z 11 is an alkyl radical having 1 to 8 C atoms.
  • a 4 is preferably an optionally substituted alkylene radical having 2 or 3 C atoms. Further preferably, X 4 is O.
  • oxazolidino group refers to both tetrahydrooxazole groups (5-membered ring) and tetrahydrooxazine groups (6-membered ring), and an oxazolidino group-containing compound VB4 of the formula
  • (XIX) is obtainable, for example, from the reaction of at least one amine B4 of the formula (XXI) with at least one aldehyde or ketone of the formula (XXII) with elimination of water.
  • X 4a is O or S or NR 15 , wherein R 15 is either a monovalent hydrocarbon radical having 1 to 20 C atoms, which optionally at least one carboxylic acid ester, nitrile, nitro, phosphonic acid ester, sulfonic or sulfonic acid ester group has, stands, or represents a substituent of the formula (XXIII),
  • a 4 , D 3 , Z 10 , Z 11 and B 1 have the meanings already mentioned.
  • Suitable amine B4 of formula (XXI) are secondary hydroxylamines such as diethanolamine, dipropanolamine and diisopropanolamine.
  • amine B4 is preferred diethanolamine, which with a ketone or aldehyde of the formula (XXII) with elimination of water to a Oxazolidino phenomenon having compound VB4 'of the formula (XIX a) can be reacted.
  • Suitable aldehydes or ketones of the formula (XXII) are ketones, for example acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl pentyl ketone, methyl isopentyl ketone, diethyl ketone, dipropyl ketone, diisopropyl ketone, dibutyl ketone, diisobutyl ketone, cyclopentanone , Cyclohexanone.
  • aldehydes such as propanal, 2-methylpropanal, butanal, 2-methylbutanal, 2-ethylbutanal, pentanal, 2-methylpentanal, 3-methylpentanal, 4-methylpentanal, 2,3-dimethylpentanal, hexanal, 2-ethyl-hexanal , Heptanal, octanal, nonanal, decanal, undecanal, 2-methyl-undecanal, dodecanal, methoxyacetaldehyde, cyclopropanecarboxaldehyde, cyclopentanecarboxaldehyde, cyclohexanecarboxaldehyde, diphenylacetaldehyde, benzaldehyde and substituted benzaldehydes.
  • Preference is given to 2-methylpropanal.
  • compounds with mixed blocked amino groups are suitable as compound VB.
  • These are compounds which carry both an active hydrogen-bearing group and two different blocked amino groups which are selected from the group consisting of ketimino groups, enamino groups, oxazolidino groups and aldimino groups of the formula (Ia) or (Ib).
  • Such compounds VB with mixed blocked amino groups usually contain a secondary amino group, which in addition to the active hydrogen carries two radicals each having a different blocked amino group.
  • Compounds VB with mixed blocked amino groups are, for example, the following:
  • the compounds VB have the property that they are monofunctional in the absence of moisture to isocyanate groups, that is, they carry only one reactive group which can react directly with isocyanate groups.
  • This active hydrogen-carrying reactive group reacts with an isocyanate group to a urethane group, thiourethane group or urea group.
  • the blocked amino groups in the form of aldimino groups, keto-imino groups, enamino groups and / or oxazolidino groups of the compounds VB react to the exclusion of moisture with isocyanate groups not or only very slowly.
  • the compounds VB1 of the formula (III a) or (III b) have one or two aldimino groups of the formula (Ia) or (Ib). Upon access of moisture or water, these aldimino groups can hydrolyze formally via intermediates to amino groups, wherein an aldehyde ALD of the formula (VII a) or (VII b) is released. Since this hydrolysis reaction is reversible and the chemical equilibrium lies clearly on the aldimine side, it can be assumed that in the absence of amine-reactive groups only a part of the aldimino groups hydrolyzes.
  • the compounds VB1 of the formula (III b) and of the formula (V), which are prepared starting from non-enolisable aldehydes ALD, furthermore have the property that their aldimino groups can not tautomerize to enamino groups. Because of this property, their aldimino groups are also very stable on storage together with the very reactive aromatic isocyanate groups.
  • the compounds VB2 of the formula (XI) have one or two ketimino groups. Upon ingress of moisture, these ketimino groups hydrolyze to amino groups, releasing a ketone of formula (XIII). In the presence of isocyanate groups, the hydrolyzing ketimino groups react with the isocyanate groups to form urea groups. In the absence of moisture, keto-imino groups together with isocyanate groups, in particular aliphatic isocyanate groups, are storage-stable for a certain time.
  • the compounds VB3 of the formula (XIV) have one or two enamino groups. Upon ingress of moisture, these enamino groups hydrolyze to secondary amino groups to release an aldehyde or ketone of formula (XVII). In the presence of isocyanate groups, the hydrolyzing enamino groups react with the isocyanate groups to form urea groups. In the absence of moisture, enamino groups together with isocyanate groups, in particular aliphatic isocyanate groups, are storage-stable for a certain time.
  • Compounds VB4 of formula (XIX) have one or two
  • the secondary amino groups react to form urea groups and the hydroxyl groups to urethane groups.
  • Blocked amino groups in the form of oxazolidino groups are thus difunctional in their hydrolysis to isocyanate groups, in contrast to blocked ones Amino groups in the form of aldimino, ketimino and enamino groups.
  • oxazolidino groups are very stable on storage together with isocyanate groups, in particular aliphatic isocyanate groups.
  • At least one isocyanate group-containing polyurethane polymer PUP is reacted with at least one compound VB.
  • the ratio between the isocyanate groups of the polyurethane polymer PUP and the sum of the blocked amino groups and the active hydrogen-bearing group of the compound VB has a value of> 1. If oxazolidino groups are present as blocked amino groups, these are advantageously counted twice, since they behave difunctionally after isocyanate hydrolysis. In this case, therefore, the ratio between the isocyanate groups of the polyurethane polymer PUP and the sum of twice the number of oxazolidino groups and the number of other blocked amino groups present and the number of an active hydrogen-bearing group of the compound VB is advantageously> 1.
  • reaction product in each case reacting the active hydrogen-bearing reactive group of the compound VB with an isocyanate group, wherein as the reaction product at least one blocked amino groups and isocyanate groups exhibiting polyurethane polymer is formed.
  • the reaction is carried out with exclusion of moisture, so that the blocked amino groups do not initially react with other isocyanate groups present.
  • the reaction is suitably carried out at a temperature at which the polyurethane polymer PUP is liquid.
  • a catalyst which accelerates the reaction of the active hydrogen-bearing reactive group with isocyanate groups may be present. This is particularly preferred for the reaction of hydroxyl or mercapto groups with isocyanate groups.
  • reaction products in this reaction mainly compounds are formed as exemplified in formula (XXIV).
  • u is 1 or 2 or 3 or 4 or 5
  • v is 1 or 2 or 3 or 4 or 5, with the proviso that (u + v) is 2 or 3 or 4 or 5 or 6 stands
  • Q is the residue of a (u + v) isocyanate group-containing polyurethane polymer PUP after removal of all isocyanate groups
  • X is X 1 or X 2 or X 3 or X 4
  • A is A 1 or A 3 or A 4 ;
  • G is a blocked amino group selected from the group consisting of aldimino groups of the formula (I a) or (I b), keto groups, enamino groups and oxazolidino groups.
  • Preferred compounds VB for the process described are the compounds VB1 of the formula (IIIa) or (IIIb) described, the compounds VB2 of the formula (XI) described, the compounds VB3 of the formula (XIV) described and the compounds VB4 of the compounds described Formula (XIX).
  • Particularly preferred compounds VB for the process described are the compounds VB1 of the formula (III a) or (III b) described, the compounds VB2 of the formula (XI) described and the compounds VB4 of the formula (XIX) described.
  • Particularly preferred compounds VB for the process described are the compounds VBV of the formula (V) which are prepared from tertiary aliphatic or cycloaliphatic aldehydes and the compounds VB4 of the formula (XIX) described.
  • Most preferred compounds VB for the described process are compounds VB1 "of the formula (XXV),
  • X 1 is O or S or NR 7" or NR 8 , where R 7 is either a monovalent hydrocarbon radical having 1 to 20 C atoms, which optionally contains at least one carboxylic acid ester, nitrile, nitro, phosphonic acid ester, Has sulfone or sulfonic acid ester group, is, or represents a substituent of the formula (XXVI),
  • a 1, B 1, Y 1, Y 2, R 3, R 5 and R 8 have the meanings already mentioned.
  • low isocyanate monomer content polyurethane compositions are obtained.
  • a residual content of unreacted monomeric diisocyanates remains in the resulting polymer due to the statistical distribution of the possible reaction products.
  • monomeric diisocyanates also called “isocyanate monomers” for short, are volatile compounds and can be detrimental because of their irritant, allergenic and / or toxic effects they are therefore undesirable. This is especially true for spray applications as well as for hot-to-process compositions such as hot melt adhesives.
  • the incomplete reaction of a polyurethane polymer PUP, which has a certain content of monomeric diisocyanate, with a compound VB in the manner previously described results in a polyurethane composition having a surprisingly low content of monomeric diisocyanates; this is significantly lower than that of the polyurethane polymer PUP before the reaction.
  • the surprisingly low content of monomeric diisocyanates is presumably achieved by virtue of the fact that, in the described reaction of an isocyanate group-containing polyurethane polymer PUP with at least one compound VB, as described above, the active hydrogen-bearing reactive group of compound VB is preferably present in the polyurethane polymer PUP reacts monomeric diisocyanates.
  • a major advantage of the method described is that it is extremely efficient, inexpensive and also has the advantage that the dual functionality of the monomers is not lost, so that they are beneficial incorporated in the resulting high molecular weight in the crosslinking of the polyurethane polymers.
  • the content of monomeric diisocyanates in a polyurethane composition is lowered to a value which corresponds to at most 50% of the initial value.
  • the polyurethane polymer PUP in the reaction with at least one compound VB optionally further Contain substances in the form of auxiliaries and additives commonly used in polyurethane compositions.
  • auxiliaries and additives are, for example
  • Plasticizers for example carboxylic esters, such as phthalates, for example dioctyl phthalate, diisononyl phthalate or diisodecyl phthalate, adipates, for example dioctyl adipate, azelates and sebacates, organic phosphoric and sulfonic acid esters or polybutenes;
  • carboxylic esters such as phthalates, for example dioctyl phthalate, diisononyl phthalate or diisodecyl phthalate
  • adipates for example dioctyl adipate, azelates and sebacates
  • organic phosphoric and sulfonic acid esters or polybutenes for example carboxylic esters, such as phthalates, for example dioctyl phthalate, diisononyl phthalate or diisodecyl phthalate, adipates, for example dioctyl adipate
  • thermoplastic polymers for example homo- or copolymers of unsaturated monomers, in particular from the group comprising ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate or higher esters thereof, and (meth) acrylate, ethylene-vinyl acetate copolymers ( EVA), atactic poly- ⁇ -olefins (APAO), polypropylenes (PP) and polyethylenes (PE) are particularly suitable;
  • EVA ethylene-vinyl acetate copolymers
  • APAO atactic poly- ⁇ -olefins
  • PP polypropylenes
  • PE polyethylenes
  • inorganic and organic fillers for example ground or precipitated calcium carbonates, optionally coated with stearates, Russian, in particular industrially produced Russian (hereinafter referred to as "soot"), baryte (BaSO 4, also called barite), kaolins, aluminum oxides, aluminum hydroxides Silicic acids, in particular finely divided silicas from pyrolysis processes, PVC powders or hollow spheres; fibers, for example polyethylene;
  • Pigments for example titanium dioxide or iron oxides
  • organic carboxylic acids such as benzoic acid, salicylic acid or 2-nitrobenzoic acid
  • organic carboxylic anhydrides such as phthalic anhydride, hexahydrophthalic and Hexahydromethylphthal Acid
  • silyl esters of organic carboxylic acids organic sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid or 4-dodecylbenzenesulfonic acid, sulfonic acid ester, others organic or inorganic acids, or mixtures of the aforementioned acids and acid esters;
  • Catalysts which accelerate the reaction of the isocyanate groups for example organotin compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dibutyltin diacetylacetonate and dioctyltin dilaurate, bismuth compounds such as bismuth trioctoate and bismuth tris (neodecanoate), and compounds containing tertiary amino groups such as 2,2'-dimorpholinodiethyl ether and 1,4-diazabicyclo [2.2.2] octane;
  • organotin compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dibutyltin diacetylacetonate and dioctyltin dilaurate, bismuth compounds such as bismuth trioctoate and bismuth tris (
  • Rheology modifiers for example thickeners or thixotropic agents, for example urea compounds, polyamide waxes,
  • Reactive diluents and crosslinkers for example oligomers of diisocyanates such as MDI, TDI and IPDI, in particular in the form of isocyanurates, carbodiimides, uretonimines, biurets, allophanates or iminooxadiazinediones, adducts of diisocyanates such as MDI, TDI and IPDI with short-chain polyols, and Adipic dihydrazide and other dihydrazides;
  • diisocyanates such as MDI, TDI and IPDI
  • isocyanurates carbodiimides, uretonimines, biurets, allophanates or iminooxadiazinediones
  • Adipic dihydrazide and other dihydrazides Adipic dihydrazide and other dihydrazides
  • latent hardeners with blocked amino groups such as ketimines, oxazolidines, enamines or aldimines;
  • Drying agents for example molecular sieves, calcium oxide, highly reactive isocyanates such as p-tosyl isocyanate, orthoformic esters, alkoxysilanes such as tetraethoxysilane, organoalkoxysilanes such as vinyltrimethoxysilane, and organoalkoxysilanes which have a functional group in the ⁇ -position relative to the silane group;
  • Adhesion promoters in particular organoalkoxysilanes ("silanes”) such as, for example, epoxysilanes, vinylsilanes, (meth) acrylsilanes, isocyanatosilanes,
  • additives such as algicides, fungicides or fungal growth inhibiting substances. It is advantageous to ensure that such additives do not affect the storage stability of the polyurethane composition. This means that during storage these additives are not allowed to trigger the reactions leading to crosslinking, such as hydrolysis of the blocked amino groups or crosslinking of the isocyanate groups, to any significant extent. In particular, this means that all of these additives should contain no or at most traces of water. It may be useful to chemically or physically dry certain additives before mixing.
  • compositions resulting from the process described preferably have a content of monomeric diisocyanates of ⁇ 1% by weight, in particular of ⁇ 0.5% by weight, based on the moisture-reactive constituents of the compositions.
  • compositions have both isocyanate groups and blocked amino groups. Upon contact with moisture or water, the blocked amino groups hydrolyze and begin to react with existing isocyanate groups in the manner already described. In relation to the isocyanate-reactive groups released from the hydrolysis, excess isocyanate groups react directly with water. As a result of these reactions, the composition cures to a high molecular weight plastic; This process is also referred to as networking.
  • the water needed for the curing reaction can either come from the air (atmospheric moisture), or the composition can be contacted with a water-containing component, for example by spraying, or it can be added to the composition in the application of a water-containing component ,
  • the application of the composition can take place in a broad temperature spectrum.
  • the composition can be applied at room temperature, as it is for an elastic adhesive or a sealant is typical.
  • the composition can also be applied at lower as well as at higher temperatures. The latter is particularly advantageous if the composition contains highly viscous or fusible components, as typically present in hotmelt adhesives, for example warm melt adhesives (hot melt) or hotmelt adhesives (hot melt adhesives).
  • the application temperatures are for warm melts, for example in the range of 40 ° C to 80 ° C, with hot-melts between 85 0 C and 200 0 C, in particular between 100 0 C and 150 0 C.
  • the composition crosslinks quickly with little water and without the formation of bubbles. When cured, it has excellent properties. For example, it has a high extensibility and a high tensile strength. Their modulus of elasticity varies depending on the components used to prepare the composition, such as the polyols, polyisocyanates and the amines used to prepare compounds VB. Thus, it can be adapted to the requirements of a particular application, for example to high values for adhesives or to low values for sealants.
  • the low isocyanate monomer content polyurethane composition can be used for a variety of purposes.
  • it is suitable as an adhesive for the bonding of various substrates, for example for bonding components in the production of
  • Automobiles, rail vehicles, ships or other industrial goods in particular as a reactive hotmelt adhesive, as a sealant of all kinds, for example for sealing joints in construction, and as a coating or
  • Protective coatings, sealants and protective coatings are preferred as coatings, and in particular primers.
  • a "primer” is understood to mean a composition which is suitable as a precursor and which, in addition to non-reactive volatile substances and optionally solid additives, contains at least one polymer and / or at least one substance with reactive groups and which is capable of being applied to one Substrate into a solid, well-adhering curing the film in a layer thickness of typically at least 10 microns, wherein the curing is achieved either solely by the evaporation of non-reactive volatiles, such as solvents or water, or by a chemical reaction, or by a combination of these factors, and which good adhesion to a subsequently applied layer, such as an adhesive or sealant, builds.
  • Floor coverings are to be mentioned as preferred among the coverings.
  • Such liners are made by typically pouring and leveling the composition where it cures into a floor covering.
  • floor coverings are used for offices, living areas, hospitals, schools, warehouses, parking garages and other private or industrial applications.
  • compositions are particularly suitable for applications in which a low content of monomeric diisocyanates is required. These are in particular applications in which the composition is sprayed, and applications in which the composition is applied at elevated temperature, for example as a hotmelt adhesive.
  • compositions obtainable from the process described can be used in a process for bonding a substrate S1 to a substrate S2, comprising the steps of: i) applying one of the previously described compositions to a substrate S1; ii) contacting the applied composition with a
  • the compositions obtainable from the process described can be used in a method for sealing between a substrate S1 and a substrate S2, which comprises the step of applying one of the previously described compositions between a substrate S1 and a substrate S2, such that the Composition is in contact with the substrate S1 and the substrate S2, wherein the substrate S2 is made of the same or a different material as the substrate S1.
  • compositions obtainable from the process described can be used in a process for coating a substrate S1, comprising the step i '") application of one of the previously described compositions to a substrate S1 within the open time of the composition.
  • composition is a so-called warm melt, the composition is applied to one before application
  • Temperature 40 0 C to 80 0 C in particular from 60 0 C to 80 0 C, heated and is applied in particular at this temperature in step i) or i ') of the method described above for bonding.
  • the composition is before application to a temperature of 85 0 C to 200 0 C, in particular from 100 0 C to 180 0 C, preferably from 120 0 C to 160 0 C, heated and is applied in particular at this temperature in step i) or i ') of the above-described method for bonding.
  • Suitable substrates S1 or S2 are, for example, inorganic
  • Substrates such as glass, glass ceramic, concrete, mortar, brick, brick, plaster and natural stones such as granite or marble; Metals or alloys such as aluminum, steel, non-ferrous metals, galvanized metals; organic substrates such as leather, fabrics, Paper, wood, resin bonded wood, resin-texil composites, plastics such as polyvinyl chloride (PVC), acrylonitrile-butadiene-styrene copolymers (ABS), SMC (sheet molding composites), polycarbonate (PC), polyamide (PA ), Polyesters, polyoxymethylene (POM), epoxy resins, polyurethanes (PUR), polyolefins (PO), in particular plasma-corona or flame-treated polyethylene (PE) and polypropylene (PP), ethylene / propylene copolymers (EPM) and Ethylene / propylene-diene terpolymers (EPDM); as well as paints and varnishes, in particular automotive paints.
  • PVC polyvinyl chlor
  • Coating creates an article.
  • This article is in particular a building, in particular a building of civil engineering, or an industrial good or a consumer good, in particular a window, a household machine, or a means of transport, in particular a vehicle on water or on land, preferably an automobile, a bus , a truck, a train or a ship, or an attachment of a means of transport, or an article of the furniture, textile or packaging industry.
  • Particularly suitable is the process described for the preparation of a hot melt adhesive composition with a low isocyanate monomer content.
  • This process results in reactive hot melt adhesives having a surprisingly low isocyanate monomer content.
  • the adhesive is meltable, that is, that it has a sufficiently low viscosity at the application temperature to be applied, and that it builds up a sufficient adhesive strength as soon as possible, already before the crosslinking reaction is complete with atmospheric moisture (initial strength). It has been found that the hotmelt adhesives obtainable from the described process with a low isocyanate monomer content at the application temperatures customary for hotmelt adhesives in the range from 85.degree. C. to 200.degree. C., typically from 120.degree. C. to 160.degree. C., are easy to handle Viscosity, and that they build up a good adhesive strength enough to cool down.
  • such a hotmelt adhesive comes into contact with moisture, in particular in the form of atmospheric moisture.
  • the chemical crosslinking with moisture also sets in, mainly by hydrolyzing the existing aldimino groups by moisture and reacting rapidly with existing isocyanate groups in the manner already described. Excess isocyanate groups also crosslink with moisture in a known manner.
  • Adhesive shows a greatly reduced tendency to form bubbles when crosslinked with moisture, since little or no carbon dioxide is formed in the crosslinking due to the presence of blocked amino groups, depending on the stoichiometry.
  • Infrared spectra were measured on an FT-IR 1600 instrument from Perkin-Elmer (horizontal ATR ZnSe crystal measuring unit), with the substances applied undiluted as a film.
  • the absorption bands are given in wavenumbers (cm "1 ) (measurement window: 4000-650 cm “ 1 ).
  • the viscosity was measured at the indicated temperature on a thermostated cone-plate viscometer Physica UM (cone diameter 20 mm, cone angle 1 °, cone tip-plate distance 0.1 mm, shear rate 10 to 1000 s -1 ).
  • the amine content of the dialdimines prepared ie the content of protected amino groups in the form of aldimino groups, was determined titrimetrically (with 0.1 N HClO 4 in glacial acetic acid, against crystal violet) and is always given in mmol N / g.
  • the content of monomeric diisocyanates was determined by means of HPLC (detection via photodiode array, 0.04 M sodium acetate / acetonitrile as mobile phase) and is given in% by weight based on the total composition.
  • Tensile strength, elongation at break and modulus of elasticity were determined in
  • IR: 3350br (OH), 2960, 2928, 2868, 1650 (C N), 1474sh, 1464, 1432, 1390, 1362, 1285, 1220, 1202, 1146, 1058, 1028, 994, 946, 927, 914, 834, 808, 713.
  • IR: 3385br (OH), 3056, 2922, 2881, 2855, 2812, 2765sh, 2695, 1644 (C C), 1452, 1386, 1346, 1300, 1282, 1270, 1204, 1188sh, 1138, 1056, 1039sh. 1016sh, 1008, 976, 952, 930, 917, 894, 876, 836, 788, 688, 666.
  • IR: 3375br (OH), 2956, 2933, 2927, 2902, 2864, 271 Obr, 1666 (C N), 1476, 1458, 1396, 1362, 1340sh, 1278, 1230sh, 1212, 1126, 1060, 958sh, 942 , 920, 894, 812, 776.
  • IR: 3380br (OH), 3084, 3061, 3029, 2934sh, 2909sh, 2858, 1959br, 1897br, 1823br, 1700, 1644 (C N), 1600, 1580, 1492, 1450, 1378, 1342, 1312, 1294, 1220, 1170, 1122, 1062, 1027, 1002sh, 968, 931, 892, 853, 810, 754, 692.
  • polyol Dynacoll 7360 ® (Degussa; crystalline polyester diol, OH number 32 mg KOH / g, acid number of about 2 mg KOH / g) and 65 g of isophorone diisocyanate (IPDI; Vestanat ® IPDI, Degussa) were reacted by a known method at 80 ° C to give an NCO-terminated polyurethane polymer.
  • the reaction product which was solid at room temperature had a titrimetrically determined content of free isocyanate groups of 2.25% by weight.
  • the respective constituents were heated to 100 ° C. in accordance with Table 1 and weighed into a screw capped polypropylene screw under a nitrogen atmosphere in the indicated parts by weight and centrifugally mixed (SpeedMixer TM DAC 150, FlackTek Inc., 1 min at 3000 rpm). min) mixed.
  • the low-viscosity mixture thus obtained was immediately filled into an internally painted aluminum tube, this hermetically sealed and stored for 1 hour at 100 ° C.
  • Table 1 Composition of the hotmelt adhesives of Examples 1 to 6 and Comparative Example 7.
  • Table 2 Properties of the hot-melt adhesives of Examples 1 to 6 and Comparative Example 7.
  • Hotmelt adhesive of Comparative Example 7 they have a significantly lower content of monomeric 4,4'-MDI, wherein this content is lowered by the inventive method to values between 6% and 27% of the initial value.
  • the respective constituents were heated to 100 ° C. according to Table 3 and weighed into a screw capped polypropylene screw under a nitrogen atmosphere in the indicated parts by weight and centrifuged (SpeedMixer TM DAC 150, FlackTek Inc., 1 min Rpm).
  • the low-viscosity mixture thus obtained was immediately filled into an internally painted aluminum tube, this hermetically sealed and stored for 1 hour at 100 ° C.
  • Table 3 Composition of the hotmelt adhesives of Examples 8 to 13 and Comparative Example 14. In Examples 8 to 13, the ratio between the
  • the hot-melt adhesives of Examples 8 to 13 and Comparative Example 14 thus prepared were tested for viscosity and monomeric isophorone diisocyanate (IPDI, sum of cis and trans isomers).
  • IPDI isophorone diisocyanate
  • the tensile strength, elongation at break and modulus of elasticity were measured on the adhesive film stored for 3 weeks. The results are shown in Table 4.
  • Table 4 Properties of the hotmelt adhesives of Examples 8 to 13 and Comparative Example 14.
  • the hot-melt adhesives of Examples 8 to 13 produced by the process according to the invention have a readily handleable viscosity and cure within 3 weeks to a well-crosslinked plastic which has a high tensile strength, a high elongation at break and a high elasticity. Module has. Compared with the hot-melt adhesive of Comparative Example 14, they have a significantly lower content of monomeric IPDI, wherein this content is lowered by the inventive method to values between 1% and 28% of the initial value. The hot-melt adhesive of Comparative Example 14 is not completely crosslinked after 3 weeks and therefore has an insufficient elongation at break.

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  • 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)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Sealing Material Composition (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un procédé de production d'une composition de polyuréthane à faible teneur en monomère isocyanate. Selon ce procédé, au moins un polymère polyuréthane présentant un groupe isocyanate réagit avec au moins un composé VB, le composé VB présentant tant un groupe porteur d'un hydrogène actif qui représente un groupe hydroxyle ou un groupe mercapto ou un groupe amino secondaire, qu'au moins un groupe amino bloqué qui est choisi dans le groupe constitué de groupes aldimino des formules (I a) ou (I b), de groupes cétimino, de groupes énamino et de groupes oxazolidino. Ce procédé permet d'obtenir de manière économique, efficace et élégante des compositions à teneur fortement réduite en diisocyanates monomériques, ces compositions étant particulièrement adaptés comme colles thermofusibles.
EP08735551A 2007-03-28 2008-03-28 Procédé de production de compositions de polyuréthane à faible teneur en monomère isocyanate Withdrawn EP2132246A1 (fr)

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EP07105145A EP1975187A1 (fr) 2007-03-28 2007-03-28 Procédé de fabrication de composition de polyuréthane ayant une teneur en isocyanat monomère moindre
EP08735551A EP2132246A1 (fr) 2007-03-28 2008-03-28 Procédé de production de compositions de polyuréthane à faible teneur en monomère isocyanate
PCT/EP2008/053709 WO2008116927A1 (fr) 2007-03-28 2008-03-28 Procédé de production de compositions de polyuréthane à faible teneur en monomère isocyanate

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Also Published As

Publication number Publication date
EP1975187A1 (fr) 2008-10-01
WO2008116927A1 (fr) 2008-10-02
US20100130674A1 (en) 2010-05-27
CN101646704A (zh) 2010-02-10
BRPI0809377A2 (pt) 2014-09-09
JP2010522269A (ja) 2010-07-01

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