Silane modified formamides

Abstract

The invention relates to novel silane-modified formamides and/or pre-polymers for bonding and/or sealing diverse substrate materials, such as, for example metal, wood, glass and/or plastic. The invention also relates to a reactive single-component adhesive system comprising the claimed silane-modified formamide and/or pre-polymers.

Claims

1. A compound of formula (I): ##STR00015## wherein: X represents an optionally substituted, linear or branched, aliphatic, alicyclic, araliphatic, heterocyclic and/or aromatic structural unit having from 1 to 40 carbon atoms, wherein one or more non-adjacent methylene groups can each be replaced by O or S; or X represents H or NCO; R represents an at least divalent, optionally substituted, linear or branched, aliphatic, alicyclic, araliphatic and/or aromatic structural unit having from 1 to 40 carbon atoms, wherein one or more non-adjacent methylene groups can each be replaced by O or S; R.sup.1 represents an at least divalent, optionally substituted, linear or branched, aliphatic, alicyclic, araliphatic and/or aromatic structural unit having from 1 to 12 carbon atoms, wherein one or more non-adjacent methylene groups can each be replaced by O or S; R.sup.2 and R.sup.3 each independently of the other represents an optionally substituted, linear or branched, aliphatic group having from 1 to 12 carbon atoms; and n represents an integer from 0 to 2.

2. The compound according to claim 1, wherein R.sup.2 and R.sup.3 each independently of the other represents methyl or ethyl.

3. The compound according to claim 1, wherein R represents hexyl, R.sup.1 represents propyl, R.sup.2 and R.sup.3 each independently of the other represents methyl or ethyl, and n represents an integer from 0 to 2.

4. The compound according to claim 1, which is represented by the following formula (III): ##STR00016## wherein R, R.sup.1, R.sup.2, R.sup.3 and n are as defined in claim 1.

5. The compound according to claim 1, which is represented by the following formula (VI): ##STR00017##

6. A process for the preparation of the compound of formula (I) according to claim 1, comprising reacting a silane-modified formamide of formula (Ia) with an isocyanate of formula (Ib): ##STR00018## wherein X, R, R.sup.1, R.sup.2, R.sup.3 and n are as defined in claim 1.

7. A method comprising utilizing the compound according to claim 1 for the preparation of a silane-modified compound of formula (IV): ##STR00019## by reacting the compound of formula (I) wherein X represents an NCO group with a compound of the formula Y(OH).sub.m, wherein R, R.sub.1, R.sup.2, R.sup.3 and n are as defined in claim 1, Y is an optionally substituted, linear or branched, aliphatic, alicyclic, araliphatic, heterocyclic and/or aromatic structural unit having from 1 to 40 carbon atoms or a structural unit reduced by m OH radicals of a polyhydric alcohol (polyol) or of a polyurethane, polyurea, polyester, polyether, polycarbonate, polyacetal, polyacrylate, polyester amide or polythioether polyol, and m represents a number from 1 to 10.

8. A silane-modified compound of formula (IV): ##STR00020## wherein Y is an optionally substituted, linear or branched, aliphatic, alicyclic, araliphatic, heterocyclic and/or aromatic structural unit having from 1 to 40 carbon atoms or a structural unit reduced by m OH radicals of a polyhydric alcohol (polyol) or of a polyurethane, polyurea, polyester, polyether, polycarbonate, polyacetal, polyacrylate, polyester amide or polythioether polyol; R represents an at least divalent, optionally substituted, linear or branched, aliphatic, alicyclic, araliphatic and/or aromatic structural unit having from 1 to 40 carbon atoms, wherein one or more non-adjacent methylene groups can each be replaced by O or S; R.sup.1 represents an at least divalent, optionally substituted, linear or branched, aliphatic, alicyclic, araliphatic and/or aromatic structural unit having from 1 to 12 carbon atoms, wherein one or more non-adjacent methylene groups can each be replaced by O or S; R.sup.2 and R.sup.3 each independently of the other represents an optionally substituted, linear or branched, aliphatic group having from 1 to 12 carbon atoms; and n represents an integer from 0 to 2, and m represents a number from 1 to 10.

9. A process for the preparation of the silane-modified prepolymer of formula (IV) according to claim 8, comprising: reacting a compound of formula (III) with a compound of the formula Y(OH).sub.m: ##STR00021## wherein R, R.sup.1, R.sup.2, R.sup.3, n and m are as defined in claim 8.

10. A method comprising utilizing the compound according to claim 1 for the production of adhesives and sealing materials, lacquers, coatings, sizes, inks and/or printing inks.

11. A reactive one-component coating system comprising at least one compound according to claim 1.

12. A method comprising utilizing the reactive one-component coating system according to claim 11 for coating metal, wood, wood-based materials, glass, leather, textiles, plastics materials, mineral materials, cork, fibres, concrete, paper, cardboard or films.

13. A reactive one-component adhesive system comprising at least one compound according to claim 1.

14. A method comprising utilizing the reactive one-component adhesive system according to claim 13 for the adhesive bonding and/or sealing of metal, wood, wood-based materials, glass, leather, textiles, plastics materials, mineral materials, cork, fibres, concrete, paper, cardboard or films.

15. A kit comprising the reactive one-component adhesive system according to claim 13, for the adhesive bonding and/or sealing of metal, wood, wood-based materials, glass, leather, textiles, plastics materials, mineral materials, cork, fibres, concrete, paper, cardboard or films.

16. A composite comprising metal, wood, wood-based materials, glass, leather, textiles, plastics materials, mineral materials, cork, fibres, concrete, paper, cardboard or films adhesively bonded by the reactive one-component adhesive system according to claim 13.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) According to the invention there are provided compounds of formula (I):

(2) ##STR00002##
wherein in formula (I): X represents an optionally substituted, linear or branched, aliphatic, alicyclic, araliphatic, heterocyclic and/or aromatic structural unit having from 1 to 40 carbon atoms, wherein one or more non-adjacent methylene groups can each be replaced by O or S; or X represents H or NCO; R represents an at least divalent, optionally substituted, linear or branched, aliphatic, alicyclic, araliphatic and/or aromatic structural unit having from 1 to 40 carbon atoms, wherein one or more non-adjacent methylene groups can each be replaced by O or S; R.sup.1 represents an at least divalent, optionally substituted, linear or branched, aliphatic, alicyclic, araliphatic and/or aromatic structural unit having from 1 to 12 carbon atoms, wherein one or more non-adjacent methylene groups can each be replaced by O or S; R.sup.2 and R.sup.3 each independently of the other represents an optionally substituted, linear or branched, aliphatic group having from 1 to 12 carbon atoms; and n represents an integer from 0 to 2.

(3) In one embodiment according to the invention, compounds of formula) are consequently provided.

(4) In a further embodiment according to the invention, a silane-modified prepolymer of formula (IV) is provided:

(5) ##STR00003##
wherein R, R.sup.1, R.sup.2, R.sup.3 and n have the meanings given above, Y is an m-valent, optionally substituted, linear or branched, aliphatic, alicyclic, araliphatic, heterocyclic and/or aromatic structural unit having from 1 to 40 carbon atoms or represents a structural unit reduced by m OH radicals of a polyhydric alcohol (polyol) or of a polyurethane, polyurea, polyester, polyether, polycarbonate, polyacetal, polyacrylate, polyester amide or polythioether polyol and m is a number from 1 to 10, wherein in this case m can also be a fraction, for example when Y is a polyacrylate having a mean OH group content of 2.4.

(6) In a further embodiment according to the invention there is provided a process for the preparation of the compound of formula (I), comprising reacting the silane-modified formamide of formula (Ia) with the isocyanate of formula (Ib):

(7) ##STR00004##
wherein the groups X, R, R.sup.1, R.sup.2, R.sup.3 and n are as defined in claim 1.

(8) In a further embodiment according to the invention there is disclosed a process (A) for the preparation of the silane-modified prepolymer of formula (IV):

(9) ##STR00005##
wherein the variables are as defined fear formula (I).

(10) In a further embodiment according to the invention there is provided a reactive one-component adhesive system or coating system comprising at least one compound of formula (I) and/or at least one compound of formula (IV).

(11) According to the invention, the compound of formula (I) and/or the compound of formula (IV) is used for the production of adhesives and sealing materials, lacquers, coatings, sizes, inks and/or printing inks.

(12) In a further embodiment according to the invention there is described the use of the reactive one-component adhesive system or coating system according to the invention for the coating, adhesive bonding and/or sealing of metal, wood, wood-based materials, glass, leather, textiles, plastics materials, mineral materials, cork, fibres, concrete, paper, cardboard and films.

(13) There is additionally disclosed according to the invention a composite that is bonded by the one-component adhesive system according to the invention.

Definitions

(14) As used herein, the term alicyclic is to denote carbocyclic or heterocyclic compounds which do not belong to the aromatic compounds, such as, for example, cycloalkanes cycloalkenes or oxa-, thia-, aza- or thiaza-cycloalkanes. Specific examples thereof are cyclohexyl groups, cyclopentyl groups and also derivatives thereof interrupted by one or two N or O atoms, such as, for example, pyrimidine, pyrazine, tetrahydropyran or tetrahydrofuran.

(15) As used herein, the term araliphatic is to denote alkyl radicals substituted by aryl groups, such as, for example, benzyl, phenylethyl, biphenyl, etc.

(16) As used in this application, the expression optionally substituted or substituted is to denote in particular the substitution of the relevant structural unit by F, Cl, I, Br, OH, OCH.sub.3, OCH.sub.2CH.sub.3, O-n-propyl or O-isopropyl, OCF.sub.3, CF.sub.3, CF.sub.3, SC.sub.1-6-alkyl and/or another linear or branched, aliphatic, alicyclic, araliphatic and/or aromatic structural unit having from 1 to 12 carbon atoms that is optionally linked via a heteroatom. Preferably, it denotes substitution by halogen (in particular F, Cl), C.sub.1-6-alkoxy (in particular methoxy and ethoxy), hydroxy, trifluoromethyl and trifluoromethoxy.

(17) As used in this application, the expression low molecular weight is to denote compounds whose molecular mass does not exceed approximately 800 g.Math.mol.sup.1.

(18) As used in this application, the expression high molecular weight is to denote compounds whose molecular mass exceeds approximately 800 g.Math.mol.sup.1.

(19) In the case of compounds whose molecular mass does not follow from an exactly defined structural formula, such as, for example, in the case of polymers, the molecular mass is to be understood as being the weight-average molecular weight in each case.

(20) As used in this application, the term monomer is to denote a low molecular weight compound with functional groups which is involved in the synthesis of oligomers and/or (pre)polymers and has a defined molar mass.

(21) As used in this application, the term oligomer is to denote a compound in which only a few monomers of the same type or of different types are linked repeatedly to one another.

(22) As used in this application, the term prepolymer is to denote oligomeric compounds with functional groups which are involved in the final synthesis of polymers.

(23) As used in this application, the term polymer is to denote high molecular weight compounds in which monomers, oligomers and/or prepolymers of the same type or of different types are linked repeatedly to one another and which can differ in terms of degree of polymerisation, molar mass distribution or chain length.

EMBODIMENTS ACCORDING TO THE INVENTION

(24) Embodiments according to the invention are described in detail hereinbelow.

(25) Compounds of Formulae (I), (II) and (III)

(26) In one embodiment there are provided the compounds of the general formula (I):

(27) ##STR00006##
wherein in formula (I): X represents hydrogen, NCO or an optionally substituted, linear or branched, aliphatic, alicyclic, araliphatic, heterocyclic and/or aromatic structural unit having from 1 to 40 carbon atoms, wherein one or more non-adjacent methylene groups can each be replaced by O or S; R represents an at least divalent, optionally substituted, linear or branched, aliphatic, alicyclic, araliphatic and/or aromatic structural unit having from 1 to 40 carbon atoms, wherein one or more non-adjacent methylene groups can each be replaced by O or S; R.sup.1 represents an at least divalent, optionally substituted, linear or branched, aliphatic, alicyclic, araliphatic and/or aromatic structural unit having from 1 to 12 carbon atoms, wherein one or more non-adjacent methylene groups can each be replaced by O or S; R.sup.2 and R.sup.3 each independently of the other represents an optionally substituted, linear or branched, aliphatic group having from 1 to 12 carbon atoms; and n represents an integer from 0 to 2.

(28) In a preferred embodiment there are provided the compounds of formula (II):

(29) ##STR00007##
wherein R, R.sup.1, R.sup.2, R.sup.3 and n are as defined for formula (I).

(30) In a particularly preferred embodiment there are provided the compounds of formula (III):

(31) ##STR00008##
wherein R, R.sup.1, R.sup.2, R.sup.3 and a are as defined for formula (I).
Preferred Substituent Meanings in Formulae (I), (II) and (III)

(32) There are preferably provided compounds of formula (I), (II) and/or (III) wherein in each case: R represents methylene (CH.sub.2), ethylene (CH.sub.2CH.sub.2), propylene (CH.sub.2CH.sub.2CH.sub.2), isophorylene, 4,4-dicyclohexylmethylene, bis(cyclohexylene), 4,4-bisphenylene, o-, m- or p-tolylene, or hexylene (in particular CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2), and particularly preferably n-hexylene; R.sup.1 represents methylene (CH.sub.2) or propylene (in particular n-propylene CH.sub.2CH.sub.2CH.sub.2), particularly preferably n-propylene; R.sup.2 and R.sup.3 each independently of the other represents methyl or ethyl, preferably ethyl; and n represents an integer from 0 to 2.

(33) There are particularly preferably provided compounds of formula (I), (II) and/or (III) wherein in each case: R represents isophorylene, 4,4-dicyclohexylmethylene, bis(cyclohexylene), bisphenylene, tolylene or n-hexylene; R.sup.1 represents n-propylene; R.sup.2 and R.sup.3 each independently of the other represents methyl or ethyl; and n represents an integer from 0 to 2.

(34) There are most particularly preferably provided compounds of formula (III) wherein R is isophorylene, tolylene or n-hexylene, R.sup.1 is n-propylene, R.sup.2 and R.sup.3 are methyl and n=0.

(35) The compounds of formulae (I), (II) and (III) according to the invention are themselves suitable as low molecular weight hinders for coatings or adhesives and/or sealing materials. Alternatively, the compounds of formula (III) according to the invention can be used for the preparation of higher molecular weight prepolymers or polymers, which in turn are suitable as binders for coatings or adhesives and/or sealing materials.

(36) The compounds of formula (I) according to the invention have viscosities (at 23 C., measured by means of a Physica MCR 51 rheometer from Anton Paar Germany GmbH (DE) in accordance with DIN EN ISO 3219) in the range of from 100 to 10,000 mPa.Math.s, preferably from 100 to 7000 mPa.Math.s, particularly preferably from 100 to 5000 mPa.Math.s.

(37) The compounds of formula (I) according to the invention are to be classified in respect of their viscosity between silane-modified polyureas and silane-modified polyurethanes, so that an inexpensive optimisation of the viscosity as compared with silane-modified polyureas is possible by means of the compounds according to the invention.

(38) Process for the Preparation of the Compounds According to the Invention

(39) The compounds of formula (I) according to the invention can be prepared by the following two-stage process, wherein the groups X, R, R.sup.1, R.sup.2, R.sup.3 and a are as defined for formula (I) and R preferably represents an alkyl group having from 1 to 4 carbon atoms:

(40) ##STR00009##

(41) An excess of the formic acid alkyl ester ROCHO is preferably first added dropwise to the amine H.sub.2NR.sup.1Si(R.sup.2).sub.n(OR.sup.3).sub.3-n, R preferably representing an alkyl group having from 1 to 4 carbon atoms. Methyl formate or ethyl formate is particularly preferred as the formic acid alkyl ester ROCHO. Preferably, 1 mol of amine is reacted with an excess of from 1.01 to 6 mol of formic acid alkyl ester ROCHO, particularly preferably from 1.05 to 4 mol, at the boiling temperature of the formic acid alkyl ester. When the reaction is complete, excess formic acid alkyl ester ROCHO and the resulting alcohol ROH are distilled off by means of film distillation and the resulting product (Ia) is optionally filtered off.

(42) The compound of formula (Ia) is then reacted with XRNCO, preferably under inert conditions, at temperatures of from 20 to 200 C., preferably from 40 to 160 C. Depending on the substituent X in XRNCO, the two components are used in an equivalent ratio of isocyanate groups to formamide groups of from at least 1:1 to not more than 40:1, preferably from 8:1 to not more than 30:1 and particularly preferably from 10:1 to not more than 25:1. The reaction can be carried out in solution or solvent-free, but preferably solvent-free. In order to separate off excess XRNCO, the reaction mixture is subsequently passed at a suitable feed rate, such as, for example, 600 ml/h, over a thin-film evaporator under reduced pressure, for example at a pressure of less than 1.0 mbar, preferably less than 0.5 mbar, particularly preferably less than 0.2 mbar, under conditions that are as gentle as possible, for example at a temperature of from 100 to 200 C., preferably from 120 to 180 C.

(43) The preparation of the compounds having the formula (I) can be carried out without the use of catalysts. However, known catalysts can optionally also be added in order to accelerate the reaction. There can be used, for example, tertiary amines, such as, for example, triethylamine, tributylamine, dimethylbenzylamine, diethylbenzylamine, pyridine, methylpyridine, dicyclohexylmethylamine, dimethyl-cyclohexylamine, N,N,N,N-tetramethyldiaminodiethyl ether, bis-(dimethylaminopropyl)-urea, N-methyl- or N-ethyl-morpholine, N-cocomorpholine, N-cyclohexylmorpholine, N,N,N,N-tetramethylethylenediamine, N,N,N,N-tetramethyl-1,3-butanediamine, N,N,N,N-tetramethyl-1,6-hexanediamine, pentamethyldiethylenetriamine, N-methylpiperidine, N-dimethyl-aminoethylpiperidine, N,N-dimethylpiperazine, N-methyl-N-dimethylaminopiperazine, 1,2-dimethylimidazole, 2-methylimidazole, N,N-dimethylimidazole-B-phenylethylamine, 1,4-diazabicyclo-(2,2,2)-octane (DABCO) and bis-(N,N-dimethylaminoethyl) adipatc, amidines, such as, for example, 1,5-diazabicyclo[4.3.0]nonene (DBN), 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU) and 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, alkanolamine compounds, such as, for example, triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyl-diethanolamine, dimethylaminoethanol and 2-(N,N-dimethylaminoethoxy)ethanol, N,N,N-tris-(dialkylaminoalkyl)hexahydrotriazines, such as, for example, N,N,N-tris-(dimethylaminopropyl)-s-hexahydrotriazine, bis(dimethylaminoethyl) ether and also metal salts, such as, for example, inorganic and/or organic compounds of iron, lead, bismuth, zinc and/or tin in conventional oxidation states of the metal, for example iron(II) chloride, iron(III) chloride, bismuth(III) 2-ethylhexanoate, bismuth(III) octoate, bismuth(III) neodecanoate, zinc chloride, zinc 2-ethylcaproate, zinc(II) trifluoromethanesulfonate (zinc triflate), tin(II) octoate, tin(II) ethylcaproate, palmitate, dibutyltin(IV) dilaurate (DBTL), dibutyltin(IV) dichloride or lead octoate.

(44) Preferred catalysts that are to be used are tertiary amines, amidines and tin compounds or zinc compounds of the mentioned type. Particularly preferred catalysts are 1,4-diazabicyclo-(2,2,2)-octane (DABCO), 1,5-diazabicyclo[4.3.0]nonene (DBN), 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU) as well as dibutyltin(IV) dilaurate (DBTL) and zinc(II) trifluoromethanesulfonate (zinc triflate).

(45) The catalysts mentioned by way of example above can be used in the reaction individually or in the form of arbitrary mixtures and are employed, if at all, in amounts of from 0.001 to 1.0 wt. %, preferably from 0.01 to 0.5 wt. %, calculated as the total amount of catalysts used, based on the total amount of starting compounds used.

(46) The progress of the reaction can be monitored, for example, by determining the NCO content by titrimetry. When the desired NCO content has been reached, the reaction is terminated.

(47) Particularly preferably, the compounds of formula (III) according to the invention are prepared by the above-mentioned process, wherein the groups R, R.sup.1, R.sup.2, R.sup.3 and n are as defined for formula (I):

(48) ##STR00010##

(49) A silane-modified formamide having the formula (Ia) is hereby reacted with a diisocyanate OCNRNCO, preferably under an inert protecting gas atmosphere e.g. nitrogen or argon).

(50) Suitable diisocyanates OCNRNCO for the preparation of silane-modified formamides of formula (III) are selected, for example, from the group consisting of 1,4-, 1,3- and/or 1,2-cyclohexane diisocyanate, 1-methyl-2,4-diisocyanato-cyclohexane, 1-methyl-2,6-diisocyanato-cyclohexane, tetramethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, H.sub.6-2,4- and/or -2,6-diisocyanatotoluene, 4,4-diisocyanatodiphenylmethane, 2,4-diisocyanatodiphenylmethane, 2,2-diisocyanatodiphenylmethane, meta- and/or para-xylylene diisocyanate, 2,4-diisocyanatotoluene and/or 2,6-diisocyanatotoluene, isopropenyldintethyltoluylene diisocyanate, , , , ,-tetra-methyl-m- and/or -p-xylylene diisocyanate, 1,6-hexamethylene diisocyanate, trimethylhexane diisocyanate, tetramethylhexane diisocyanate, nonane triisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate), 4,4-diisocyanatodicyclohexylmethane and/or 2,4-diisocyanatodicyclohexylmethane and/or 2,2-diisocyanatodicyclohexylmethane and mono- and di-methyl-substituted derivatives thereof.

(51) There are particularly preferably used for OCNRNCO hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,4-diisocyanatotoluene (TIM) and/or 2,6-diisocyanatotoluene, 4,4-diisocyanatodiphenylmethane, 2,4-diisocyanatodiphenylmethane, 2,2-diisocyanatodiphenylmethane or isomer mixtures thereof.

(52) The reaction of the compounds of formula (Ia) with OCNRNCO takes place at temperatures of from 20 to 200 C., preferably from 40 to 160 C. The two components are thereby used in an equivalent ratio of isocyanate groups to formamide groups of from at least 6:1 to not more than 40:1, preferably from 8:1 to not more than 30:1 and particularly preferably from 10:1 to not more than 25:1. The reaction can be carried out in solution or solvent-free, but preferably solvent-free.

(53) The preparation of the compounds having the formula (III) can be carried out without use of catalysts. However, the catalysts mentioned above for the preparation of the compounds of formula (I) can optionally also be used concomitantly in order to accelerate the reaction.

(54) Particularly preferred catalysts are 1,4-diazabicyclo-(2,2,2)-octane (DABCO), 1,5-diazabicyclo[4.3.0]nonene (DBN), 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU) as well as dibutyltin(IV) dilaurate (DBTL) and zinc(II) trifluoromethanesulfonate (zinc triflate).

(55) The catalysts mentioned by way of example above can be used in the reaction individually or in the form of arbitrary mixtures and are employed, if at all, in amounts of from 0.001 to 1.0 wt. %, preferably from 0.01 to 0.5 wt. %, calculated as the total amount of catalysts used, based on the total amount of starting compounds used.

(56) The progress of the reaction can again be monitored, for example, by determining the NCO content by titrimetry. When the desired NCO content has been reached, the reaction is terminated.

(57) In a preferred embodiment, after the reaction of the compounds of formula (Ia) with the diisocyanate OCNRNCO, an unreacted excess of monomeric diisocyanate OCNRNCO is separated from the reaction product to a residual content of less than 1 wt. %, preferably of less than 0.5 wt. %, particularly preferably of less than 0.3 wt. %, based on the total mass of the reaction product. The reaction mixture is preferably freed of excess monomeric diisocyanates OCNRNCO by film distillation in vacuo, for example at a pressure of less than 1.0 mbar, preferably less than 0.5 mbar, particularly preferably less than 0.2 mbar, under conditions that are as gentle as possible, for example at a temperature of from 100 to 200 C., preferably from 120 to 180 C.

(58) The reaction mixtures worked up in that manner generally yield product mixtures which comprise more than 85 wt. %, preferably more than 95 wt. %, of compounds of formula (III) according to the invention, less than 1 wt. % of monomeric (unreacted) diisocyanate and less than 15 wt. %, preferably less than 10 wt. %, of compounds of formula (IIIa) hereinbelow, based on the total mass of the reaction product.

(59) ##STR00011##
wherein the variables are as defined for formula (I).

(60) The compounds of formula (III) prepared in that manner are clear, virtually colourless products which, depending on the chosen starting diisocyanate, are low- to high-viscosity liquids and have residual contents of monomeric starting diisocyanates of less than 1.0 wt. %, preferably of less than 0.5 wt. %, particularly preferably of less than 0.3 wt. %, based on the total mass of the reaction product.

(61) In order to prevent premature crosslinking of the silane groups of the compounds of formula (I) and/or (III) during the preparation according to the invention, it can be advantageous to add water acceptors. For example, there can be used orthoformic esters, such as, for example, triethyl orthoformate, vinylsilanes, such as, for example, vinyitrimethoxysilane, or organic phosphates, such as, for example, dibutyl phosphate. The water acceptors are used, if necessary, in amounts of up to 5 wt. %, preferably up to 2 wt. %, based on the total amount of starting materials.

(62) If catalysts and/or water acceptors are used, they can be added to the starting compounds before the start of the actual reaction. It is, however, also possible to add these auxiliary substances to the reaction mixture at any desired point in time during the reaction.

(63) In a preferred embodiment, the processes described herein take place under a protecting gas atmosphere, such as, for example, nitrogen.

(64) Silane-Modified Compounds of Formula (IV)

(65) Particularly preferably, the compounds of formula (III) as defined above are used for the preparation of silane-modified compounds or prepolymers having the formula (IV):

(66) ##STR00012##
wherein R, R.sup.1, R.sup.2, R.sup.3 and n have the meanings given in claim 1, Y is an m-valent, optionally substituted, linear or branched, aliphatic, alicyclic, araliphatic, heterocyclic and/or aromatic structural unit having from 1 to 40 carbon atoms or a structural unit reduced by m OH radicals of a polyol or of a polyurethane, polyurea, polyester, polyether, polycarbonate, polyacetal, polyacrylate, polyester amide or polythioether polyol, and m is a number (optionally also a rational number) from 1 to 10.

(67) There are particularly preferably provided compounds of formula (IV) wherein it is n-hexylene, R.sup.1 is n-propylene, R.sup.2 and R.sup.3 are methyl and n=0.

(68) Process for the Preparation of the Silane-Modified Compounds of Formula (IV)

(69) The silane-modified prepolymers of formula (IV) according to the invention can be prepared by process (A) described hereinbelow:

(70) ##STR00013##
wherein R, R.sup.1, R.sup.2, R.sup.3, n, Y and m are as defined in claim 7.

(71) According to the invention, the compound of formula (IV) can be prepared by reacting Y(OH).sub.m with a compound of formula (III) prepared as described above.

(72) There can be used for Y(OH).sub.m, for example, polyhydric alcohols and/or ether or ester alcohols having from 2 to 14 carbon atoms, preferably from 4 to 10 carbon atoms, such as, for example, 1,2-ethanediol, 1,2- and 1,3-propanediol, the isomeric butanediols, pentanediols, hexanediols, heptanediols and octanediols, 1,10-decanediol, 1,12-dodecanediol, 1,2- and 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-bis(2-hydroxyethoxy)-benzene, 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A), 2,2-bis-(4-hydroxycyclohexyl)-propane (perhydro-bisphenol), 1,2,3-propanetriol, 1,2,4-butanetriol, 1,1,1-trimethylolethane, 1,2,6-hexanetriol, 1,1,1-trimethylolpropane (TMP), bis-(2-hydroxyethyl)-hydroquinone, 1,2,4- and 1,3,5-trihydroxy-cyclohexane, 1,3,5-tris(2-hydroxyethyl) isocyanurate, 3(4),8(9)-bis-(hydroxymethyl)-tricyclo[5.2.1.0.sup.2,6]decane, di-trimethylolpropane, 2,2-bis(hydroxymethyl)-1,3-propanediol (pentaerythritol), 2,2,6,6-tetrakis(hydroxymethyl)-4-oxa-heptane-1,7-diol (dipentaerythritol), mannitol or sorbitol, low molecular weight ether alcohols, such as, for example, diethylene glycol, triethylene tetraethylene glycol, dipropylene glycol or dibutylene glycol, or low molecular weight ester alcohols, such as, for example, hydroxypivalic acid neopentyl glycol ester, and/or mixtures of the compounds mentioned above.

(73) The radical Y is preferably a radical which is derived from a polymeric polyol, polyether polyol, polyester polyol, polycarbonate polyol and/or polyacrylate polyol, as are known in polyurethane chemistry. These polymeric polyols usually have a number-average molecular weight of from 200 to 22,000, preferably from 250 to 18,000, particularly preferably from 250 to 12,000. A broad overview of suitable polymeric polyols will be found, for example, in N. Adam et al.: Polyurethanes, Ullmann's Encyclopedia of Industrial Chemistry, Electronic Release, 7th ed., chap. 3.2-3.4, Wiley-Val, Weinheim 2005.

(74) Suitable polyether polyols are, for example, those of the type mentioned in DE 26 22 951 B, column 6, line 65 to column 7, line 26, in EP-A 0 978 523, page 4, line 45 to page 5, line 14 or in WO 2011/069966, page 4, line 20 to page 5, line 23, provided they comply with the requirements given above in respect of functionality and molecular weight. Particularly preferred polyether polyols are addition products of ethylene oxide and/or propylene oxide on 1,2-propanediol, 1,3-propanediol, glycerol, trimethylolpropane, ethylenediamine and/or pentaerythritol, or the polytetramethylene ether glycols having number-average molecular weights of from 400 g/mol to 4000 g/mol obtainable, for example, according to Angew. Chem, 7, 927 (1960) by polymerisation of tetrahydrofuran.

(75) Suitable polyester polyols are, for example, those of the type mentioned in EP-A 0 978 523, page 5, lines 17 to 47 or in EP-A 0 659 792, page 6, lines 32 to 45, provided they comply with the requirements given above in respect of functionality and molecular weight. Particularly preferred polyester polyols are condensation products of polyhydric alcohols, such as, for example, 1,2-ethanediol, 1,2-propanediol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, perhydrobisphenol, 1,1,1-trimethylolpropane, 1,2,3-propanetriol, pentaerythritol and/or sorbitol, with deficient amounts of polyvalent carboxylic acids or carboxylic anhydrides, such as, for example, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, glutaric anhydride, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic acid, hexahydrophthalic anhydride and/or tetrahydrophthalic anhydride, or those which are obtainable in a manner known per se from lactones, such as, for example, -caprolactone, and simple monohydric alcohols, such as, for example, those mentioned above, as starter molecules with ring opening.

(76) Suitable polycarbonate polyols are in particular the reaction products known per se of dihydric alcohols, for example those mentioned by way of example above in the list of polyhydric alcohols, with diaryl carbonates, such as, for example, diphenyl carbonate, dimethyl carbonate or phosgene. Suitable poly-carbonate polyols are also those which, as well as comprising carbonate structures, additionally comprise ester groups. They are in particular the polyester carbonate diols known per se, as can be obtained, for example, according to the teaching of DE-AS 1 770 245 by reaction of dihydric alcohols with lactones, such as in particular -caprolactone, and subsequent reaction of the resulting polyester diols with diphenyl carbonate or dimethyl carbonate. Suitable polycarbonate polyols are also those which, as well as comprising carbonate structures, additionally comprise ether groups. They are in particular the polyether carbonate polyols known per se, as are obtainable, for example, by the process of EP-A 2046861 by catalytic reaction of alkylene oxides (epoxides) and carbon dioxide in the presence of H-functional starter substances.

(77) Suitable polyacrylate polyols are, for example, those of the type mentioned in WO 2011/124710, page 10, line 32 to page 13, line 18, provided they comply with the requirements given above in respect of functionality and molecular weight. Particularly preferred polyacrylate polyols are polymers or copolymers of hydroxyalkyl esters of acrylic acid or methacrylic acid, such as, for example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate or hydroxybutyl (meth)acrylate, optionally together with acrylic acid alkyl esters and/or methacrylic acid alkyl esters, such as, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, lauryl (meth)acrylate, styrene or other copolymerisable olefinically unsaturated monomers, such as, for example, acrylic acid, methacrylic acid or maleic acid dimethyl ester.

(78) Suitable polyols are, for example, also the known polyacetal polyols obtainable by reaction of simple glycols, such as, for example, diethylene glycol, triethylene glycol, 4,4-dioxethoxy-diphenyl-dimethylmethane (adduct of 2 mol of ethylene oxide on bisphenol A) or hexanediol, with formaldehyde, or also polyacetals prepared by polycondensation of cyclic acetals, such as, for example, trioxane.

(79) Further suitable polyols are, for example, also the specific polyols described in EP-A 0 689 556 and EP-A 0 937 110, for example obtainable by reaction of epoxidised fatty acid esters with aliphatic or aromatic polyols with epoxide ring opening.

(80) Hydroxyl-group-containing polybutadienes can likewise be used as polyols. In a preferred embodiment of the invention, polyether, polyester, polycarbonate anchor polyacrylate polyols are used as component Y(OH).sub.m.

(81) The polyols are used in the process according to the invention individually or in the form of arbitrary mixtures with one another. They can be present both in solvent-free form and in solution in conventional solvents.

(82) The reaction of the compounds of the formula Y(OH).sub.m with compounds of formula (III) takes place at temperatures of from 20 to 200 C., preferably from 40 to 160 C. An equivalent ratio of isocyanate groups to hydroxyl groups of from 0.7:1 to 1.2:1, preferably from 0.8:1 to 1.1:1, particularly preferably from 0.9:1 to 1.05:1, is maintained.

(83) The process according to the invention can be carried out without catalysis. However, in order to accelerate the urethanisation reaction, catalysts conventional in isocyanate chemistry can optionally also be used concomitantly. Suitable catalysts have already been described above for the preparation of the compound of formula (I).

(84) Particularly preferred catalysts are 1,4-diazabicyclo-(2,2,2)-octane (DABCO), 1,5-diazabicyclo[4.3.0]nonene (DBN), 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU) and dibutyltin(IV) dilaurate (DBTL).

(85) These catalysts can be used in the process according to the invention individually or in the form of arbitrary mixtures with one another and are employed, if necessary, in amounts of from 0.001 to 1.0 wt. %, preferably from 0.01 to 0.5 wt. %, calculated as the total amount of catalysts used, based on the total amount of starting materials.

(86) The silane-modified compounds or prepolymers of formula (IV) according to the invention that are prepared by the process are clear, virtually colourless products which, depending on the chosen starting diisocyanate and polyol, are low- to high-viscosity liquids and contain residual contents of monomeric starting diisocyanates of less than 1.0 wt. %, preferably of less than 0.5 wt. %, particularly preferably of less than 0.3 wt. %, based on the total mass of the reaction product.

(87) Any residual NCO contents that are still detectable can generally be taken up by addition of methanol.

(88) In order to prevent premature crosslinking of the silane groups during the process according to the invention, it can be advantageous to add water acceptors. For example, orthoformic esters, such as, for example, triethyl orthoformate, vinylsilanes, such as, for example, vinyltrimethoxysilane, or organic phosphates, such as, for example, dibutyl phosphate, can be used. The water acceptors are used, if necessary, in amounts of up to 5 wt. %, preferably tip to 2 wt. %, based on the total amount of starting materials.

(89) When catalysts and/or water acceptors are used concomitantly, they can be added to the starting compounds before the start of the actual reaction. It is, however, also possible to add these auxiliary substances to the reaction mixture at any desired point in time during the urethanisation reaction.

(90) The progress of the reaction can be monitored according to the invention, for example, by titrimetric determination of the NCO content or by IR spectroscopy. Following the urethanisation reaction, that is to say when the isocyanate and hydroxyl groups or formamide groups have reacted completely, there are obtained as products of the process according to the invention the silane-modified acylurea-group-containing prepolymers of formula (IV) according to the invention.

(91) Depending on the field of application, the compounds or prepolymers of formula (IV) according to the invention have viscosities in the range of from 10 to 1,000,000 mPa.Math.s, preferably from 50 to 500,000 mPa.Math.s, particularly preferably from 500 to 200,000 mPa.Math.s.

(92) The silane-modified prepolymers of formula (IV) disclosed herein can be used according to the invention for the production of adhesives and sealing materials, coatings, sizes, inks and/or printing inks.

(93) The advantage of this process is that the properties of the silane-modified prepolymers of formula (IV) can be adapted to a large number of very different applications via the compounds of the formula Y(OH).sub.m that are used or the diisocyanates that are used.

(94) Reactive One-Component Adhesive System

(95) According to the invention, the compounds of formula (I) as described above and/or the compounds of formula (IV) as described above are used for a reactive one-component adhesive system. The reactive one-component adhesive system is characterised in that it comprises at least one compound of formula (I) and/or at least one compound of formula (IV).

(96) Under the action of moisture or water, hydrolysis of the hydrolysable radicals of the silane groups takes place, followed by crosslinking (curing) of the silanols formed thereby, with cleavage of water.

(97) Catalysts that accelerate the hydrolysis and condensation of the silanol groups can also be used concomitantly. Such catalysts are known to a person skilled in the art. There can be used, for example, acids, such as, for example, sulfuric acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, acetic acid, trifluoroacetic acid and dibutyl phosphate, bases, such as, for example, N-substituted amidines, such as 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) and 1,5-diazabicyclo-[5.4.0]undec-7-ene (EMU), but also metal salts and metal chelates, such as, for example, tetraisopropyl titanate, tetrabutyl titanate, titanium(IV) acetylacetonate, aluminium tri-sec-butylate, aluminium acetylacetonate, aluminium triflate or tin triflate.

(98) These catalysts are used, if at all, in amounts of up to 5 wt. %, preferably up to 2 wt. %, based on the weight of the silane-modified prepolymers that are used. Depending on the nature and amount of the catalyst used, curing of the one-component adhesive system formulated from the compounds of formula (I) and/or (IV) according to the invention can take place over a wide temperature range, for example from 20 to 200 C., preferably from 0 to 180 C., particularly preferably from 20 to 160 C.

(99) There can optionally be added to the reactive one-component adhesive system according to the invention as reaction partners also any desired further hydrolysable silane compounds, such as, for example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, octyltriethoxysilane, octyltrimethoxysilane, (3-glycidyloxypropyl)-methyldiethoxysilane, (3-glycidyloxypropyl)-trimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane or silane-functional copolymers of the type mentioned in U.S. Pat. No. 4,499,150, or mixtures of such silane compounds.

(100) The reactive one-component adhesive system of the invention can likewise optionally comprise further additives and/or auxiliary substances which are known in the prior art. Mention may be made of for example, pigments, antioxidants, water acceptors, fillers, slip additives, flow agents, rheology additives, foam stabilisers, hydrophobising agents, air void formers, adhesion-enhancing additives (adhesion promoters), compounding agents, plasticisers, anti-ageing agents, flame retardants and/or UV stabilisers.

(101) There may be mentioned as suitable fillers, for example, carbon black, precipitated silicas, pyrogenic silicas, mineral chalks and precipitated chalks. Examples of suitable plasticisers which may be mentioned are phthalic acid esters, adipic acid esters, alkylsulfonic acid esters of phenol, phosphoric acid esters or also higher molecular weight polypropylene glycols.

(102) There may be mentioned as water acceptors in particular alkoxysilyl compounds such as vinyltrimethoxysilane, methyltrimethoxysilane, isobutyltrimethoxysilane, hexadecyltrimethoxy-silane.

(103) There are used as adhesion promoters the known functional silanes such as, for example, aminosilanes of the type mentioned above, but also N-aminoethyl-3-amino-propyl-trimethoxy- and/or N-aminoethyl-3-aminopropyl-methyl-dimethoxy-silane, epoxysilanes and/or mercaptosilanes.

(104) As well as being used as a one-component adhesive system, the compounds of formula (I) and/or (IV) according to the invention can also be added to conventional one-component and/or two-component polyurethane adhesive systems, for example as an additive.

(105) If the reactive one-component adhesive system according to the invention, as described above, is applied beforehand to the substrates that are to be bonded, permanent bonding or sealing of the substrates occurs as a result of the above-described crosslinking.

(106) It may be necessary for the surfaces of the substrates that are to be bonded to be pretreated by a physical, chemical and/or physical-chemical process. The application of a primer or of an adhesion promoter composition, for example, is advantageous here but is not absolutely necessary according to the invention.

(107) Substrates

(108) Suitable substrates which are suitable for adhesive bonding and/or sealing by means of the reactive one-component adhesive system according to the invention are metals, glass, wood, concrete, stone, ceramics, textiles and/or plastics materials. The substrates that are to be bonded can be the same or different.

(109) In a preferred embodiment, the reactive one-component adhesive system according to the invention is used for the adhesive bonding and/or sealing of metals, glass and/or plastics materials.

(110) Suitable metal substrates can generally be produced from all metals or metal alloys that are conventional in the field. Metals such as, for example, aluminium, stainless steel, steel, titanium, iron-containing metals and alloys are preferably used. The substrates that are to be bonded can additionally be composed of different metals.

(111) The plastics substrates that are to be bonded are, for example, polycarbonates (PC), polyamides, polyvinyl chloride, polyurethanes, polyvinyl acetate, polyacrylates or polymethacrylates, polyethylene, polystyrene, polypropylene and/or polyesters, such as, for example, polybutylene terephthalate (PBT) and/or polyethylene terephthalate (PET).

(112) The substrates can additionally be lacquered or printed.

(113) The substrates that are to be bonded can further have any desired form necessary for the use of the resulting composite. In the simplest form, the substrates are planar. Three-dimensional substrates can, however, also be bonded using the reactive one-component adhesive system according to the invention.

(114) Composite

(115) There is likewise provided according to the invention a composite that is bonded by the reactive one-component adhesive system according to the invention, as defined above.

EXPERIMENTAL PART

(116) The examples which follow serve to illustrate the present invention but are not to be interpreted as being a limitation of the scope of protection.

(117) All percentages relate to weight, unless specified otherwise.

(118) The NCO contents were determined titrimetrically in accordance with DIN EN ISO 11909.

(119) OH numbers were determined titrimetrically in accordance with DIN 53240-2: 2007 November, and acid numbers were determined in accordance with DIN 3682 5. The indicated OH contents were calculated from the analytically determined OH numbers.

(120) The residual monomer contents were measured in accordance with DIN EN ISO 10283 by gas chromatography with an internal standard.

(121) The proportions of bisadduct and molecular weights were determined by gel permeation chromatography in accordance with DIN 55672-1 (Gel permeation chromatography (GPC)Part 1: Tetrahydrofuran (THF) as eluant) against polystyrene standards, with the difference that a flow rate of 0.6 ml/min instead of 1.0 ml/min was used. The proportions of bisadduct in % by unit area taken from the chromatograms, which were determined with software assistance, were each equated approximately to proportions in wt. % and indicated as such, based on the total amount of mono- and bis-adduct.

(122) All viscosity measurements were carried out using a Physica MCR 51 rheometer from Anton Paar Germany GmbH (DE) in accordance with DIN EN ISO 3219.

Synthesis of Silane-Modified Formamides having the Formula (Ia)

Example 1: N-(3-Trimethoxysilylpropyl)formamide

(123) 1075.8 g (6 mol) of 3-aminopropyltrimethoxysilane are placed at room temperature, under a nitrogen atmosphere, in a flask having a thermometer, a KPG stirrer, a reflux condenser and a dropping funnel. 378.6 g (6.3 mol) of methyl formate are added dropwise, with stirring, in such a manner that the temperature does not exceed 50 C. When the exothermic reaction has subsided, stirring is continued for 4 hours at room temperature, and then excess methyl formate and the resulting methyl alcohol are distilled off under reduced pressure (0.1 mbar at 50 C.). A colourless liquid having a viscosity of 11 mPa.Math.s at 23 C. is obtained.

Example 2: N-(3-Methyldimethoxysilylpropyl)formamide

(124) 99.6 g (0.6 mol) of 3-aminopropylmethyldimethoxysilane are placed at room temperature, under a nitrogen atmosphere, in a flask having a thermometer, a KPG stirrer, a reflux condenser and a dropping funnel. 40.3 g (0.67 mol) of methyl formate are added dropwise, with stirring, in such a manner that the temperature does not exceed 50 C. When the exothermic reaction has subsided, stirring is continued for 4 hours at room temperature, and then excess methyl formate and the resulting methyl alcohol are distilled off under reduced pressure (0.1 mbar at 50 C.). A colourless liquid having a viscosity of 11 mPas at 23 C. is obtained.

Example 3: N-(3-Triethoxysilylpropyl)formamide

(125) 221.4 g (1 mop of 3-aminopropyl-triethoxysilane are placed at room temperature, under a nitrogen atmosphere, in a flask having a thermometer, a KPG stirrer, a reflux condenser and a dropping funnel. 77.8 g (1.05 mol) of ethyl formate are added dropwise, with stirring, in such a manner that the temperature does not exceed 50 C. When the exothermic reaction has subsided, stirring is continued for 4 hours at room temperature, and then excess ethyl formate and the resulting ethyl alcohol are distilled off under reduced pressure (0.1 mbar at 80 C.). A colourless liquid having a viscosity of 13 mPa.Math.s at 23 C. is obtained.

Example 4: N-(3-Methyldiethoxysilylpropyl)formamide

(126) 497.9 g (2.6 mol) of 3-aminopropylmethyldiethoxysilane are placed at room temperature, under a nitrogen atmosphere, in a flask having a thermometer, a KPG stirrer, a reflux condenser and a dropping funnel. 212.1 g (2.8 mol) of ethyl formate are added dropwise, with stirring, in such a manner that the temperature does not exceed 50 C. When the exothermic reaction has subsided, stirring is continued for 4 hours at room temperature, and then excess ethyl formate and the resulting ethyl alcohol are distilled off under reduced pressure (0.1 mbar at 80 C.). A colourless liquid having a viscosity of 12 mPas at 23 C. is obtained.

Synthesis of Silane-Modified Compounds having the General Formula(I)

Example 5

(127) 672 g (4 mol) of HDI (1,6-hexamethylene diisocyanate) are placed at 80 C., under a nitrogen atmosphere, in a flask having a thermometer, a KPG stirrer, a reflux condenser and a dropping funnel. 207.1 g (1 mol) of N-(3-trimethoxysilylpropyl)formamide (from Example 1) are then metered in, with stirring, over a period of one hour. When the addition is complete, the batch is stirred at 80 C. until a constant isocyanate content (34.7 wt. %) is reached. The resulting reaction mixture is passed at a feed rate of 600 ml/h over a thin-film evaporator at a pressure of 0.03 mbar and a temperature of 130 C. in order to remove excess HDI. A colourless liquid having a viscosity of 103 mPa.Math.s at 23 C., an isocyanate content of 10.36 wt. %, a free HDI content of 0.07 wt. % and a proportion of bis-adduct of 15.7% is obtained.

(128) The main component of the obtained product corresponds to the formula (VI):

(129) ##STR00014##

Example 6: Comparison Example to Example 5

(130) 3150 g (18.75 mol) of HDI (1,6-hexamethylene diisocyanate) are placed at 80 C., under a nitrogen atmosphere, in a flask having a thermometer, a KPG stirrer, a reflux condenser and a dropping funnel. 448.2 g (2.5 mol) of 3-aminopropyltrimethoxysilane are than metered in, with stirring, over a period of one hour. Immediately after the addition of the first drop, the formation of a haze is to be observed, which increases in the course of the addition and agglomerates to form a solid. Constructive further processing of the batch as in Example 5 is not possible.

Example 7

(131) 1667.3 g (7.5 mol) of IPDI (isophorone diisocyanate) are placed at 80 C., under a nitrogen atmosphere, in a flask having a thermometer, a KPG stirrer, a reflux condenser and a dropping funnel. 207.1 g (1 mol) of N-(3-trimethoxysilylpropyl)formamide (from Example 1) are then metered in, with stirring, over a period of one hour. When the addition is complete, the hatch is stirred at 80 C. until a constant isocyanate content (31.3 wt. %) is reached. The resulting reaction mixture is passed at a feed rate of 800 ml/h over a thin-film evaporator at a pressure of 0.02 mbar and a temperature of 140 C. in order to remove excess IPDI. A colourless liquid having a viscosity of 6900 mPa.Math.s at 23 C., an isocyanate content of 9.9 wt. %, a free IPDI content of 0.32 wt. % and a proportion of bis-adduct of 10.3% is obtained.

Example 8

(132) 3960.0 g (22.5 mol) of TDI (2,4-toluene diisocyanate) are placed at 80 C., under a nitrogen atmosphere, in a flask having a thermometer, a KPG stirrer, a reflux condenser and a dropping funnel. 621.3 g (3 mol) of N-(3-trimethoxysilylpropyl)formamide (from Example 1) are then metered in, with stirring, over a period of one hour. When the addition is complete, the batch is stirred at 80 C. until a constant isocyanate content (38.1 wt. %) is reached. The resulting reaction mixture is passed at a feed rate of 400 ml/h over a thin-film evaporator at a pressure of 0.02 mbar and a temperature of 140C. in order to remove excess TDI. A yellowish liquid having a viscosity of 7080 mPa.Math.s 23 C., isocyanate content of 11.6 wt. %, a free TDI content of 0.41 wt. % and a proportion of bis-adduct of 14.7% is obtained.

Synthesis of Silane-Modified Prepolymers Having the Formula (IV)

Example 9

(133) 262.5 g of castor oil and 13 mg of DBTL, are placed at 80 C., under a nitrogen atmosphere, in a flask having a thermometer, a KPG stirrer, a reflux condenser and a dropping funnel, and 307.3 g of the silane-modified formamide from Example 6 are added dropwise in such a manner that the reaction temperature does not exceed 90 C. When the addition is complete, the reaction mixture is stirred at 60 C. until a constant isocyanate content is reached (0.7 wt. %). The remaining isocyanate content is taken up by addition of methanol. The resulting binder is clear and has a viscosity of 13,500 mPa.Math.s at 23C.

(134) For further processing, the binder is adjusted to a solids content of 50% with 1-methoxy-2-propyl acetate (MPA), and 0.25% Lupragen N 700 (1,8-diazabicyclo-5,4,0-undec-7-ene) from BASF SE is added; the whole is applied with a knife in a layer thickness (wet) of 50 m to glass plates. After a drying time of 4 hours at 23 C. and a relative humidity of 50%, the coating is touch-dry and after 4 days exhibits good solvent resistance to xylene, 1-methoxy-2-propyl acetate, ethyl acetate and acetone.

Example 10

(135) 92.8 g of Desmophen A 160 SN (60% acrylic resin in solvent naphtha 100; hydroxyl content 2.7% on solid resin), Bayer Material Science AG, 67.3 g of 2-ethyl-1,3-hexanediol and 9 g of orthoformic acid triethyl ester are placed with 10 mg of DBTL at 80 C., under a nitrogen atmosphere, in a flask having a thermometer, a KPG stirrer, a reflux condenser and a dropping funnel, and 413.0 g of the silane formamide-HDI adduct (from Example 5) are added dropwise in such a manner that the reaction temperature does not exceed 90 C. When the addition is complete, the reaction mixture is stirred at 60 C. until no further isocyanate can be detected. The resulting binder is clear and has a viscosity of 230,000 mPas at 23 C.

(136) For further processing, the binder is adjusted to a solids content of 50% with 1-methoxy-2-propyl acetate (MPA), and 0.25% Lupragen N 700 (1,8-diazabicyclo-5,4,0-undec-7-ene) from BASF SE is added; the whole is applied with a knife in a layer thickness (wet) of 50 m to glass plates. After a drying time of 4 hours at 23 C. and a relative humidity of 50%, the coating is touch-dry and after 4 days exhibits good solvent resistance to xylene, 1-methoxy-2-propyl acetate, ethyl acetate and acetone.

Example 11

(137) 1024 g (0.12 mol) of a polypropylene glycol (Acclaim Polyol 8200N; OH number 14 mg KOH/g) are placed with 50 mg of DBTL at 60 C., under a nitrogen atmosphere, in a flask having a thermometer, a KPG stirrer, a reflux condenser and a dropping funnel, and 109 g of the silane formamide-HDI adduct (from Example 5) are added dropwise in such a manner that the reaction temperature does not exceed 80 C., When the addition is complete, the reaction mixture is stirred at 60 C. until a constant isocyanate content is reached (0.05 wt. %). The remaining isocyanate content is taken up by addition of methanol and the reaction mass is stabilised by adding 100 mg of dibutyl phosphate and 2 g of vinyltrimethoxysilane as water acceptor. The resulting binder is clear and has a viscosity of 11,600 mPas at 23 C.

Example 12

(138) 950 g (0.1 mol) of a polypropylene glycol (Acclaim Polyol 18200N; OH number 6.5 rug KOH/g) are placed with 50 mg of DBTL at 60 C., under a nitrogen atmosphere, in a flask having a thermometer, a KPG stirrer, a reflux condenser and a dropping funnel, and 50 g of the silane formamide-HDI adduct (from Example 5) are added dropwise in such a manner that the reaction temperature does not exceed 80 C. When the addition is complete, the reaction mixture is stirred at 60 C. until a constant isocyanate content is reached (0.08 wt. %). The remaining isocyanate content is taken up by addition of methanol and the reaction mass is stabilised by adding 50 mg of dibutyl phosphate and 2 g of vinyltrimethoxysilane as water acceptor. The resulting binder is clear and has a viscosity of 75,700 mPas at 23 C.

Example 13

(139) 999 g (0.12 mol) of a polypropylene glycol (Acclaim Polyol 8200N; OH number 14 mg KOH/g; Bayer Material Science AG) are placed with 60 mg of DBTL at 60 C., under a nitrogen atmosphere, in a flask having a thermometer, a KPG stirrer, a reflux condenser and a dropping funnel, and 101.0 g of the silane formamide-TDI adduct (from Example 8) are added dropwise in such a manner that the reaction temperature does not exceed 80 C. When the addition is complete, the reaction mixture is stirred at 60 C. until a constant isocyanate content is reached (0.02 wt. %). The remaining isocyanate content is taken up by addition of methanol and the reaction mass is stabilised by adding 60 mg of dibutyl phosphate and 2.2 g of vinyltrimethoxysilane as water acceptor. The resulting binder is clear and has a viscosity of 63,000 mPas at 23 C.

(140) Application Examples for Adhesives and Sealing Materials

(141) In order to assess the application properties of the different polymers, they were processed in the following formulation:

(142) TABLE-US-00001 Amount used in wt. % Polymer 31.34 Filler (Socal U.sub.1S.sub.2) 47.01 Plasticiser (Jayflex DINP) 18.80 Drying agent (Dynasylan VTMO) 1.88 Adhesion promoter (Dynasylan 1146) 0.94 Catalyst (Lupragen N 700) 0.03

(143) In order to prepare the formulation, the filler (Socal U1S2 from Solvay), the plasticiser (Jayflex DINP from Exxon) and the drying agent (Dynasylan MAO from Evonik) are added to the binder, and mixing is carried out at 3000 rpm in a vacuum dissolver with a wall scraper. The adhesion promoter (Dynasylan 1146 from Evonik) is then added and incorporated by stirring in the course of 5 minutes at 1000 rpm. Lastly, the catalyst (Lupragen N700 from BASE SE) is stirred in at 1000 rpm, and the finished mixture is finally exposed to the air in vacuo.

(144) In order to measure the physical properties, both membranes having a thickness of 2 mm and test specimens on a glass substrate are prepared in accordance with DIN EN ISO 11600. Testing of the Shore hardness was carried out on the membranes in accordance with DIN 53505. The modulus at 50% elongation is measured in accordance with DIN EN ISO 11600 at 23 C.

(145) The following table shows the results that were obtained:

(146) TABLE-US-00002 Ex. 14 (polymer Ex. 15 (polymer from Ex. 11) from Ex. 12) Shore A hardness 61 17 50% modulus [N/mm.sup.2] 3.0 0.8 Film drying time, 100 m 45 30 [min]