CA2229299A1 - Compounds containing urea and alkoxysilane groups - Google Patents
Compounds containing urea and alkoxysilane groups Download PDFInfo
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- CA2229299A1 CA2229299A1 CA002229299A CA2229299A CA2229299A1 CA 2229299 A1 CA2229299 A1 CA 2229299A1 CA 002229299 A CA002229299 A CA 002229299A CA 2229299 A CA2229299 A CA 2229299A CA 2229299 A1 CA2229299 A1 CA 2229299A1
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- groups
- polyisocyanate
- compound
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- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
Abstract
The present invention relates to compounds containing alkoxysilane and urea groups corresponding to the formula wherein X represents identical or different organic groups which are inert to isocyanate groups below 100°C, provided that at least one of these groups is an alkoxy group, Z represents COOR, or an aromatic ring, R represents the residue obtained by removing the isocyanate groups from an organic monomeric polyisocyanate or a polyisocyanate adduct, R, and R2 are identical or different and represent organic groups which are inert to isocyanate groups at a temperature of 100°C or less, R3 and R4 are identical or different and represent hydrogen or organic groups which are inert to isocyanate groups at a temperature of 100°C or less and n is an integer from 1 to 8.
The present invention also relates to the use of these compounds for the preparation of coatings, sealants and adhesives.
The present invention also relates to the use of these compounds for the preparation of coatings, sealants and adhesives.
Description
Mo4649 COMPOUNDS CONTAINING UREA
AND ALKOXYSILANE GROUPS
BACKGROUND OF THE INVENTION
Field of the Invention The present invention relates to new compounds containing alkoxysilane groups and urea groups and to their use as coatings, sealants, or adhesives.
Description of the Prior Art Hydrolyzable organofunctional silanes are key components for 10 linking conventional polymer chemistry with silicone chemistry.
Compounds of technical importance for this purpose are in particular those corresponding to the formula (Ro)3si-(cH2)3-y wherein 15 R is an alkyl group and Y is a functional group.
Such compounds contain both hydrolyzable silyl groups, OR, which crosslink by "silane polycondensation" in the presence of moisture, and other functional groups, Y, which enable them to be chemically 20 linked to conventional polymer materials. (See e.g., Anqew. Chem. 98 (1986) 237-253.) Hydrolyzable functional silanes corresponding to the above formula in which the functional group Y contains Zerewitinoff active H-atoms are potentially capable of modifying polyisocyanates. (See, e.g., 25 WO 92/05212). Commercially available products suitable for this purpose contain NH2 and/or NH groups as Zerewitinoff active H-atoms.
Also available are compounds containing SH groups.
Alkoxysilanes containing SH groups are described, for Mo4649 -2-example, in GB-A-1,102,251; EP-A-0,018,094; DE-A-1,162,818; U S
Patent 3,590,065; U S Patent 3,849,471; U S Patent 4,082,790; U S
Patent 4,012,403; and U S Patent 4,401,286 All alkoxysilanes containing SH groups have the unpleasant odor which is typical of 5 mercaptans The polymer may, therefore, have an unpleasant odor due to residues of these compounds.
a-Aminoalkyl silane derivatives which can be cross-linked by moisture may be prepared accor-li,rg to German Offenlegungs-schriften Nos. 1,812,504 and 1,812,562 The functional silanes 10 described there have, however, failed to achieve technical importance due to the complicated process for their synthesis Alkoxysilanes containing amino groups are described, e g, in J.
Or~ Chem 36 (1971), p 3120; DE-A-1,152,695; DE-A-1,271,712; DE-A-2,161,716; DE-A-2,408,480; DE-A-2,521,399; DE-A-2,749,316; U S
15 Patent 2,832,754; U S Patent 2,971,864; and U S Patent 4,481,364 Common to all amino-functional silanes known in the art is the disadvantage of being extremely reactive with isocyanates Thererore, it is difficult to react these alkoxysilanes with polyisocyanates due to the incompatibility, inhomogeneity and extremely high viscosities of the 20 reaction products U S Patent 5,554,709 discloses that amino-functional silanes can be reacted with certain NCO prepolymers, provided that the functionality of the prepolymer is less than 2 U S Patent 5,364,955 discloses that by initially reacting amino-25 functional silanes with maleic or fumaric acid esters to form secondaryamino groups (i e, asparldles), it is then possible to react these aspartates with NCO prepolymers without encountering incompatibility, inhomogeneity or extremely high viscosities in the reaction products However, this reference does not disclose that it is possible to react all Mo4649 -3-types of polyisocyanates with aspartates, i.e., polyisocyanate monomers and polyisocyanate adducts are not disclosed.
It is an object of the present invention to provide compounds containing urea and alkoxysilane groups that are either liquid or capable 5 of being dissolved in commonly used organic solvents, are based on polyisocyanate monomers and/or polyisocyanate adducts, and do not suffer from the incompatibility, inhomogeneity and viscosity problems encountered with the prior art reaction products of isocyanates with alkoxysilanes containing NH groups. It is an additional object of the 10 present invention to provide compounds containing alkoxysilane groups that can be cured by silane polycondensation to form coatings, sealants, and adhesives.
These objects may be achieved with the compounds containing alkoxysilane groups and urea groups according to the present invention 15 described hereinafter. These compounds are prepared by reacting polyisocyanate monomers and/or adducts with aspartates (obtained by reacting aminoalkyl alkoxysilanes with maleic or fumaric acid esters) to form compounds containing urea groups.
It is surprising that the products according to the invention are 20 liquid at room temperature because the corresponding products prepared by the direct reaction of polyisocyanate monomers and/or adducts with aminoalkyl alkoxysilanes are solids that cannot be dissolved with conventional coating solvents. The prior art, i.e., U.S. Patents 5,554,709 and 5,364,955, only teaches that the reaction product of an NC0 25 prepolymer with either an aminoalkyl alkoxysilane or an aspartate prepared from an aminoalkyl alkoxy silane is liquid. It does teach that it would be possible to convert the solid reaction products prepared from polyisocyanate monomer and/or adducts to liquid products by using the aspartate form of the aminoalkyl alkoxysilanes.
Mo4649 ~-SUMMARY OF THE INVENTION
The present invention relates to compounds containing alkoxysilane and urea groups corresponding to the formula Z CHR3 CR4\ 1~l IH R (~
Q93 Si (CH2)~
m wherein 5 X represents identical or different organic groups which are inert to isocyanate groups below 1 00~C, provided that at least one of these groups is an alkoxy group, Z represents COOR, or an aromatic ring, R represents the residue obtained by removing the isocyanate groups from an organic monomeric polyisocyanate or a polyisocyanate adduct, R, and R2 are identical or clifrerent and represent organic groups which are inert to isocyanate groups at a temperature of 100~C or less, R3 and R4 are identical or different and represent hydrogen or organic groups which are inert to isocyanate groups at a temperature of 100~C or less and n is an integer from 1 to 8.
The present invention also relates to the use of these compounds for the preparalion of coatings, sealants and adhesives.
DETAILED DESCRIPTION OF THE INVENTION
The compounds CGI ,tai"ing alkoxysilane groups and urea groups of formula I are prepared by reacting polyisocyanate monomers and/or adducts with compounds containing alkoxysilane and aspartate groups (secondary amino groups) corresponding to the formula Mo4649 -5-Z--CHR3 CR4 ~ l (CH2)n Si X ( ) to form compounds containing alkoxysilane and urea groups.
The compounds of formula ll are prepared by reacting aminoalkyl alkoxysilanes corresponding to the formula H2N--(CH2)n--Si (X)3 (Ill) 5 with maleic, fumaric or cinnamic acid esters corresponding to the formula Z-cR3=cR4-cooR2 (IV) In formulas I to IV
X represents identical or different organic groups which are inert to isocyanate groups below 1 00~C, provided that at least one of these groups is an alkoxy group, preferably alkyl or alkoxy groups having 1 to 4 carbon atoms, more preferably alkoxy groups;
Z represents COOR, or an aromatic ring, preferably COOR"
R represents the residue obtained by removing the isocyanate groups from an organic monomeric polyisocyanate or a polyisocyanate adduct, R1 and R2 are identical or different and represent organic groups which are inert to isocyanate groups at a temperature of 100~C or less, preferably alkyl groups having 1 to 9 carbon atoms, more preferably methyl, ethyl or butyl groups Mo4649 -6-R3 and R4 are identical or different and represent hydrogen or organic groups which are inert towards isocyanate groups at a temperature of 100~C or less, preferably hydrogen and n is an integer from 1 to 8, prererably 2 to 4 and more preferably 3.
Especially preferred are compounds in which X represents methoxy, ethoxy groups or propoxy groups, more preferably methoxy or ethoxy groups and most p,eferably methoxy groups, and n is 3.
Examples of suitable aminoalkyl alkoxysilanes of formula lll include 2-aminoethyl-dimethylmethoxysilane; 6-aminohexyl-10 tributoxysilane; 3-aminopropyl-trimethoxysilane; 3-aminopropyl-triethoxysilane; 3-aminopropyl-methyldiethoxysilane; 5-aminopentyl-trimethoxysilane; 5-aminopentyl-triethoxysilane and 3-aminopropyl-triisopropoxysilane. 3-aminopropyl-trimethoxysilane and 3-aminopropyl-triethoxysilane are particularly preferred.
Examples of optionally substituted maleic, fumaric or cinnamic acid esters suitable for use in the preparation of the polyasparlates include dimethyl, diethyl, dibutyl (e.g., di-n-butyl), diamyl, di-2-ethylhexyl esters and mixed esters based on mixture of these and/or other alkyl groups of maleic acid and fumaric acid; the methyl, ethyl and butyl esters of cinnamic acid; and the corresponding maleic, fumaric and ci"nal"ic acid esters substituted by methyl in the 2- and/or 3-position. The dimethyl esters of maleic acid are preferred and the diethyl and dibutyl esters are especially prefe"ed.
The reaction of primary amines with maleic, fumaric or cinnamic acid esters to form the aspartates of formula lll is known and described, e.g. in EP-A-0,403,921; DE-OS 1,670,812; and DE-OS 2,158,945. While none of these publications suggests the reaction of alkoxysilane-functional amines with maleic or fumaric acid esters, this reaction is described in U.S. Patent 5,364,955. The preparation of the aspa,lates may be carried out, for example, at a temperature of 0 to 100~C using Mo4649 -7-the starting materials in such proportions that at least 1, preferably 1, olefinic double bond is present for each primary amino group. Excess starting materials may be removed by distillation after the reaction. The reaction may be carried out with or without a solvent, but the use of a 5 solvent is less preferred. If a solvent is used, dioxane is an example of a suitable solvent.
The compounds of formula ll are colorless to pale yellow. They may be reacted with polyisocyanate monomer andtor adducts to form the compounds of formula I without further purification.
Suitable polyisocyanates for preparing the compounds of formula I
are those having a functionality of 1.8 to 6, preferably 2 to 6 and more preferably 2 to 4. Suitable polyisocyanate starting materials include monomeric diisocyanates and polyisocyanate adducts.
Suitable monomeric diisocyanates may be represented by the 1 5 formula R(NCO)2 in which R represents an organic group obtained by removing the isocyanate groups from an organic diisocyanate having a molecular weight of about 112 to 1,000, preferably about 140 to 400.
20 Diisocyanates preferred for the process according to the invention are those in which R represents a divalent aliphatic hydrocarbon group having 4 to 40, preferably 4 to 18 carbon atoms, a divalent cycloaliphatic hydrocarbon group having 5 to 15 carbon atoms, a divalent araliphatic hydrocarbon group having 7 to 15 carbon atoms or a divalent aromatic 25 hydrocarbon group having 6 to 15 carbon atoms.
Examples of the suitable organic diisocyanates include 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate, 1-isocyanato-2-30 isocyanatomethyl cyclopentane, 1-isocyanato-3-isocyanatomethyl-3,5,5-. CA 02229299 1998-02-11 Mo4649 -8-trimethyl-cyclohexane (isophorone diisocyanate or IPDI), bis-(4-iso-cyanatocyclohexyl)-methane, 2,4'-dicyclohexyl-methane diisocyanate, - 1,3- and 1,4-bis-(isocyanatomethyl)-cyclohexane, bis-(4-isocyanato-3-methyl-cyclohexyl)-methane, a,a,a',a'-tetramethyl-1,3- and/or-1,4-5 xylylene diisocyanate, 1-isocyanato-1-methyl-4(3)-isocyanatomethyl cyclohexane, 2,4- and/or 2,6-hexahydrotoluylene diisocyanate, 1,3-and/or 1,4-phenylene diisocyanate, 2,4- and/or 2,6-toluylene diisocyanate, 2,4- and/or 4,4'-diphenyl-methane diisocyanate, 1,5-diisocyanato naphthalene and mixtures thereof.
Polyisocyanates containing 3 or more isocyanate groups such as 4-isocyanantomethyl-1,8-octamethylene diisocyanate and aromatic polyisocyanates such as 4,4',4"-triphenylmethane triisocyanate and polyphenyl polymethylene polyisocyanates obtained by phosgenating aniline/formaldehyde condensates may also be used.
Preferred organic diisocyanates include 1,6-hexamethylene diisocyanate, 1 -isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane (isophorone diisocyanate or IPDI), bis-(4-isocyanato-cyclohexyl)-methane, 1-isocyanato-1-methyl-4(3)-isocyandlo,llethyl cyclohexane, 2,4- and/or 2,6-toluylene diisocyanate, and 2,4- and/or 4,4'-20 diphenyl-methane diisocyanate.
In accordance with the present invention the polyisocyanate component may also be in the form of a polyisocyanate adduct. Suitable polyisocyanate adducts are those containing isocyanurate, uretdione, biuret, urethane, allophanate, carbodiimide and/or oxadiazine-trione 25 groups. The polyisocyanates adducts have an average functionality of 2 to 6 and an NCO content of 5 to 30% by weight.
1) Isocyanurate group-containing polyisocyanates which may be prepared as set forth in DE-PS 2,616,416, EP-OS 3,765, EP-OS 10,589, EP-OS 47,452, US-PS 4,288,586 and US-PS 4,324,879.
30 The isocyanato-isocyanurates generally have an average NCO
Mo4649 -9-functionality of 3 to 3.5 and an NCO content of 5 to 30%, preferably 10 to 25% and most preferably 15 to 25% by weight.
2) Uretdione diisocyanates which may be prepared by oligomerizing a portion of the isocyanate groups of a diisocyanate in the 5 presence of a suitable catalyst, e.g, a trialkyl phosphine catalyst, and which may be used in admixture with other aliphatic and/or cycloaliphatic polyisocyanates, particularly the isocyanurate group-containing polyisocyanates set forth under (1) above.
AND ALKOXYSILANE GROUPS
BACKGROUND OF THE INVENTION
Field of the Invention The present invention relates to new compounds containing alkoxysilane groups and urea groups and to their use as coatings, sealants, or adhesives.
Description of the Prior Art Hydrolyzable organofunctional silanes are key components for 10 linking conventional polymer chemistry with silicone chemistry.
Compounds of technical importance for this purpose are in particular those corresponding to the formula (Ro)3si-(cH2)3-y wherein 15 R is an alkyl group and Y is a functional group.
Such compounds contain both hydrolyzable silyl groups, OR, which crosslink by "silane polycondensation" in the presence of moisture, and other functional groups, Y, which enable them to be chemically 20 linked to conventional polymer materials. (See e.g., Anqew. Chem. 98 (1986) 237-253.) Hydrolyzable functional silanes corresponding to the above formula in which the functional group Y contains Zerewitinoff active H-atoms are potentially capable of modifying polyisocyanates. (See, e.g., 25 WO 92/05212). Commercially available products suitable for this purpose contain NH2 and/or NH groups as Zerewitinoff active H-atoms.
Also available are compounds containing SH groups.
Alkoxysilanes containing SH groups are described, for Mo4649 -2-example, in GB-A-1,102,251; EP-A-0,018,094; DE-A-1,162,818; U S
Patent 3,590,065; U S Patent 3,849,471; U S Patent 4,082,790; U S
Patent 4,012,403; and U S Patent 4,401,286 All alkoxysilanes containing SH groups have the unpleasant odor which is typical of 5 mercaptans The polymer may, therefore, have an unpleasant odor due to residues of these compounds.
a-Aminoalkyl silane derivatives which can be cross-linked by moisture may be prepared accor-li,rg to German Offenlegungs-schriften Nos. 1,812,504 and 1,812,562 The functional silanes 10 described there have, however, failed to achieve technical importance due to the complicated process for their synthesis Alkoxysilanes containing amino groups are described, e g, in J.
Or~ Chem 36 (1971), p 3120; DE-A-1,152,695; DE-A-1,271,712; DE-A-2,161,716; DE-A-2,408,480; DE-A-2,521,399; DE-A-2,749,316; U S
15 Patent 2,832,754; U S Patent 2,971,864; and U S Patent 4,481,364 Common to all amino-functional silanes known in the art is the disadvantage of being extremely reactive with isocyanates Thererore, it is difficult to react these alkoxysilanes with polyisocyanates due to the incompatibility, inhomogeneity and extremely high viscosities of the 20 reaction products U S Patent 5,554,709 discloses that amino-functional silanes can be reacted with certain NCO prepolymers, provided that the functionality of the prepolymer is less than 2 U S Patent 5,364,955 discloses that by initially reacting amino-25 functional silanes with maleic or fumaric acid esters to form secondaryamino groups (i e, asparldles), it is then possible to react these aspartates with NCO prepolymers without encountering incompatibility, inhomogeneity or extremely high viscosities in the reaction products However, this reference does not disclose that it is possible to react all Mo4649 -3-types of polyisocyanates with aspartates, i.e., polyisocyanate monomers and polyisocyanate adducts are not disclosed.
It is an object of the present invention to provide compounds containing urea and alkoxysilane groups that are either liquid or capable 5 of being dissolved in commonly used organic solvents, are based on polyisocyanate monomers and/or polyisocyanate adducts, and do not suffer from the incompatibility, inhomogeneity and viscosity problems encountered with the prior art reaction products of isocyanates with alkoxysilanes containing NH groups. It is an additional object of the 10 present invention to provide compounds containing alkoxysilane groups that can be cured by silane polycondensation to form coatings, sealants, and adhesives.
These objects may be achieved with the compounds containing alkoxysilane groups and urea groups according to the present invention 15 described hereinafter. These compounds are prepared by reacting polyisocyanate monomers and/or adducts with aspartates (obtained by reacting aminoalkyl alkoxysilanes with maleic or fumaric acid esters) to form compounds containing urea groups.
It is surprising that the products according to the invention are 20 liquid at room temperature because the corresponding products prepared by the direct reaction of polyisocyanate monomers and/or adducts with aminoalkyl alkoxysilanes are solids that cannot be dissolved with conventional coating solvents. The prior art, i.e., U.S. Patents 5,554,709 and 5,364,955, only teaches that the reaction product of an NC0 25 prepolymer with either an aminoalkyl alkoxysilane or an aspartate prepared from an aminoalkyl alkoxy silane is liquid. It does teach that it would be possible to convert the solid reaction products prepared from polyisocyanate monomer and/or adducts to liquid products by using the aspartate form of the aminoalkyl alkoxysilanes.
Mo4649 ~-SUMMARY OF THE INVENTION
The present invention relates to compounds containing alkoxysilane and urea groups corresponding to the formula Z CHR3 CR4\ 1~l IH R (~
Q93 Si (CH2)~
m wherein 5 X represents identical or different organic groups which are inert to isocyanate groups below 1 00~C, provided that at least one of these groups is an alkoxy group, Z represents COOR, or an aromatic ring, R represents the residue obtained by removing the isocyanate groups from an organic monomeric polyisocyanate or a polyisocyanate adduct, R, and R2 are identical or clifrerent and represent organic groups which are inert to isocyanate groups at a temperature of 100~C or less, R3 and R4 are identical or different and represent hydrogen or organic groups which are inert to isocyanate groups at a temperature of 100~C or less and n is an integer from 1 to 8.
The present invention also relates to the use of these compounds for the preparalion of coatings, sealants and adhesives.
DETAILED DESCRIPTION OF THE INVENTION
The compounds CGI ,tai"ing alkoxysilane groups and urea groups of formula I are prepared by reacting polyisocyanate monomers and/or adducts with compounds containing alkoxysilane and aspartate groups (secondary amino groups) corresponding to the formula Mo4649 -5-Z--CHR3 CR4 ~ l (CH2)n Si X ( ) to form compounds containing alkoxysilane and urea groups.
The compounds of formula ll are prepared by reacting aminoalkyl alkoxysilanes corresponding to the formula H2N--(CH2)n--Si (X)3 (Ill) 5 with maleic, fumaric or cinnamic acid esters corresponding to the formula Z-cR3=cR4-cooR2 (IV) In formulas I to IV
X represents identical or different organic groups which are inert to isocyanate groups below 1 00~C, provided that at least one of these groups is an alkoxy group, preferably alkyl or alkoxy groups having 1 to 4 carbon atoms, more preferably alkoxy groups;
Z represents COOR, or an aromatic ring, preferably COOR"
R represents the residue obtained by removing the isocyanate groups from an organic monomeric polyisocyanate or a polyisocyanate adduct, R1 and R2 are identical or different and represent organic groups which are inert to isocyanate groups at a temperature of 100~C or less, preferably alkyl groups having 1 to 9 carbon atoms, more preferably methyl, ethyl or butyl groups Mo4649 -6-R3 and R4 are identical or different and represent hydrogen or organic groups which are inert towards isocyanate groups at a temperature of 100~C or less, preferably hydrogen and n is an integer from 1 to 8, prererably 2 to 4 and more preferably 3.
Especially preferred are compounds in which X represents methoxy, ethoxy groups or propoxy groups, more preferably methoxy or ethoxy groups and most p,eferably methoxy groups, and n is 3.
Examples of suitable aminoalkyl alkoxysilanes of formula lll include 2-aminoethyl-dimethylmethoxysilane; 6-aminohexyl-10 tributoxysilane; 3-aminopropyl-trimethoxysilane; 3-aminopropyl-triethoxysilane; 3-aminopropyl-methyldiethoxysilane; 5-aminopentyl-trimethoxysilane; 5-aminopentyl-triethoxysilane and 3-aminopropyl-triisopropoxysilane. 3-aminopropyl-trimethoxysilane and 3-aminopropyl-triethoxysilane are particularly preferred.
Examples of optionally substituted maleic, fumaric or cinnamic acid esters suitable for use in the preparation of the polyasparlates include dimethyl, diethyl, dibutyl (e.g., di-n-butyl), diamyl, di-2-ethylhexyl esters and mixed esters based on mixture of these and/or other alkyl groups of maleic acid and fumaric acid; the methyl, ethyl and butyl esters of cinnamic acid; and the corresponding maleic, fumaric and ci"nal"ic acid esters substituted by methyl in the 2- and/or 3-position. The dimethyl esters of maleic acid are preferred and the diethyl and dibutyl esters are especially prefe"ed.
The reaction of primary amines with maleic, fumaric or cinnamic acid esters to form the aspartates of formula lll is known and described, e.g. in EP-A-0,403,921; DE-OS 1,670,812; and DE-OS 2,158,945. While none of these publications suggests the reaction of alkoxysilane-functional amines with maleic or fumaric acid esters, this reaction is described in U.S. Patent 5,364,955. The preparation of the aspa,lates may be carried out, for example, at a temperature of 0 to 100~C using Mo4649 -7-the starting materials in such proportions that at least 1, preferably 1, olefinic double bond is present for each primary amino group. Excess starting materials may be removed by distillation after the reaction. The reaction may be carried out with or without a solvent, but the use of a 5 solvent is less preferred. If a solvent is used, dioxane is an example of a suitable solvent.
The compounds of formula ll are colorless to pale yellow. They may be reacted with polyisocyanate monomer andtor adducts to form the compounds of formula I without further purification.
Suitable polyisocyanates for preparing the compounds of formula I
are those having a functionality of 1.8 to 6, preferably 2 to 6 and more preferably 2 to 4. Suitable polyisocyanate starting materials include monomeric diisocyanates and polyisocyanate adducts.
Suitable monomeric diisocyanates may be represented by the 1 5 formula R(NCO)2 in which R represents an organic group obtained by removing the isocyanate groups from an organic diisocyanate having a molecular weight of about 112 to 1,000, preferably about 140 to 400.
20 Diisocyanates preferred for the process according to the invention are those in which R represents a divalent aliphatic hydrocarbon group having 4 to 40, preferably 4 to 18 carbon atoms, a divalent cycloaliphatic hydrocarbon group having 5 to 15 carbon atoms, a divalent araliphatic hydrocarbon group having 7 to 15 carbon atoms or a divalent aromatic 25 hydrocarbon group having 6 to 15 carbon atoms.
Examples of the suitable organic diisocyanates include 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate, 1-isocyanato-2-30 isocyanatomethyl cyclopentane, 1-isocyanato-3-isocyanatomethyl-3,5,5-. CA 02229299 1998-02-11 Mo4649 -8-trimethyl-cyclohexane (isophorone diisocyanate or IPDI), bis-(4-iso-cyanatocyclohexyl)-methane, 2,4'-dicyclohexyl-methane diisocyanate, - 1,3- and 1,4-bis-(isocyanatomethyl)-cyclohexane, bis-(4-isocyanato-3-methyl-cyclohexyl)-methane, a,a,a',a'-tetramethyl-1,3- and/or-1,4-5 xylylene diisocyanate, 1-isocyanato-1-methyl-4(3)-isocyanatomethyl cyclohexane, 2,4- and/or 2,6-hexahydrotoluylene diisocyanate, 1,3-and/or 1,4-phenylene diisocyanate, 2,4- and/or 2,6-toluylene diisocyanate, 2,4- and/or 4,4'-diphenyl-methane diisocyanate, 1,5-diisocyanato naphthalene and mixtures thereof.
Polyisocyanates containing 3 or more isocyanate groups such as 4-isocyanantomethyl-1,8-octamethylene diisocyanate and aromatic polyisocyanates such as 4,4',4"-triphenylmethane triisocyanate and polyphenyl polymethylene polyisocyanates obtained by phosgenating aniline/formaldehyde condensates may also be used.
Preferred organic diisocyanates include 1,6-hexamethylene diisocyanate, 1 -isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane (isophorone diisocyanate or IPDI), bis-(4-isocyanato-cyclohexyl)-methane, 1-isocyanato-1-methyl-4(3)-isocyandlo,llethyl cyclohexane, 2,4- and/or 2,6-toluylene diisocyanate, and 2,4- and/or 4,4'-20 diphenyl-methane diisocyanate.
In accordance with the present invention the polyisocyanate component may also be in the form of a polyisocyanate adduct. Suitable polyisocyanate adducts are those containing isocyanurate, uretdione, biuret, urethane, allophanate, carbodiimide and/or oxadiazine-trione 25 groups. The polyisocyanates adducts have an average functionality of 2 to 6 and an NCO content of 5 to 30% by weight.
1) Isocyanurate group-containing polyisocyanates which may be prepared as set forth in DE-PS 2,616,416, EP-OS 3,765, EP-OS 10,589, EP-OS 47,452, US-PS 4,288,586 and US-PS 4,324,879.
30 The isocyanato-isocyanurates generally have an average NCO
Mo4649 -9-functionality of 3 to 3.5 and an NCO content of 5 to 30%, preferably 10 to 25% and most preferably 15 to 25% by weight.
2) Uretdione diisocyanates which may be prepared by oligomerizing a portion of the isocyanate groups of a diisocyanate in the 5 presence of a suitable catalyst, e.g, a trialkyl phosphine catalyst, and which may be used in admixture with other aliphatic and/or cycloaliphatic polyisocyanates, particularly the isocyanurate group-containing polyisocyanates set forth under (1) above.
3) Biuret group-containing polyisocyanates which may be 10 prepared according to the processes disclosed in U.S. Patent Nos.
3,124,605; 3,358,010; 3,644,490; 3,862,973; 3,906,126; 3,903,127;
3,124,605; 3,358,010; 3,644,490; 3,862,973; 3,906,126; 3,903,127;
4,051,165; 4,147,714; or 4,220,749 by using co-reactants such as water, tertiary alcohols, primary and secondary monoamines, and primary and/or secondary diamines. These polyisocyanates preferably have an NCO content of 18 to 22% by weight and an average NC0 functionality of 3 to 3.5.
4) Urethane group-containing polyisocyanates which may be prepared in accordance with the process disclosed in U.S. Patent No.
3,183,112 by reacting excess quantities of polyisocyanates, ,c referably diisocyanates, with low molecular weight glycols and polyols having molecular weights of less than 400, such as trimethylol propane, glycerine, 1,2-dihydroxy propane and mixtures thereof. The urethane group-containing polyisocyanates have a most preferred NC0 content of 12 to 20% by weight and an (average) NC0 functionality of 2.5 to 3.
4) Urethane group-containing polyisocyanates which may be prepared in accordance with the process disclosed in U.S. Patent No.
3,183,112 by reacting excess quantities of polyisocyanates, ,c referably diisocyanates, with low molecular weight glycols and polyols having molecular weights of less than 400, such as trimethylol propane, glycerine, 1,2-dihydroxy propane and mixtures thereof. The urethane group-containing polyisocyanates have a most preferred NC0 content of 12 to 20% by weight and an (average) NC0 functionality of 2.5 to 3.
5) Allophanate group-containing polyisocyanates which may be prepared accor~ g to the processes disclosed in U.S. Patent Nos.
3,769,318, 4,160,080 and 4,177,342. The allophanate group-containing polyisocyanates have a most preferred NC0 content of 12 to 21% by weight and an (average) NCO functionality of 2 to 4.5.
Mo4649 -1 0-6) Isocyanurate and allophanate group-containing polyiso-cyanates which may be prepared in accordance with the processes set forth in U.S. Patents 5,124,427, 5,208,334 and 5,235,018, the disclosures of which are herein incorporated by reference, preferably polyisocyanates containing these groups in a ratio of monoisocyanurate groups to mono-allophanate groups of about 10:1 to 1:10, preferably about 5:1 to 1:7.
3,769,318, 4,160,080 and 4,177,342. The allophanate group-containing polyisocyanates have a most preferred NC0 content of 12 to 21% by weight and an (average) NCO functionality of 2 to 4.5.
Mo4649 -1 0-6) Isocyanurate and allophanate group-containing polyiso-cyanates which may be prepared in accordance with the processes set forth in U.S. Patents 5,124,427, 5,208,334 and 5,235,018, the disclosures of which are herein incorporated by reference, preferably polyisocyanates containing these groups in a ratio of monoisocyanurate groups to mono-allophanate groups of about 10:1 to 1:10, preferably about 5:1 to 1:7.
7) Carbodiimide group-containing polyisocyanates which may be prepared by oligomerizing di- or polyisocyanates in the presence of known carbodiimidization catalysts as described in DE-PS 1,092,007, 10 US-PS 3,152,162 and DE-OS 2,504,400, 2,537,685 and 2,552,350.
8) Polyisocyanates containing oxadiazinetrione groups and containing the reaction product of two moles of a diisocyanate and one mole of carbon dioxide.
Prefer,ed polyisocyanate adducts are the polyisocyanates 15 containing isocyanurate groups, biuret groups, allophanate groups and/or uretdione groups.
The compounds of formula I containing alkoxysilane groups and hydantoin groups are prepared by reacting the polyisocyanate monomers and/or adducts with the compounds of formula ll at an equivalent ratio of 20 aspartate groups (i.e., secondary amino groups) to isocyanate groups of approximately 1:1. The reaction is preferably carried out by incrementally adding the aspartate to the polyisocyanate. The reaction to form the urea groups is conducted at a temperature of 10 to 100~C, preferably 20 to 80~C and more preferably 20 to 50~C.
The compounds of the present invention are suitable for the production of sealant (including caulks), coating or adhesive compositions which can be cross-linked by "silane polycondensation," i.e., the condensation of silane groups (Si-OR) to form siloxane groups (Si-O-Si).
When used for this purpose, these compounds may be used as mixtures 30 with suitable acidic or basic catalysts. Examples include acids such as Mo4649 -11-paratoluene sulfonic acid; metallic salts such as dibutyl tin dilaurate;
tertiary amines such as triethylamine or triethylene diamine; and mixtures of these catalysts. Low molecular weight, basic aminoalkyl trialkoxysilanes, such as those represented by formula IV, also accelerate 5 hardening of the compounds according to the invention.
The invention is further illustrated but is not intended to be limited by the following examples in which all parts and percentages are by weight unless otherwise specified.
E)CAMPLES
10 Polyisocyanate 1 An isocyanurate group-containing polyisocyanate prepared from 1,6-hexamethylene diisocyanate and having an isocyanate content of 21.6%, a content of monomeric diisocyanate of ~0.2% and a viscosity at 20~C of 3000 mPa.s (available from Bayer Corporation as Desmodur N
3300).
Polyisocyanate 2 A mixture containing 70 parts by weight of a uretdione group-containing polyisocyanate, i.e., dimerized 1,6-hexamethylene diisocyanate and 30 parts by weight of N,N',N"-tris-(6-isocyanatohexyl)-isocyanurate together with minor quantities of higher homologs of both products and having a average viscosity of 150 mPa.s at 23~C and an average NC0 content of 22.5% (available from Bayer Corporation as Desmodur N 3400).
Polvisocyanate 3 An aniline/formaldehyde condensation product containing a mixture of diphenylmethane diisocyanate isomers as well as their higher homologs, having an NC0 content of about 31 % and a viscosity of about 40 mPa s at 23~C (available from Bayer Corporation as Mondur MRS-4).
Mo4649 -1 2-Polvisocyanate 4 87.5 parts (1 equiv) of a mixture of 2,4- and 2,6-toluylene diisocyanate (80:20 isomer ratio) was combined with 22.5 parts of 1,4-butanediol (0.5 equiv) in a round bottom flask. The reaction mixture was heated to 60~C and held at that temperature until the % NCO
reached 19.1.
Polyisocyanate 5 87.5 parts (1 equiv) of a mixture of 2,4- and 2,6-toluylene diisocyanate (80:20 isomer ratio) was combined with 33.5 parts of 10 1,4-butanediol (0.5 equiv) in a round bottom flask. The reaction mixture was heated to 60~C and held at that temperature until the % NCO
reached 17.4.
Polyisocyanate 6 A urethane group-containing polyisocyanate based on toluene 15 diisocyanate and trimethylol propane; having an isocyanate content of 13.0%, a content of monomeric diisocyanate of ~0.5% and a viscosity at 20~C of about 1000 mPa.s; and present as a 75% solution in ethyl acetate (available from Bayer Corporation as Desmodur CB-75.
Preparation of N-(3-triethoxysilylPropYI) aspartic acid diethvl ester 8.27 equiv of 3-aminopropyltrialkoxysilane were added to a 5 liter flask fitted with agitator, thermocouple, nitrogen inlet and addition funnel with condenser. 8.27 equiv of diethyl maleate were added dropwise over a period of 2 hours. The temperature of the reactor was maintained at 25~C during the addition. The reactor was maintained at 25~C for an 25 additional 5 hours at which time the product was poured into glass containers and sealed under a blanket of nitrogen. After one week the unsaturation number was 0.6 illdicalillg the reaction was ~99% complete.
Mo4649 -1 3-The following compounds were prepared: Viscosity at 25~C
N-(3-trimethoxysilylpropyl) aspartic acid diethyl ester 11 mPa.s N-(3-triethoxysilylpropyl) aspartic acid dibutyl ester 11 mPa.s N-(3-trimethoxysilylpropyl) aspartic acid dibutyl ester 18 mPa.s 5 Alkoxvsilane Resin 1 Tris-[3-(trimethoxysilyl)propyl]-isocyanurate (Silquest Y-11597, available from Witco Corp.).
Example 1 669.0 parts (1.7 equiv) of N-(3-trimethoxysilylpropyl) aspartic acid 10 diethyl ester and 331 parts (1.7 equiv) of polyisocyanate 1 were added to a three neck, 5 liter, round bottom flask equipped with an agitator, nitrogen inlet, thermocouple and condenser. The reaction to form the urea was accompanied by an exotherm which increased the temperature of the reaction mixture to 80~C. The reaction was held at 80~C for 14 15 hours at which time the IR spectrum showed no residual isocyanate in the urea. The product was cooled and the viscosity of the product was determined to be >300,000 at 25~C.
Analysis via GC, IR, NMR and GPC were consistent with the following structure:
Mo4649 -1 4-~~'s,--~~
0~ ~ o~
--\ ~NH~O
/~j,1,, W ~ ~
o~ ~/ si--o ~~~o The product was separately mixed with n-butyl acetate and xylene to form solutions having solids contents of 90%, 80% and 70%. The viscosities of these solutions are set forth in Table 1.
Solids content (%)Solvent Viscosity at25~C (mPa.s) 100 - >300,000 n-butyl acetate11,470 n-butyl acetate 2123 n-butyl acetate 492 xylene 13,760 xylene 1311 xylene 234 The product was also soluble in toluene and tetrahydrofuran.
Mo4649 -1 5-Examples 2-18 Example 1 was repeated with the exception that Polyisocyanate 1 was replaced with an equivalent amount of polyisocyanates 2-7 and also with 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate 5 (IPDI) and bis-(4-isocyanatocyclohexyl)-methane (HMDI). In Example 11 an additional 100 g of propylene glycol methyl ether acetate was added to lower the viscosity of the reaction mixture. All of the resulting products were liquid and, more importantly, were soluble in toluene, xylene, butyl acetate and tetrahydrofuran.
In the comparison examples all of the preceding examples were repeated with the exception that each of the polyisocyanates was directly reacted with 3-aminopropyltrialkoxysilane instead of the aspartate of this silane. In every comparison example (except for comparison example 4) the resulting urea product solidified to form an entrained mixture of 15 solvent and product. The product from comparison example 4 was an extremely high viscosity oil. In contrast to the examples accordi"g to the invention, the products of the comparison examples, including the product of comparison example 4, were not soluble in toluene, xylene, butyl acetate or tetrahydrofuran. Because the silane functional ureas 20 could not be dissolved, they could not be used to prepare coatings.
Mo4649 -16-The results are set forth in Table 2.
Example No. Polyisocyanate Viscosity of Urea at 25~C (mPa s) Polyisocyanate 1 >300,000 52 (Comp) Polyisocyanate 1 Insoluble Solid*
3 Polyisocyanate 2 21,600 4 (Comp) Polyisocyanate 2 HighlyViscous Oil*
Polyisocyanate 3 251,000 6 (Comp) Polyisocyanate 3 Insoluble Solid*
7 Polyisocyanate 4 >300,000 8 (Comp) Polyisocyanate 4 Insoluble Solid*
Prefer,ed polyisocyanate adducts are the polyisocyanates 15 containing isocyanurate groups, biuret groups, allophanate groups and/or uretdione groups.
The compounds of formula I containing alkoxysilane groups and hydantoin groups are prepared by reacting the polyisocyanate monomers and/or adducts with the compounds of formula ll at an equivalent ratio of 20 aspartate groups (i.e., secondary amino groups) to isocyanate groups of approximately 1:1. The reaction is preferably carried out by incrementally adding the aspartate to the polyisocyanate. The reaction to form the urea groups is conducted at a temperature of 10 to 100~C, preferably 20 to 80~C and more preferably 20 to 50~C.
The compounds of the present invention are suitable for the production of sealant (including caulks), coating or adhesive compositions which can be cross-linked by "silane polycondensation," i.e., the condensation of silane groups (Si-OR) to form siloxane groups (Si-O-Si).
When used for this purpose, these compounds may be used as mixtures 30 with suitable acidic or basic catalysts. Examples include acids such as Mo4649 -11-paratoluene sulfonic acid; metallic salts such as dibutyl tin dilaurate;
tertiary amines such as triethylamine or triethylene diamine; and mixtures of these catalysts. Low molecular weight, basic aminoalkyl trialkoxysilanes, such as those represented by formula IV, also accelerate 5 hardening of the compounds according to the invention.
The invention is further illustrated but is not intended to be limited by the following examples in which all parts and percentages are by weight unless otherwise specified.
E)CAMPLES
10 Polyisocyanate 1 An isocyanurate group-containing polyisocyanate prepared from 1,6-hexamethylene diisocyanate and having an isocyanate content of 21.6%, a content of monomeric diisocyanate of ~0.2% and a viscosity at 20~C of 3000 mPa.s (available from Bayer Corporation as Desmodur N
3300).
Polyisocyanate 2 A mixture containing 70 parts by weight of a uretdione group-containing polyisocyanate, i.e., dimerized 1,6-hexamethylene diisocyanate and 30 parts by weight of N,N',N"-tris-(6-isocyanatohexyl)-isocyanurate together with minor quantities of higher homologs of both products and having a average viscosity of 150 mPa.s at 23~C and an average NC0 content of 22.5% (available from Bayer Corporation as Desmodur N 3400).
Polvisocyanate 3 An aniline/formaldehyde condensation product containing a mixture of diphenylmethane diisocyanate isomers as well as their higher homologs, having an NC0 content of about 31 % and a viscosity of about 40 mPa s at 23~C (available from Bayer Corporation as Mondur MRS-4).
Mo4649 -1 2-Polvisocyanate 4 87.5 parts (1 equiv) of a mixture of 2,4- and 2,6-toluylene diisocyanate (80:20 isomer ratio) was combined with 22.5 parts of 1,4-butanediol (0.5 equiv) in a round bottom flask. The reaction mixture was heated to 60~C and held at that temperature until the % NCO
reached 19.1.
Polyisocyanate 5 87.5 parts (1 equiv) of a mixture of 2,4- and 2,6-toluylene diisocyanate (80:20 isomer ratio) was combined with 33.5 parts of 10 1,4-butanediol (0.5 equiv) in a round bottom flask. The reaction mixture was heated to 60~C and held at that temperature until the % NCO
reached 17.4.
Polyisocyanate 6 A urethane group-containing polyisocyanate based on toluene 15 diisocyanate and trimethylol propane; having an isocyanate content of 13.0%, a content of monomeric diisocyanate of ~0.5% and a viscosity at 20~C of about 1000 mPa.s; and present as a 75% solution in ethyl acetate (available from Bayer Corporation as Desmodur CB-75.
Preparation of N-(3-triethoxysilylPropYI) aspartic acid diethvl ester 8.27 equiv of 3-aminopropyltrialkoxysilane were added to a 5 liter flask fitted with agitator, thermocouple, nitrogen inlet and addition funnel with condenser. 8.27 equiv of diethyl maleate were added dropwise over a period of 2 hours. The temperature of the reactor was maintained at 25~C during the addition. The reactor was maintained at 25~C for an 25 additional 5 hours at which time the product was poured into glass containers and sealed under a blanket of nitrogen. After one week the unsaturation number was 0.6 illdicalillg the reaction was ~99% complete.
Mo4649 -1 3-The following compounds were prepared: Viscosity at 25~C
N-(3-trimethoxysilylpropyl) aspartic acid diethyl ester 11 mPa.s N-(3-triethoxysilylpropyl) aspartic acid dibutyl ester 11 mPa.s N-(3-trimethoxysilylpropyl) aspartic acid dibutyl ester 18 mPa.s 5 Alkoxvsilane Resin 1 Tris-[3-(trimethoxysilyl)propyl]-isocyanurate (Silquest Y-11597, available from Witco Corp.).
Example 1 669.0 parts (1.7 equiv) of N-(3-trimethoxysilylpropyl) aspartic acid 10 diethyl ester and 331 parts (1.7 equiv) of polyisocyanate 1 were added to a three neck, 5 liter, round bottom flask equipped with an agitator, nitrogen inlet, thermocouple and condenser. The reaction to form the urea was accompanied by an exotherm which increased the temperature of the reaction mixture to 80~C. The reaction was held at 80~C for 14 15 hours at which time the IR spectrum showed no residual isocyanate in the urea. The product was cooled and the viscosity of the product was determined to be >300,000 at 25~C.
Analysis via GC, IR, NMR and GPC were consistent with the following structure:
Mo4649 -1 4-~~'s,--~~
0~ ~ o~
--\ ~NH~O
/~j,1,, W ~ ~
o~ ~/ si--o ~~~o The product was separately mixed with n-butyl acetate and xylene to form solutions having solids contents of 90%, 80% and 70%. The viscosities of these solutions are set forth in Table 1.
Solids content (%)Solvent Viscosity at25~C (mPa.s) 100 - >300,000 n-butyl acetate11,470 n-butyl acetate 2123 n-butyl acetate 492 xylene 13,760 xylene 1311 xylene 234 The product was also soluble in toluene and tetrahydrofuran.
Mo4649 -1 5-Examples 2-18 Example 1 was repeated with the exception that Polyisocyanate 1 was replaced with an equivalent amount of polyisocyanates 2-7 and also with 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate 5 (IPDI) and bis-(4-isocyanatocyclohexyl)-methane (HMDI). In Example 11 an additional 100 g of propylene glycol methyl ether acetate was added to lower the viscosity of the reaction mixture. All of the resulting products were liquid and, more importantly, were soluble in toluene, xylene, butyl acetate and tetrahydrofuran.
In the comparison examples all of the preceding examples were repeated with the exception that each of the polyisocyanates was directly reacted with 3-aminopropyltrialkoxysilane instead of the aspartate of this silane. In every comparison example (except for comparison example 4) the resulting urea product solidified to form an entrained mixture of 15 solvent and product. The product from comparison example 4 was an extremely high viscosity oil. In contrast to the examples accordi"g to the invention, the products of the comparison examples, including the product of comparison example 4, were not soluble in toluene, xylene, butyl acetate or tetrahydrofuran. Because the silane functional ureas 20 could not be dissolved, they could not be used to prepare coatings.
Mo4649 -16-The results are set forth in Table 2.
Example No. Polyisocyanate Viscosity of Urea at 25~C (mPa s) Polyisocyanate 1 >300,000 52 (Comp) Polyisocyanate 1 Insoluble Solid*
3 Polyisocyanate 2 21,600 4 (Comp) Polyisocyanate 2 HighlyViscous Oil*
Polyisocyanate 3 251,000 6 (Comp) Polyisocyanate 3 Insoluble Solid*
7 Polyisocyanate 4 >300,000 8 (Comp) Polyisocyanate 4 Insoluble Solid*
9 Polyisocyanate 5 >300,000 10 (Comp) Polyisocyanate 5 Insoluble Solid*
11 Polyisocyanate 6 >300,000 1512 (Comp) Polyisocyanate 6 Insoluble Solid*
14 (Comp) HDI Insoluble Solid*
IPDI 160,000 16 (Comp) IPDI Insoluble Solid*
17 HMDI 324,000 18 (Comp) HMDI Insoluble Solid*
* These products could not be dissolved in xylene, toluene, butyl acetate or tetrahydrofuran.
Mo4649 -17-Examples 19-22 Polyisocyanate 1 and HDI were each reacted with N-(3-triethoxysilylpropyl) aspartic acid dibutyl ester and N-(3-trimethoxysilylpropyl) aspartic acid dibutyl ester following the procedure of Example 1. All of the resulting products were 5 liquid and soluble in toluene, xylene, butyl acetate and tetrahydrofuran. The results are set forth in the Table 3.
ExamplePolyisocyanate Trialkoxy Silane Viscosity of Urea No. Aspartate at 25~C (mPas) 19 Polyisocyanate 1 Ethoxy 801300 Polyisocyanate 1 Methoxy 158,000 21 HDI Ethoxy 2200 22 HDI Methoxy 3100 Example 23 - Comparison A coating composition was prepared by adding 1 part of dibutyl tin dilaurate to 100 parts (70% solids) of alkoxysilane resin 1, dissolved at 70% solids in toluene. The compositions were applied to steel panels at a wet film thickness of 5 mils (3.5 mils dry film thickness). The film cured with a cracked surface, was very friable and had no adhesion to 20 the substrate.
Examples 24-25 - Pre,c,aratioil of coatings from the urea group-containing compound of Example 1 Coatings were prepared from the urea group-containing compound prepared in Example 1. In addiliol1 to these compounds the coating 25 compositions contained the ingredients set forth in Table 3. The levelling agent was Byk 358, a silicone based additive, available form Byk Mo4649 -18-Chemie; the catalyst was dibutyl tin dilaurate. The properties of the resulting coatings are also set forth in Table 4.
Table 4 Example 24 25 5 Ingredient Urea from Ex. 1 200 100 Alkoxysilane Resin 1 0 100 Ethanol 200 200 Levelling Agent 10 Catalyst 2 2 Pendulum Hardness, sec.
Day 1 0 0 Pencil Hardness, Day 26 2B 3H
MEK Double Rubs Day 1 wet wet Mo4649 -1 9-Table 4 (Cont'd) Example 24 25 Chemical Spot Test: 1,4 and 24 hour spots Gasoline ne,s,s ne,ne,ne Motor oil ne,ne,ne ne,ne,ne Methyl ethyl ketone ds,ds,ds, ne,ne,ne Isopropanol s,s,s ne,ne,ne Propylene glycol s,s,ds ne,ne,ne methyl ether acetate HCI, 37% ne,st,bl ne,st,ds H2S04, 50% ne,ne,ne ne,ne,st Acetic acid ds,ds,ds s,ds,ds Aniline ds,ds,ds ne,ne,ne Tg, ~C S9 61 This example demonstrates the ability of compounds containing urea and alkoxysilane groups according to the invention to flexibilize other silane containing compounds that are not capable of forming films on their own. See comparison example 23.
MEK double rubs was determined by wetting a cloth with methyl 20 ethyl ketone and then rubbing each panel up to 100 times. A double rub consists of one back and forth rub against the coated panel. Values of less than 100 indicate the number of double rubs before the coatings was destroyed.
Mo4649 -20-Pendulum hardness was determined in accordance with ASTM D-4366-87 (Koenig Pendulum Hardness).
Chemical spot resistance was determined by placing a drop of the particular liquid on a coated panel and covering it with a 4 oz. glass jar.
5 For those solvents that rapidly evaporate a cotton ball was placed on the coated panel liquids and kept saturated. After the appropriate time interval, the coated panels were washed, evaluated to determine the effect of the liquid, and assigned one of the following classiricalio,ls:
ne No effect s Film softened, but recovered after 1 hour ds Dissolved st Stained bl Blistered Although the invention has been described in detail in the 15 foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
14 (Comp) HDI Insoluble Solid*
IPDI 160,000 16 (Comp) IPDI Insoluble Solid*
17 HMDI 324,000 18 (Comp) HMDI Insoluble Solid*
* These products could not be dissolved in xylene, toluene, butyl acetate or tetrahydrofuran.
Mo4649 -17-Examples 19-22 Polyisocyanate 1 and HDI were each reacted with N-(3-triethoxysilylpropyl) aspartic acid dibutyl ester and N-(3-trimethoxysilylpropyl) aspartic acid dibutyl ester following the procedure of Example 1. All of the resulting products were 5 liquid and soluble in toluene, xylene, butyl acetate and tetrahydrofuran. The results are set forth in the Table 3.
ExamplePolyisocyanate Trialkoxy Silane Viscosity of Urea No. Aspartate at 25~C (mPas) 19 Polyisocyanate 1 Ethoxy 801300 Polyisocyanate 1 Methoxy 158,000 21 HDI Ethoxy 2200 22 HDI Methoxy 3100 Example 23 - Comparison A coating composition was prepared by adding 1 part of dibutyl tin dilaurate to 100 parts (70% solids) of alkoxysilane resin 1, dissolved at 70% solids in toluene. The compositions were applied to steel panels at a wet film thickness of 5 mils (3.5 mils dry film thickness). The film cured with a cracked surface, was very friable and had no adhesion to 20 the substrate.
Examples 24-25 - Pre,c,aratioil of coatings from the urea group-containing compound of Example 1 Coatings were prepared from the urea group-containing compound prepared in Example 1. In addiliol1 to these compounds the coating 25 compositions contained the ingredients set forth in Table 3. The levelling agent was Byk 358, a silicone based additive, available form Byk Mo4649 -18-Chemie; the catalyst was dibutyl tin dilaurate. The properties of the resulting coatings are also set forth in Table 4.
Table 4 Example 24 25 5 Ingredient Urea from Ex. 1 200 100 Alkoxysilane Resin 1 0 100 Ethanol 200 200 Levelling Agent 10 Catalyst 2 2 Pendulum Hardness, sec.
Day 1 0 0 Pencil Hardness, Day 26 2B 3H
MEK Double Rubs Day 1 wet wet Mo4649 -1 9-Table 4 (Cont'd) Example 24 25 Chemical Spot Test: 1,4 and 24 hour spots Gasoline ne,s,s ne,ne,ne Motor oil ne,ne,ne ne,ne,ne Methyl ethyl ketone ds,ds,ds, ne,ne,ne Isopropanol s,s,s ne,ne,ne Propylene glycol s,s,ds ne,ne,ne methyl ether acetate HCI, 37% ne,st,bl ne,st,ds H2S04, 50% ne,ne,ne ne,ne,st Acetic acid ds,ds,ds s,ds,ds Aniline ds,ds,ds ne,ne,ne Tg, ~C S9 61 This example demonstrates the ability of compounds containing urea and alkoxysilane groups according to the invention to flexibilize other silane containing compounds that are not capable of forming films on their own. See comparison example 23.
MEK double rubs was determined by wetting a cloth with methyl 20 ethyl ketone and then rubbing each panel up to 100 times. A double rub consists of one back and forth rub against the coated panel. Values of less than 100 indicate the number of double rubs before the coatings was destroyed.
Mo4649 -20-Pendulum hardness was determined in accordance with ASTM D-4366-87 (Koenig Pendulum Hardness).
Chemical spot resistance was determined by placing a drop of the particular liquid on a coated panel and covering it with a 4 oz. glass jar.
5 For those solvents that rapidly evaporate a cotton ball was placed on the coated panel liquids and kept saturated. After the appropriate time interval, the coated panels were washed, evaluated to determine the effect of the liquid, and assigned one of the following classiricalio,ls:
ne No effect s Film softened, but recovered after 1 hour ds Dissolved st Stained bl Blistered Although the invention has been described in detail in the 15 foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Claims (13)
1. The present invention relates to compounds containing alkoxysilane and urea groups corresponding to the formula wherein X represents identical or different organic groups which are inert to isocyanate groups below 100°C, provided that at least one of these groups is an alkoxy group, Z represents COOR, or an aromatic ring, R represents the residue obtained by removing the isocyanate groups from an organic monomeric polyisocyanate or a polyisocyanate adduct, R1 and R2 are identical or different and represent organic groups which are inert to isocyanate groups at a temperature of 100°C or less, R3 and R4 are identical or different and represent hydrogen or organic groups which are inert to isocyanate groups at a temperature of 100°C or less and n is an integer from 1 to 8.
2. The compound of Claim 1 wherein X represents identical or different alkyl or alkoxy groups having 1 to 4 carbon atoms, Z represents COOR,, R, is an alkyl group having 1 to 9 carbon atoms, R3 and R4 represent hydrogen and n is an integer from 2 to 4.
3. The compound of Claim 1 wherein X represents identical or different alkoxy groups having 1 to 4 carbon atoms, Z represents COOR1, R1 is methyl, ethyl or butyl, R3 and R4 represent hydrogen and n is 3.
4. The compound of Claim 1 wherein R represents the residue obtained by removing the isocyanate groups from an organic monomeric polyisocyanate.
5. The compound of Claim 2 wherein R represents the residue obtained by removing the isocyanate groups from an organic monomeric polyisocyanate.
6. The compound of Claim 3 wherein R represents the residue obtained by removing the isocyanate groups from an organic monomeric polyisocyanate.
7. The compound of Claim 1 wherein R represents the residue obtained by removing the isocyanate groups from a polyisocyanate adduct.
8. The compound of Claim 2 wherein R represents the residue obtained by removing the isocyanate groups from a polyisocyanate adduct.
9. The compound of Claim 3 wherein R represents the residue obtained by removing the isocyanate groups from a polyisocyanate adduct.
10. The compound of Claim 1 wherein R represents the residue obtained by removing the isocyanate groups from a polyisocyanate adduct containing isocyanurate groups, biuret groups, allophanate groups and/or uretdione groups.
11. The compound of Claim 2 wherein R represents the residue obtained by removing the isocyanate groups from a polyisocyanate adduct containing isocyanurate groups, biuret groups, allophanate groups and/or uretdione groups.
12. The compound of Claim 3 wherein R represents the residue obtained by removing the isocyanate groups from a polyisocyanate adduct containing isocyanurate groups, biuret groups, allophanate groups and/or uretdione groups.
13. A coating, sealant or adhesive prepared from the compounds of Claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/814,561 US5908948A (en) | 1997-03-11 | 1997-03-11 | Compounds containing urea and alkoxysilane groups |
| US08/814,561 | 1997-11-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2229299A1 true CA2229299A1 (en) | 1999-05-03 |
Family
ID=25215434
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002229299A Abandoned CA2229299A1 (en) | 1997-03-11 | 1998-02-11 | Compounds containing urea and alkoxysilane groups |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5908948A (en) |
| EP (1) | EP0864575B1 (en) |
| JP (1) | JP4163782B2 (en) |
| AT (1) | ATE223423T1 (en) |
| CA (1) | CA2229299A1 (en) |
| DE (1) | DE69807549T2 (en) |
| ES (1) | ES2183244T3 (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6005047A (en) * | 1998-10-14 | 1999-12-21 | Bayer Corporation | Moisture-curable compounds containing isocyanate and alkoxysilane groups |
| US6096823A (en) * | 1998-10-14 | 2000-08-01 | Bayer Corporation | Moisture-curable compounds containing isocyanate and alkoxysilane groups |
| US6077902A (en) * | 1998-10-14 | 2000-06-20 | Bayer Corporation | Moisture-curable compounds containing isocyanate and alkoxysilane groups |
| US6046270A (en) * | 1998-10-14 | 2000-04-04 | Bayer Corporation | Silane-modified polyurethane resins, a process for their preparation and their use as moisture-curable resins |
| US6063863A (en) * | 1998-12-23 | 2000-05-16 | Bayer Corporation | Aqueous compositions containing colloidal silica and compounds with alkoxysilane and/or silanol groups |
| US6111010A (en) * | 1998-12-23 | 2000-08-29 | Bayer Corporation | Aqueous compounds containing alkoxysilane and/or silanol groups |
| WO2001000632A2 (en) | 1999-06-25 | 2001-01-04 | Bayer Aktiengesellschaft | Piperazinone derivatives with alkoxysilane groups |
| US6265517B1 (en) * | 1999-09-07 | 2001-07-24 | Bostik, Inc. | Silylated polyether sealant |
| US7057000B2 (en) | 2000-12-22 | 2006-06-06 | Bayer Materialscience Llc | Two-component coating compositions containing silane adhesion promoters |
| US6444325B1 (en) * | 2000-12-22 | 2002-09-03 | Bayer Corporation | Two-component coating compositions containing silane adhesion promoters |
| US7482420B2 (en) * | 2004-03-24 | 2009-01-27 | Construction Research & Technology Gmbh | Silane-terminated polyurethanes with high strength and high elongation |
| EP1717254A1 (en) | 2005-04-29 | 2006-11-02 | Sika Technology AG | Moisture-curable composition with improved elongation |
| WO2007085622A1 (en) * | 2006-01-26 | 2007-08-02 | Sika Technology Ag | Moisture-curing compositions containing silane-functional polymers and aminosilane adducts with good adhesive properties |
| DE102008050916A1 (en) * | 2008-10-10 | 2010-04-15 | Basf Coatings Ag | Two-component polyurethane lacquer containing silanized polyisocyanate hardeners, process for the preparation of silanized polyisocyanate hardeners and hardeners prepared by the process |
| US8293836B2 (en) | 2009-05-20 | 2012-10-23 | Basf Coatings Gmbh | Curable coating composition containing a compound having a uretdione group and a different functional group and cured coatings |
| MX2012010550A (en) | 2010-04-21 | 2012-11-16 | Basf Coatings Gmbh | Coating materials with high solids content and good levelling, multi-coat paint systems produced therefrom and use thereof. |
| KR101906618B1 (en) * | 2010-11-19 | 2018-10-10 | 바스프 코팅스 게엠베하 | Coating composition having a high solids content and good levelling and also multilayer surface coatings produced therefrom and their use |
| WO2014137694A1 (en) * | 2013-03-04 | 2014-09-12 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Silane end capped substituted urea resins and coatings thereof |
| US20160230042A1 (en) * | 2013-03-04 | 2016-08-11 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Silane end capped substituted urea resins and coatings thereof |
| JP6932249B2 (en) * | 2018-04-12 | 2021-09-08 | 日本パーカライジング株式会社 | Polysiloxane compounds and compositions |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2832754A (en) * | 1955-01-21 | 1958-04-29 | Union Carbide Corp | Alkoxysilylpropylamines |
| US2971864A (en) * | 1958-03-26 | 1961-02-14 | Dow Corning | Aminated mono-organosilanes and method of dyeing glass therewith |
| GB1243189A (en) * | 1967-12-05 | 1971-08-18 | British Petroleum Co | Oxo process |
| GB1243190A (en) * | 1967-12-05 | 1971-08-18 | British Petroleum Co | Oxo catalyst |
| US3676478A (en) * | 1968-12-04 | 1972-07-11 | Bayer Ag | Silyl-substituted urea derivatives |
| US4481364A (en) * | 1983-09-26 | 1984-11-06 | Union Carbide Corporation | Preparation of aminopropyltrialkoxysilanes and/or aminoalkylalkoxysilanes |
| EP0403921B1 (en) * | 1989-06-23 | 1994-11-02 | Bayer Ag | Process for the preparation of coatings |
| US5236741A (en) * | 1989-06-23 | 1993-08-17 | Bayer Aktiengesellschaft | Process for the production of polyurethane coatings |
| DE4011044A1 (en) * | 1990-04-05 | 1991-10-10 | Fraunhofer Ges Forschung | SILANES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR THE PRODUCTION OF POLYMERISATS AND POLYCONDENSATES |
| DE4029505A1 (en) * | 1990-09-18 | 1992-03-19 | Henkel Kgaa | MOISTURIZING, ALKOXYSILANE-TERMINATED POLYURETHANE |
| US5312943A (en) * | 1992-10-13 | 1994-05-17 | Caschem, Inc. | Dual curing conformal coatings |
| US5523443A (en) * | 1992-10-13 | 1996-06-04 | Caschem, Inc. | Dual curing conformal coatings |
| DE4237468A1 (en) * | 1992-11-06 | 1994-05-11 | Bayer Ag | Compounds containing alkoxysilane and amino groups |
| US5550272A (en) * | 1995-10-02 | 1996-08-27 | General Electric Company | Method for hydrosilating unsaturated monomers |
-
1997
- 1997-03-11 US US08/814,561 patent/US5908948A/en not_active Expired - Lifetime
-
1998
- 1998-02-11 CA CA002229299A patent/CA2229299A1/en not_active Abandoned
- 1998-02-26 EP EP98103320A patent/EP0864575B1/en not_active Expired - Lifetime
- 1998-02-26 ES ES98103320T patent/ES2183244T3/en not_active Expired - Lifetime
- 1998-02-26 AT AT98103320T patent/ATE223423T1/en not_active IP Right Cessation
- 1998-02-26 DE DE69807549T patent/DE69807549T2/en not_active Expired - Lifetime
- 1998-03-09 JP JP07306298A patent/JP4163782B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP4163782B2 (en) | 2008-10-08 |
| EP0864575A3 (en) | 1999-09-15 |
| US5908948A (en) | 1999-06-01 |
| JPH10251272A (en) | 1998-09-22 |
| ES2183244T3 (en) | 2003-03-16 |
| DE69807549D1 (en) | 2002-10-10 |
| DE69807549T2 (en) | 2003-01-16 |
| ATE223423T1 (en) | 2002-09-15 |
| EP0864575B1 (en) | 2002-09-04 |
| EP0864575A2 (en) | 1998-09-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |