CA2015043A1 - Prepolymers containing ester and isocyanate groups and a process for their production - Google Patents
Prepolymers containing ester and isocyanate groups and a process for their productionInfo
- Publication number
- CA2015043A1 CA2015043A1 CA 2015043 CA2015043A CA2015043A1 CA 2015043 A1 CA2015043 A1 CA 2015043A1 CA 2015043 CA2015043 CA 2015043 CA 2015043 A CA2015043 A CA 2015043A CA 2015043 A1 CA2015043 A1 CA 2015043A1
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- hydroxyl groups
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/771—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/302—Water
- C08G18/307—Atmospheric humidity
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/71—Monoisocyanates or monoisothiocyanates
- C08G18/712—Monoisocyanates or monoisothiocyanates containing halogens
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Emergency Medicine (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
Mo3350 LeA 26,871 PREPOLYMERS CONTAINING ESTER AND ISOCYANATE
GROUPS AND A PROCESS FOR THEIR PRODUCTION
ABSTRACT OF THE DISCLOSURE
The present invention relates to a process for the production of prepolymers containing ester and isocyanate groups by reacting a) isocyanatocarboxylic acid chlorides with b) organic compounds which contain at least two silylated hydroxyl groups, contain only 0-silylated hydroxyl groups and are otherwise inert to isocyanate and chlorocarbonyl groups under the reaction conditions, and are based on polyhydroxyl compounds having a molecular weight of 400 to about 20,000.
The present invention also relates to the prepolymers containing ester and isocyanate groups obtained by this process.
Mo3350
GROUPS AND A PROCESS FOR THEIR PRODUCTION
ABSTRACT OF THE DISCLOSURE
The present invention relates to a process for the production of prepolymers containing ester and isocyanate groups by reacting a) isocyanatocarboxylic acid chlorides with b) organic compounds which contain at least two silylated hydroxyl groups, contain only 0-silylated hydroxyl groups and are otherwise inert to isocyanate and chlorocarbonyl groups under the reaction conditions, and are based on polyhydroxyl compounds having a molecular weight of 400 to about 20,000.
The present invention also relates to the prepolymers containing ester and isocyanate groups obtained by this process.
Mo3350
Description
2 ~ 3 Mo3350 LeA 26,871 PREPOLYMER _CONTAINING ESTER AND ISOCYANATE
GROUPS AND A PROCESS FOR THEIR PRODUCTION
BACKGROUND OF THE INVENTION
Field of the Invention This invention relates to a new process for the production of prepolymers containing isocyanate groups and to the prepolymers obtained by this process.
Description of the Prior Art Prepolymers containing isocyanate groups are normally o prepared by reacting relatively high molecular weight polyhydroxyl compounds with excess quantities of low molecular weight diisocyanates or polyisocyanates. The reaction products initially contain relatively large amounts of monomeric diisocyanates or polyisocyanates which have to be removed for industrial hygiene reasons. This may be done, for example, by thin-layer distillation.
The monomer-free NCO prepolymers obtained always have much higher viscosities than the starting compounds. Accordingly, prepolymers such as these can often only be used for the production of paints or coating materials after the addition of organic solvents or plasticizers.
However, it is known that the use of solvents is undesirable for ecological reasons. lhe use of plasticizers also involves disadvantages. Plasticizers remain in the coatings, can adversely affect the mechanical properties of the polymers, can impair adhesion to the substrate and, finally, can migrate from the coatings over time.
Accordingly, an object of the present invention is to provide a new process for the production of relatively high molecular weight, monomer-free isocyanate prepolymers which is not attended by the above-mentioned disadvantages and results in NCO prepolymers having viscosities which substantially correspond to the viscosities of the corresponding polyhydroxyl compounds.
This object may be achieved in accordance with the process of the present invention which is described in detail hereinafter. In the process the relatively high molecular weight polyhydroxyl compounds used as starting materials are 5 reacted in O-silylated form with isocyanatocarboxylic acid chlorides to provide NCO prepolymers having viscosities which substantially correspond to the viscosities of the basic unsilylated polyhydroxyl compounds.
Although the reaction of isocyanatocarboxylic acid o chlorides with O-silylated alcohols is known from DE-OS
GROUPS AND A PROCESS FOR THEIR PRODUCTION
BACKGROUND OF THE INVENTION
Field of the Invention This invention relates to a new process for the production of prepolymers containing isocyanate groups and to the prepolymers obtained by this process.
Description of the Prior Art Prepolymers containing isocyanate groups are normally o prepared by reacting relatively high molecular weight polyhydroxyl compounds with excess quantities of low molecular weight diisocyanates or polyisocyanates. The reaction products initially contain relatively large amounts of monomeric diisocyanates or polyisocyanates which have to be removed for industrial hygiene reasons. This may be done, for example, by thin-layer distillation.
The monomer-free NCO prepolymers obtained always have much higher viscosities than the starting compounds. Accordingly, prepolymers such as these can often only be used for the production of paints or coating materials after the addition of organic solvents or plasticizers.
However, it is known that the use of solvents is undesirable for ecological reasons. lhe use of plasticizers also involves disadvantages. Plasticizers remain in the coatings, can adversely affect the mechanical properties of the polymers, can impair adhesion to the substrate and, finally, can migrate from the coatings over time.
Accordingly, an object of the present invention is to provide a new process for the production of relatively high molecular weight, monomer-free isocyanate prepolymers which is not attended by the above-mentioned disadvantages and results in NCO prepolymers having viscosities which substantially correspond to the viscosities of the corresponding polyhydroxyl compounds.
This object may be achieved in accordance with the process of the present invention which is described in detail hereinafter. In the process the relatively high molecular weight polyhydroxyl compounds used as starting materials are 5 reacted in O-silylated form with isocyanatocarboxylic acid chlorides to provide NCO prepolymers having viscosities which substantially correspond to the viscosities of the basic unsilylated polyhydroxyl compounds.
Although the reaction of isocyanatocarboxylic acid o chlorides with O-silylated alcohols is known from DE-OS
3 634 248, this publication is directed solely to the production of low molecular weight isocyanates containing ester and/or amide groups. It was not foreseeable based on the teachings of DE-OS 3 634 248 that isocyanate prepolymers having 15 viscosities which substantially correspond to the viscosities of the corresponding polyhydroxyl compounds would be obtained in accordance with the present invention.
The process according to the invention provides prepolymers containing ester and isocyanate groups which are similar to those described in DE-OS 2 120 090. According to this prior publication, however, the compounds are prepared by reaction of polyhydroxyl compounds containing free hydroxyl groups with isocyanatocarboxylic acid chlorides in the presence of a hydrogen halide absorber. The disadvantage of this process is in particular the formation of large quantities of salts and the considerably higher viscosities of the resulting NCO prepolymers when compared to the corresponding polyhydroxyl compounds.
_UMMARY OF THE INVENTION
3C The present invention relates to a process for the production of prepolymers containing ester and isocyanate groups by reacting a) isocyanatocarboxylic acid chlorides with b) organic compounds which contain at least two silylated hydroxyl groups, contain only O-silylated hydroxyl groups Mo3350 2 ~
and are otherwise inert to isocyanate and chlorocarbonyl groups under the reaction conditions, and are based on polyhydroxyl compounds having a molecular weight of 400 to about 20,000.
~he present invention also relates to the prepolymers containing ester and isocyanate groups obtained by this process.
DETAILED DESCRIPTION OF THE INVENTION
Suitable isocyanatocarboxylic acid chlorides for use as o component a) in accordance with the present invention are organic compounds which contain at least one isocyanate group and at least one chlorocarbonyl group per molecule and which, apart from the chlorocarbonyl group, are inert to silylated hydroxyl compounds of the type used as component b) under the 15 process conditions. Preferred starting components a) are isocyanatocarboxylic acid chlorides corresponding to the formula Cl-CO-B-NCO
20 wherein B is an organic radical inert to silylated hydroxyl groups, preferably an aliphatic hydrocarbon radical containing 2 to 11 carbon atoms or a cycloaliphatic hydrocarbon radical containing 6 carbon atoms, provided that at least 2 carbon atoms are arranged between the carbonyl group and the isocyanate group.
Examples of suitable isocyanatocarboxylic acid chlorides a) include 3-isocyanatopropionic acid chloride, 4-isocyanatobutyric acid chloride, 6-isocyanatocaproic acid chloride, 12-isocyanatododecanoic acid chloride or 4-isocyanatocyclohexane carboxylic acid chloride.
Other suitable, although less preferred, starting components a) include isocyanatocarboxylic acid chlorides corresponding to the above formula wherein B represents an Mo3350 2 ~ ~ ~#~ ~ 3 aromatic hydrocarbon radical containing 6 to 10 carbon atoms and optionally containing other substituents which are inert under the reaction conditions, especially a phenylene radical.
4-isocyanatobenzoic acid chloride is mentioned as an example of 5 such compounds.
Relatively high molecular weight polyhydroxyl compounds having an average molecular weight of 400 to 20,000 as determined by gel permeation chromatography (molecular weights above 5,000) or from the hydroxyl group content and OH
functionality (molecular weights up to 5,000) in the range from 400 to 20,000, wherein the hydroxyl groups have been completely silylated, are used as component b) in the process according to the invention. The molecular weights mentioned here and also in the following are the molecular weights of the non-silylated 15 polyhydroxyl compounds. Apart from the silylated hydroxyl groups, the starting components b) otherwise contain no groups that are reactive to acid chloride or isocyanate groups under the reaction conditions, e.g., urethane groups, if any, present in the starting compounds b) may be regarded as inert under the 20 reaction conditions.
~ he silylated starting components b) are prepared in accordance with known methods (cf. for example E.M. Lalonde and C.H. Chan, Synthesis (1985), pages 817 to 845) by reacting suitable polyhydroxyl compounds with chlorosilanes or 25 disilazanes corresponding to the formulas R3SiCl and R3Si NH SiR3 wherein in both formulas, R is an alkyl or aryl radical, 30 preferably a C1-C4 alkyl radical or a phenyl radical, more preferably a methyl rad;cal. However, the nature of the radical R is of no relevance to the practicability of the : process according to the invention.
The polyhydroxyl compounds are silylated, for example, by 35 reaction with disilazanes corresponding to the above formula, Mo3350 a ~ 3 in a molar ratio of hydroxyl groups to disilazane of approximately 1:0.7 at a temperature of about 60 to 140C, optionally in the presence of acidic catalysts such as p-toluene sulfonic acid or trimethyl chlorosilane. The 5 reaction is complete when the elimination of ammonia stops.
The reaction may be carried out in suitable inert solvents such as hydrocarbons, ethyl acetate, butyl acetate, methoxypropyl acetate, methyl isobutyl ketone or mixtures of such solvents.
The polyhydroxyl compounds suitable for the preparation of component b) contain at least 2, preferably 2 to lO and more preferably 2 to 4 terminal and/or lateral hydroxyl groups.
Suitable relatively high molecular weight polyols for use as starting materials are known in polyurethane chemistry.
Representatives of such compounds are described, for example, in High Polymers, Vol. XVI, "Polyurethanes, Chemistry and Technology", edited by Saunders-Frisch, Interscience Publishers, New York, London, Vol. I, 1962, pages 32 to 42 and Vol. II, 1964, pages 5-6 and 198-199 and in Kunststoff-Handbuch, Vol. VII, Vieweg-Hochtlen, Carl-Hanser-Verlag, Munchen, 1966, for example on pages 45 to 71.
The polyhydroxyl compounds are preferably polyhydroxyl compounds containing ether, ester, carbonate and/or urethane groups and having a molecular weight of about 800 to 5,000. It is possible to use both polyhydroxyl compounds containing one of the groups mentioned and also polyhydroxyl compounds containing two or more groups mentioned in the same molecule.
It is also possible to use mixtures of different polyhydroxyl compounds of the type mentioned in 0-silylated form.
The polyether polyols suitable for use in accordance with the invention are prepared, for example, by the polymerization of epoxides (such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin) on their own, for example in the presence of Lewis acid catalysts (such as BF3), or by addition of these epoxides (preferably Mo3350 L~ 3 ethylene oxide and propylene oxide, optionally in admixture or successively) onto starter compounds containing reactive hydrogen atoms (such as water, alcohols, ammonia or amines).
Examples of starter compounds include ethylene glycol, 1,3- or 5 1,2-propylene glycol, trimethylol propane, glycerol, sorbitol, 4,4'-dihydroxydiphenyl propane, aniline, ethanolamine or ethylenediamine. Sucrose polyethers of the type described, for example, in DE-AS 1 176 358 and 1 064 938 and formitol- or formose-initiated polyethers (DE-OS 2 639 083 and 2 737 951) o may also be used.
Suitable polyester polyols for use in accordance with the present invention are also known and include reaction products of polyhydric, preferably dihydric and, optionally, trihydric alcohols with polybasic, preferably dibasic, carboxylic acids.
15 Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof for the preparation of the polyesters. The polycarboxylic acids may be aliphatic, cycloaliphatic, aromatic 20 and/or heterocyclic and may optionally be unsaturated or substituted, for example by halogen atoms.
Examples of suitable carboxylic acids and their derivatives include succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, 25 trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylene tetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimerized and trimerized unsaturated fatty acids (optionally in 30 admixture with monomeric unsaturated fatty acids such as oleic acids), terephthalic acid dimethyl ester and terephthalic acid-bis-glycol ester. Suitable polyhydric alcohols include ethylene glycol, 1,2- and 1,3-propylene glycol, 1,4- and 2,3-butylene glycol, 1,6-hexanediol, 1,8-octanediol, neopentyl 35 glycol, 1,4-bis-hydroxymethyl cyclohexane, Mo3350 2 ~ ~ 3 2-methyl-1,3-propanediol, glycerol, trimethylol propane, 1,2,6-hexanetriol, 1,2,4-butanetriol, trimethylol ethane, pentaerythritol, quinito'l, mannitol and sorbitol, formitol, methyl glycoside, diethylene glycol, triethylene glycol, 5 tetraethylene glycol and higher MW polyethylene glycols, dipropylene glycol and higher MW polypropylene glycols and also dibutylene glycol and higher MW polybutylene glycols.
Polyesters of lactones such as ~-capro'lactone, or hydroxycarboxylic acids such as ~-hydroxycaproic acid, may also be used.
Suitable polycarbonates containing hydroxyl groups are known and may be obtained, for example, by reacting diols such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol and/or 15 thiodiglycol with phosgene or diaryl carbonates such as diphenyl carbonate (DE-AS 1 694 080, 1 915 908 and 2 221 751;
DE-OS 2 605 024~.
Polyester polycarbonates containing hydroxyl groups and obtained, for exampl'e, in accordance with DE-AS 1 770 245 are 20 also suitable. These compounds are prepared by reacting ~-caprolactone with polyols such as 1,6-hexanediol and subsequent reaction of the resulting ester glycols with diphenyl carbonate.
Suitable polyurethane polyols for use in accordance with 25 the invention are prepared by reacting such relatively high molecular weight polyhydroxyl compounds or low molecular weight polyols such as ethylene glycol, 1,2- and 1,3-propylene glycol, 1,4- and 2,3-butylene glycol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, l,4-bis-hydroxymethyl cyclohexane, 30 2-methyl-1,3-propanediol, glycerol, trimethylol propane, diethylene glycol, dipropylene glycol, or mixtures of low molecular weight and relatively high molecular weight polyols with polyisocyanates such as 2,4- and/or 2,6-toluylene diisocyanate, diphenyl methane-2,4'- and/or -4,4'-diisocyanate, Mo3350 2 ~ 3 1,6-hexamethylene diisocyanate, cyclohexane-1,3- and/or -1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanato-methyl cyclohexane (isophorone diisocyanate), 4,4'-dicyclohexyl methane diisocyanate and/or adducts of the above-mentioned 5 polyisocyanates containing biuret or isocyanurate groups. The quantitative ratio of polyhydroxyl compound to polyisocyanate is selected so that the hydroxyl groups are present in a stoichiometric excess to the isocyanate groups.
Tne preferred starting components b) are those corresponding to the formula A[-O-SiR3]n 5 wherein n is an integer of 2 or greater, A is an organic radical of the type obtained by removing the hydroxyl groups from a polyhydroxyl compound having a molecular weight of 400 to about 20,000 and 0 R is a C1-C4 alkyl radical or a phenyl radical.
Particularly preferred compounds b) are those corresponding to the above formula wherein A is a radical of the type obtained by removing the hydroxyl groups from a polyhydric alcohol containing ether, ester, carbonate and/or urethane groups and having a molecular weight of about 800 to 5,000 and n is an integer from 2 to 10.
In the practical application of the process, the quantitative ratios between the reactants are selected so that the molar ratio of chlorocarbonyl groups to silylated hydroxyl groups is at least 1:1.2, preferably 1:0.8 to 1:1.2. The starting materials are preferably used in equimolar quantities, although it is also possible to use a large excess of isocyanatocarboxylic acid chloride and to remove the unreacted Mo3350 excess, for example by distillation, on completion of the reaction. ~lowever, this procedure is not preferred.
The reaction of the silylated hydroxyl compounds with isocyanatocarboxylic acid chlorides generally takes place at temperatures of about 50 to 150C, optionally in the presence of known catalysts for this reaction such as quinoline or pyridine.
A trialkyl or triaryl chlorosilane is formed as the secondary product of the reaction according to the invention and may be conveniently removed from the reaction mixture by distillation.
The reaction may be carried out in the presence or absence of solvents. Suitable solvents are those which do not contain any active hydrogen atoms and include aliphatic, cycloaliphatic 15 and aromatic hydrocarbons; ethers; ketones; and esters. There is generally no need to use a solvent if the silylated hydroxyl compounds used have a sufficiently low viscosity for carrying out the process according to the invention.
In order to obtain substantially solvent-free 20 polyisocyanate prepolymers, particular preference is attributed to the procedure where no solvents are used. Residues of volatile constituents may be removed from the prepolymers by thin-layer distillation.
The polyisocyanate prepolymers thus obtained are 25 distinguished by the absence of monomers and by unusually low viscosities.
The polyisocyanate prepolymers produced in accordance with the invention are particularly suitable starting materials for the formulation of solventless or low-solvent coating 30 compositions or sealing compounds. The prepolymers may be cured by atmospheric moisture (optionally after the addition of known catalysts such as dibutyltin (IV) dilaurate, and optionally the known pigments, fillers and auxiliaries used in coating technology) to provide polymer films having excellent 3 5 mechanical properties.
Mo3350 The following examples are intended to illustrate the process according to the invention without limiting it in any manner. All percentages are by weight unless otherwise indicated.
EXAMPLES
General procedure for the silylation of the polyhydroxyl compounds:
One OH equivalent of a polyhydroxyl compound and 0.7 moles of hexamethyl disilazane were stirred with the addition of 2 ml o trimethyl chlorosilane at 80 to 120C until the elimination of ammonia was complete. The progress of the reaction was followed by IR spectroscopy by observing the disappearance of the OH band. When the OH band was no longer visible, excess disilazane was removed by distillation under reduced pressure.
In Examples 1 to 5 below, the silylated polyhydroxyl compounds b) were always initially introduced into a suitable reaction vessel and the isocyanatocarboxylic acid chloride a) was subsequently added with stirring under the described reaction conditions.
Prepolymer based on a silylated polyether:
1073 9 of the bis-trimethylsiloxypolyether of a polypropylene glycol having an OH number of 56 and a viscosity of 300 mPa.s (22C) and 175~5 g 6-isocyanatocaproic acid chloride were stirred with addition of 1 ml pyridine at 80 to 100C until the IR spectrum showed no acid chloride band. The trimethyl chlorosilane which was formed was continuously distilled off during the reaction. After the removal of residues of volatile constituents by thin-layer distillation at 140C/0.05 mbar, an NCO prepolymer having the following characteristic data was obtained:
NCO content: 3.34%
Viscosity at 22C: 480 mPa.s Prepolymer based on a silylated polyester carbonate:
Mo3350 '~,' 1073 g of the bis-trimethylsiloxypolyester carbonate [polyester carbonate diol: prepared in accordance with DE-AS 1 770 245 (U.S. Patent 3,6407967) from 1,6-hexanediol, ~-caprolactone and diphenyl carbonate in a molar ratio of approximately 8:8.7, OH value = 56, viscosity at 22C = 20,000 mPa.s] were reacted as in Example 1 with 175.5 g 6-isocyanatocaproic acid chloride. After the removal of residues of volatile constituents by thin-layer distillation, an NCO prepolymer was obtained having the following o characteristic data:
NCO content: 3.2%
Viscosity at 22C: 20,000 mPa.s Prepolymer based on a silylated polyester:
1373 g of the bis-trimethylsiloxypolyester of adipic acid and diethylene glycol (polyesterdiol: OH value = 43, viscosity at 22C = 15,000 mPa.s) were reacted as in Example 1 with 175.5 g 6-isocyanatocaproic acid chloride. After the removal of residues of volatile constituents by thin-layer distillation, an NCO prepolymer was obtained having the following characteristic data:
NCO content: 2.1%
Viscosity at 22C: 30,000 mPa.s Prepolymer based on a silylated polyether containing urethane groups:
1725 g of an OH-functional prepolymer prepared from 4 moles of the polyether of Example 1 and 1 mole of 2,4-toluylene diisocyanate (viscosity at 22C = 3,000 mPa.s) was completely silylated and then reacted as in Example 1 with 175.5 g 6-isocyanatocaproic acid chloride. After the removal of residues of volatile constituents by thin-layer distillation, an NCO prepolymer having the following characteristic data was obtained:
35 NCO content: 1.9%
Mo3350 ~5~3 Viscosity at 22C: 4,700 mPa.s.
Prepolymer based on a silylated polyether:
1073 g of the tris-trimethylsiloxypolyether of trimethylol 5 propane and propylene oxide (polyether triol: OH value = 56, viscosity at 22C = 650 mPa.s) and 175.5 9 6-isocyanatocaproic acid chlor-ide were reacted as in Example 1. After the removal of residues of volatile constituents by thin-layer distillation, an NCO prepolymer having the ~ollowing o characteristic data was obtained:
NCO content: 3.45%
Viscosity at 22C: 650 mPa.s EXAMPLE 6 - Comparison Example 1000 9 of the polyester carbonate of Example 2 were reacted with 168 g hexamethylene diisocyanate at 80C until the NCO content was constant. The NCO prepolymer obtained had an NCO content of 3.5%, a viscosity of 500,000 mPa.s at 22C and a monomer content of 3.1%. The high viscosity of the prepolymer made thin-layer distillation impossible.
20 EXAMPLE 7 - Comparison Example 840 g hexamethylene diisocyanate were introduced into a suitable reaction vessel. 1000 9 of the polyester carbonate of Example 2 were gradually added at 80C with continued stirring.
The reaction mixture was then stirred at 80C until the NCO
25 content was constant. Free diisocyanate present after completion of the reaction was then removed by thin-layer distillation at 130C/0.05 mbar. An NCO prepolymer having the following characteristic data was obtained:
NCO content: 3.4%
30 Monomer content: 0.12%
Viscosity: 70,000 mPa.s EXAMPLE 8 - Comparison Example with DE-OS 2 120 090 (U.S.
Patent 3,870,556) A mixture of 1000 9 of the polyester carbonate of Example 2, 500 ml ethyl acetate and 102 g triethylamine was slowly Mo3350 .
., .3 added dropwise at room temperature to a solution of 175.5 g 6-isocyanatocaproic acid chloride in 300 ml ethyl acetate so that the temperature did not rise above 30C. The mixture was stirred overnight and then filtered off from the ammonium salt 5 precipitated. The filtrate was separated from volatile constituents by thin-layer distillation. The NC0 prepolymer obtained had the following characteristic data:
NC0 content: 3.16%
Viscosity at 22C: 80,000 mPa.s Moisture-hardening coating composition:
A sample of the NC0 prepolymer prepared in accordance with Example 2 was stirred with 0.05% by weight dibutyltin (IV) dilaurate. A film, which was applied to a glass plate, hardened in air in 12 hours. A tough, elastic film having good abrasion resistance was obtained after aging.
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that 20 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.
Mo3350
The process according to the invention provides prepolymers containing ester and isocyanate groups which are similar to those described in DE-OS 2 120 090. According to this prior publication, however, the compounds are prepared by reaction of polyhydroxyl compounds containing free hydroxyl groups with isocyanatocarboxylic acid chlorides in the presence of a hydrogen halide absorber. The disadvantage of this process is in particular the formation of large quantities of salts and the considerably higher viscosities of the resulting NCO prepolymers when compared to the corresponding polyhydroxyl compounds.
_UMMARY OF THE INVENTION
3C The present invention relates to a process for the production of prepolymers containing ester and isocyanate groups by reacting a) isocyanatocarboxylic acid chlorides with b) organic compounds which contain at least two silylated hydroxyl groups, contain only O-silylated hydroxyl groups Mo3350 2 ~
and are otherwise inert to isocyanate and chlorocarbonyl groups under the reaction conditions, and are based on polyhydroxyl compounds having a molecular weight of 400 to about 20,000.
~he present invention also relates to the prepolymers containing ester and isocyanate groups obtained by this process.
DETAILED DESCRIPTION OF THE INVENTION
Suitable isocyanatocarboxylic acid chlorides for use as o component a) in accordance with the present invention are organic compounds which contain at least one isocyanate group and at least one chlorocarbonyl group per molecule and which, apart from the chlorocarbonyl group, are inert to silylated hydroxyl compounds of the type used as component b) under the 15 process conditions. Preferred starting components a) are isocyanatocarboxylic acid chlorides corresponding to the formula Cl-CO-B-NCO
20 wherein B is an organic radical inert to silylated hydroxyl groups, preferably an aliphatic hydrocarbon radical containing 2 to 11 carbon atoms or a cycloaliphatic hydrocarbon radical containing 6 carbon atoms, provided that at least 2 carbon atoms are arranged between the carbonyl group and the isocyanate group.
Examples of suitable isocyanatocarboxylic acid chlorides a) include 3-isocyanatopropionic acid chloride, 4-isocyanatobutyric acid chloride, 6-isocyanatocaproic acid chloride, 12-isocyanatododecanoic acid chloride or 4-isocyanatocyclohexane carboxylic acid chloride.
Other suitable, although less preferred, starting components a) include isocyanatocarboxylic acid chlorides corresponding to the above formula wherein B represents an Mo3350 2 ~ ~ ~#~ ~ 3 aromatic hydrocarbon radical containing 6 to 10 carbon atoms and optionally containing other substituents which are inert under the reaction conditions, especially a phenylene radical.
4-isocyanatobenzoic acid chloride is mentioned as an example of 5 such compounds.
Relatively high molecular weight polyhydroxyl compounds having an average molecular weight of 400 to 20,000 as determined by gel permeation chromatography (molecular weights above 5,000) or from the hydroxyl group content and OH
functionality (molecular weights up to 5,000) in the range from 400 to 20,000, wherein the hydroxyl groups have been completely silylated, are used as component b) in the process according to the invention. The molecular weights mentioned here and also in the following are the molecular weights of the non-silylated 15 polyhydroxyl compounds. Apart from the silylated hydroxyl groups, the starting components b) otherwise contain no groups that are reactive to acid chloride or isocyanate groups under the reaction conditions, e.g., urethane groups, if any, present in the starting compounds b) may be regarded as inert under the 20 reaction conditions.
~ he silylated starting components b) are prepared in accordance with known methods (cf. for example E.M. Lalonde and C.H. Chan, Synthesis (1985), pages 817 to 845) by reacting suitable polyhydroxyl compounds with chlorosilanes or 25 disilazanes corresponding to the formulas R3SiCl and R3Si NH SiR3 wherein in both formulas, R is an alkyl or aryl radical, 30 preferably a C1-C4 alkyl radical or a phenyl radical, more preferably a methyl rad;cal. However, the nature of the radical R is of no relevance to the practicability of the : process according to the invention.
The polyhydroxyl compounds are silylated, for example, by 35 reaction with disilazanes corresponding to the above formula, Mo3350 a ~ 3 in a molar ratio of hydroxyl groups to disilazane of approximately 1:0.7 at a temperature of about 60 to 140C, optionally in the presence of acidic catalysts such as p-toluene sulfonic acid or trimethyl chlorosilane. The 5 reaction is complete when the elimination of ammonia stops.
The reaction may be carried out in suitable inert solvents such as hydrocarbons, ethyl acetate, butyl acetate, methoxypropyl acetate, methyl isobutyl ketone or mixtures of such solvents.
The polyhydroxyl compounds suitable for the preparation of component b) contain at least 2, preferably 2 to lO and more preferably 2 to 4 terminal and/or lateral hydroxyl groups.
Suitable relatively high molecular weight polyols for use as starting materials are known in polyurethane chemistry.
Representatives of such compounds are described, for example, in High Polymers, Vol. XVI, "Polyurethanes, Chemistry and Technology", edited by Saunders-Frisch, Interscience Publishers, New York, London, Vol. I, 1962, pages 32 to 42 and Vol. II, 1964, pages 5-6 and 198-199 and in Kunststoff-Handbuch, Vol. VII, Vieweg-Hochtlen, Carl-Hanser-Verlag, Munchen, 1966, for example on pages 45 to 71.
The polyhydroxyl compounds are preferably polyhydroxyl compounds containing ether, ester, carbonate and/or urethane groups and having a molecular weight of about 800 to 5,000. It is possible to use both polyhydroxyl compounds containing one of the groups mentioned and also polyhydroxyl compounds containing two or more groups mentioned in the same molecule.
It is also possible to use mixtures of different polyhydroxyl compounds of the type mentioned in 0-silylated form.
The polyether polyols suitable for use in accordance with the invention are prepared, for example, by the polymerization of epoxides (such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin) on their own, for example in the presence of Lewis acid catalysts (such as BF3), or by addition of these epoxides (preferably Mo3350 L~ 3 ethylene oxide and propylene oxide, optionally in admixture or successively) onto starter compounds containing reactive hydrogen atoms (such as water, alcohols, ammonia or amines).
Examples of starter compounds include ethylene glycol, 1,3- or 5 1,2-propylene glycol, trimethylol propane, glycerol, sorbitol, 4,4'-dihydroxydiphenyl propane, aniline, ethanolamine or ethylenediamine. Sucrose polyethers of the type described, for example, in DE-AS 1 176 358 and 1 064 938 and formitol- or formose-initiated polyethers (DE-OS 2 639 083 and 2 737 951) o may also be used.
Suitable polyester polyols for use in accordance with the present invention are also known and include reaction products of polyhydric, preferably dihydric and, optionally, trihydric alcohols with polybasic, preferably dibasic, carboxylic acids.
15 Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof for the preparation of the polyesters. The polycarboxylic acids may be aliphatic, cycloaliphatic, aromatic 20 and/or heterocyclic and may optionally be unsaturated or substituted, for example by halogen atoms.
Examples of suitable carboxylic acids and their derivatives include succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, 25 trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylene tetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimerized and trimerized unsaturated fatty acids (optionally in 30 admixture with monomeric unsaturated fatty acids such as oleic acids), terephthalic acid dimethyl ester and terephthalic acid-bis-glycol ester. Suitable polyhydric alcohols include ethylene glycol, 1,2- and 1,3-propylene glycol, 1,4- and 2,3-butylene glycol, 1,6-hexanediol, 1,8-octanediol, neopentyl 35 glycol, 1,4-bis-hydroxymethyl cyclohexane, Mo3350 2 ~ ~ 3 2-methyl-1,3-propanediol, glycerol, trimethylol propane, 1,2,6-hexanetriol, 1,2,4-butanetriol, trimethylol ethane, pentaerythritol, quinito'l, mannitol and sorbitol, formitol, methyl glycoside, diethylene glycol, triethylene glycol, 5 tetraethylene glycol and higher MW polyethylene glycols, dipropylene glycol and higher MW polypropylene glycols and also dibutylene glycol and higher MW polybutylene glycols.
Polyesters of lactones such as ~-capro'lactone, or hydroxycarboxylic acids such as ~-hydroxycaproic acid, may also be used.
Suitable polycarbonates containing hydroxyl groups are known and may be obtained, for example, by reacting diols such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol and/or 15 thiodiglycol with phosgene or diaryl carbonates such as diphenyl carbonate (DE-AS 1 694 080, 1 915 908 and 2 221 751;
DE-OS 2 605 024~.
Polyester polycarbonates containing hydroxyl groups and obtained, for exampl'e, in accordance with DE-AS 1 770 245 are 20 also suitable. These compounds are prepared by reacting ~-caprolactone with polyols such as 1,6-hexanediol and subsequent reaction of the resulting ester glycols with diphenyl carbonate.
Suitable polyurethane polyols for use in accordance with 25 the invention are prepared by reacting such relatively high molecular weight polyhydroxyl compounds or low molecular weight polyols such as ethylene glycol, 1,2- and 1,3-propylene glycol, 1,4- and 2,3-butylene glycol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, l,4-bis-hydroxymethyl cyclohexane, 30 2-methyl-1,3-propanediol, glycerol, trimethylol propane, diethylene glycol, dipropylene glycol, or mixtures of low molecular weight and relatively high molecular weight polyols with polyisocyanates such as 2,4- and/or 2,6-toluylene diisocyanate, diphenyl methane-2,4'- and/or -4,4'-diisocyanate, Mo3350 2 ~ 3 1,6-hexamethylene diisocyanate, cyclohexane-1,3- and/or -1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanato-methyl cyclohexane (isophorone diisocyanate), 4,4'-dicyclohexyl methane diisocyanate and/or adducts of the above-mentioned 5 polyisocyanates containing biuret or isocyanurate groups. The quantitative ratio of polyhydroxyl compound to polyisocyanate is selected so that the hydroxyl groups are present in a stoichiometric excess to the isocyanate groups.
Tne preferred starting components b) are those corresponding to the formula A[-O-SiR3]n 5 wherein n is an integer of 2 or greater, A is an organic radical of the type obtained by removing the hydroxyl groups from a polyhydroxyl compound having a molecular weight of 400 to about 20,000 and 0 R is a C1-C4 alkyl radical or a phenyl radical.
Particularly preferred compounds b) are those corresponding to the above formula wherein A is a radical of the type obtained by removing the hydroxyl groups from a polyhydric alcohol containing ether, ester, carbonate and/or urethane groups and having a molecular weight of about 800 to 5,000 and n is an integer from 2 to 10.
In the practical application of the process, the quantitative ratios between the reactants are selected so that the molar ratio of chlorocarbonyl groups to silylated hydroxyl groups is at least 1:1.2, preferably 1:0.8 to 1:1.2. The starting materials are preferably used in equimolar quantities, although it is also possible to use a large excess of isocyanatocarboxylic acid chloride and to remove the unreacted Mo3350 excess, for example by distillation, on completion of the reaction. ~lowever, this procedure is not preferred.
The reaction of the silylated hydroxyl compounds with isocyanatocarboxylic acid chlorides generally takes place at temperatures of about 50 to 150C, optionally in the presence of known catalysts for this reaction such as quinoline or pyridine.
A trialkyl or triaryl chlorosilane is formed as the secondary product of the reaction according to the invention and may be conveniently removed from the reaction mixture by distillation.
The reaction may be carried out in the presence or absence of solvents. Suitable solvents are those which do not contain any active hydrogen atoms and include aliphatic, cycloaliphatic 15 and aromatic hydrocarbons; ethers; ketones; and esters. There is generally no need to use a solvent if the silylated hydroxyl compounds used have a sufficiently low viscosity for carrying out the process according to the invention.
In order to obtain substantially solvent-free 20 polyisocyanate prepolymers, particular preference is attributed to the procedure where no solvents are used. Residues of volatile constituents may be removed from the prepolymers by thin-layer distillation.
The polyisocyanate prepolymers thus obtained are 25 distinguished by the absence of monomers and by unusually low viscosities.
The polyisocyanate prepolymers produced in accordance with the invention are particularly suitable starting materials for the formulation of solventless or low-solvent coating 30 compositions or sealing compounds. The prepolymers may be cured by atmospheric moisture (optionally after the addition of known catalysts such as dibutyltin (IV) dilaurate, and optionally the known pigments, fillers and auxiliaries used in coating technology) to provide polymer films having excellent 3 5 mechanical properties.
Mo3350 The following examples are intended to illustrate the process according to the invention without limiting it in any manner. All percentages are by weight unless otherwise indicated.
EXAMPLES
General procedure for the silylation of the polyhydroxyl compounds:
One OH equivalent of a polyhydroxyl compound and 0.7 moles of hexamethyl disilazane were stirred with the addition of 2 ml o trimethyl chlorosilane at 80 to 120C until the elimination of ammonia was complete. The progress of the reaction was followed by IR spectroscopy by observing the disappearance of the OH band. When the OH band was no longer visible, excess disilazane was removed by distillation under reduced pressure.
In Examples 1 to 5 below, the silylated polyhydroxyl compounds b) were always initially introduced into a suitable reaction vessel and the isocyanatocarboxylic acid chloride a) was subsequently added with stirring under the described reaction conditions.
Prepolymer based on a silylated polyether:
1073 9 of the bis-trimethylsiloxypolyether of a polypropylene glycol having an OH number of 56 and a viscosity of 300 mPa.s (22C) and 175~5 g 6-isocyanatocaproic acid chloride were stirred with addition of 1 ml pyridine at 80 to 100C until the IR spectrum showed no acid chloride band. The trimethyl chlorosilane which was formed was continuously distilled off during the reaction. After the removal of residues of volatile constituents by thin-layer distillation at 140C/0.05 mbar, an NCO prepolymer having the following characteristic data was obtained:
NCO content: 3.34%
Viscosity at 22C: 480 mPa.s Prepolymer based on a silylated polyester carbonate:
Mo3350 '~,' 1073 g of the bis-trimethylsiloxypolyester carbonate [polyester carbonate diol: prepared in accordance with DE-AS 1 770 245 (U.S. Patent 3,6407967) from 1,6-hexanediol, ~-caprolactone and diphenyl carbonate in a molar ratio of approximately 8:8.7, OH value = 56, viscosity at 22C = 20,000 mPa.s] were reacted as in Example 1 with 175.5 g 6-isocyanatocaproic acid chloride. After the removal of residues of volatile constituents by thin-layer distillation, an NCO prepolymer was obtained having the following o characteristic data:
NCO content: 3.2%
Viscosity at 22C: 20,000 mPa.s Prepolymer based on a silylated polyester:
1373 g of the bis-trimethylsiloxypolyester of adipic acid and diethylene glycol (polyesterdiol: OH value = 43, viscosity at 22C = 15,000 mPa.s) were reacted as in Example 1 with 175.5 g 6-isocyanatocaproic acid chloride. After the removal of residues of volatile constituents by thin-layer distillation, an NCO prepolymer was obtained having the following characteristic data:
NCO content: 2.1%
Viscosity at 22C: 30,000 mPa.s Prepolymer based on a silylated polyether containing urethane groups:
1725 g of an OH-functional prepolymer prepared from 4 moles of the polyether of Example 1 and 1 mole of 2,4-toluylene diisocyanate (viscosity at 22C = 3,000 mPa.s) was completely silylated and then reacted as in Example 1 with 175.5 g 6-isocyanatocaproic acid chloride. After the removal of residues of volatile constituents by thin-layer distillation, an NCO prepolymer having the following characteristic data was obtained:
35 NCO content: 1.9%
Mo3350 ~5~3 Viscosity at 22C: 4,700 mPa.s.
Prepolymer based on a silylated polyether:
1073 g of the tris-trimethylsiloxypolyether of trimethylol 5 propane and propylene oxide (polyether triol: OH value = 56, viscosity at 22C = 650 mPa.s) and 175.5 9 6-isocyanatocaproic acid chlor-ide were reacted as in Example 1. After the removal of residues of volatile constituents by thin-layer distillation, an NCO prepolymer having the ~ollowing o characteristic data was obtained:
NCO content: 3.45%
Viscosity at 22C: 650 mPa.s EXAMPLE 6 - Comparison Example 1000 9 of the polyester carbonate of Example 2 were reacted with 168 g hexamethylene diisocyanate at 80C until the NCO content was constant. The NCO prepolymer obtained had an NCO content of 3.5%, a viscosity of 500,000 mPa.s at 22C and a monomer content of 3.1%. The high viscosity of the prepolymer made thin-layer distillation impossible.
20 EXAMPLE 7 - Comparison Example 840 g hexamethylene diisocyanate were introduced into a suitable reaction vessel. 1000 9 of the polyester carbonate of Example 2 were gradually added at 80C with continued stirring.
The reaction mixture was then stirred at 80C until the NCO
25 content was constant. Free diisocyanate present after completion of the reaction was then removed by thin-layer distillation at 130C/0.05 mbar. An NCO prepolymer having the following characteristic data was obtained:
NCO content: 3.4%
30 Monomer content: 0.12%
Viscosity: 70,000 mPa.s EXAMPLE 8 - Comparison Example with DE-OS 2 120 090 (U.S.
Patent 3,870,556) A mixture of 1000 9 of the polyester carbonate of Example 2, 500 ml ethyl acetate and 102 g triethylamine was slowly Mo3350 .
., .3 added dropwise at room temperature to a solution of 175.5 g 6-isocyanatocaproic acid chloride in 300 ml ethyl acetate so that the temperature did not rise above 30C. The mixture was stirred overnight and then filtered off from the ammonium salt 5 precipitated. The filtrate was separated from volatile constituents by thin-layer distillation. The NC0 prepolymer obtained had the following characteristic data:
NC0 content: 3.16%
Viscosity at 22C: 80,000 mPa.s Moisture-hardening coating composition:
A sample of the NC0 prepolymer prepared in accordance with Example 2 was stirred with 0.05% by weight dibutyltin (IV) dilaurate. A film, which was applied to a glass plate, hardened in air in 12 hours. A tough, elastic film having good abrasion resistance was obtained after aging.
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that 20 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.
Mo3350
Claims (18)
1. A process for the production of a prepolymer containing ester and isocyanate groups which comprises reacting a) an isocyanatocarboxylic acid chloride with b) an organic compound which contains at least two silylated hydroxyl groups, contains only O-silylated hydroxyl groups and is otherwise inert to isocyanate and chlorocarbonyl groups under the reaction conditions, and is based on a polyhydroxyl compound having a molecular weight of 400 to about 20,000.
2. The process of Claim 1 wherein said organic compound corresponds to the formula A-[-O-SiR3]
wherein n is an integer of 2 or greater, A is an organic radical obtained by removing the hydroxyl groups from an n-functional polyhydroxyl compound and R is a C1-C4 alkyl radical or a phenyl radical.
wherein n is an integer of 2 or greater, A is an organic radical obtained by removing the hydroxyl groups from an n-functional polyhydroxyl compound and R is a C1-C4 alkyl radical or a phenyl radical.
3. The process Claim 2 wherein A is an organic radical obtained by removing the hydroxyl groups from an n-functional polyhydroxyl compound containing ether, ester, carbonate and/or urethane groups and having a molecular weight of about 800 to 5,000.
4. The process of Claim 2 wherein n is an integer from 2 to 10.
5. The process of Claim 3 wherein n is an integer from 2 to 10.
6. The process of Claim 1 wherein said isocyanatocarboxylic acid chloride corresponds to the formula Cl-CO-B-NCO
wherein Mo3350 B is an organic radical which is inert to component b) under the reaction conditions.
wherein Mo3350 B is an organic radical which is inert to component b) under the reaction conditions.
7. The process of Claim 3 wherein said isocyanatocarboxylic acid chloride corresponds to the formula Cl-CO-B-NCO
wherein B is an organic radical which is inert to component b) under the reaction conditions.
wherein B is an organic radical which is inert to component b) under the reaction conditions.
8. The process of Claim 6 wherein B is an aliphatic hydrocarbon radical containing from 2 to 11 carbon atoms or a cycloaliphatic hydrocarbon radical containing 6 carbon atoms.
9. The process of Claim 7 wherein B is an aliphatic hydrocarbon radical containing from 2 to 11 carbon atoms or a cycloaliphatic hydrocarbon radical containing 6 carbon atoms.
10. A prepolymer containing ester and isocyanate groups which is prepared by a process which comprises reacting a) an isocyanatocarboxylic acid chloride with b) an organic compound which contains at least two silylated hydroxyl groups, contains only 0-silylated hydroxyl groups and is otnerwise inert to isocyanate and chlorocarbonyl groups under the reaction conditions, and is based on a polyhydroxyl compound having a molecular weight of 400 to about 20,000.
11. The prepolymer of Claim 10 wherein said organic compound corresponds to the formula A-[-O-SiR3]n wherein n is an integer of 2 or greater, A is an organic radical obtained by removing the hydroxyl groups from an n-functional polyhydroxyl compound and R is a C1-C4 alkyl radical or a phenyl radical.
Mo3350
Mo3350
12. The prepolymer Claim 11 wherein A is an organic radical obtained by removing the hydroxyl groups from an n-functional polyhydroxyl compound containing ether, ester, carbonate and/or urethane groups and having a molecular weight of about 800 to 5,000.
13. The prepolymer of Claim 11 wherein n is an integer from 2 to 10.
14. The prepolymer of Claim 12 wherein n is an integer from 2 to 10.
15. The prepolymer of Claim 10 wherein said isocyanatocarboxylic acid chloride corresponds to the formula Cl-CO-B-NCO
wherein B is an organic radical which is inert to component b) under the reaction conditions.
wherein B is an organic radical which is inert to component b) under the reaction conditions.
16. The prepolymer of Claim 12 wherein said isocyanatocarboxylic acid chloride corresponds to the formula Cl-CO-B-NCO
wherein B is an organic radical which is inert to component b) under the reaction conditions.
wherein B is an organic radical which is inert to component b) under the reaction conditions.
17. The prepolymer of Claim 15 wherein B is an aliphatic hydrocarbon radical containing from 2 to 11 carbon atoms or a cycloaliphatic hydrocarbon radical containing 6 carbon atoms.
18. The prepolymer of Claim 16 wherein B is an aliphatic hydrocarbon radical containing from 2 to 11 carbon atoms or a cycloaliphatic hydrocarbon radical containing 6 carbon atoms.
Mo3350
Mo3350
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3913406 | 1989-04-24 | ||
| DEP3913406.7 | 1989-04-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2015043A1 true CA2015043A1 (en) | 1990-10-24 |
Family
ID=6379313
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2015043 Abandoned CA2015043A1 (en) | 1989-04-24 | 1990-04-20 | Prepolymers containing ester and isocyanate groups and a process for their production |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0394759A1 (en) |
| JP (1) | JPH02300225A (en) |
| BR (1) | BR9001868A (en) |
| CA (1) | CA2015043A1 (en) |
| DD (1) | DD297981A5 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102006015280A1 (en) * | 2006-03-18 | 2007-09-20 | Bayer Materialscience Ag | Preparation of storage-stable, isocyanate-functional prepolymers using NCO-functional carboxylic acid and carbamoyl halides |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1668069A1 (en) * | 1968-01-02 | 1971-07-15 | Bayer Ag | Process for the preparation of isocyanatoarylcarboxylic acid esters |
| DE2120090A1 (en) * | 1971-04-24 | 1972-11-09 | Bayer Ag | New auxiliary materials for finishing textiles containing keratin fibers |
| DE3634248A1 (en) * | 1986-10-08 | 1988-04-21 | Bayer Ag | METHOD FOR PRODUCING ISOCYANATES |
-
1990
- 1990-04-11 EP EP90106979A patent/EP0394759A1/en not_active Withdrawn
- 1990-04-20 CA CA 2015043 patent/CA2015043A1/en not_active Abandoned
- 1990-04-23 DD DD33999890A patent/DD297981A5/en not_active IP Right Cessation
- 1990-04-23 BR BR9001868A patent/BR9001868A/en unknown
- 1990-04-23 JP JP10549090A patent/JPH02300225A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0394759A1 (en) | 1990-10-31 |
| DD297981A5 (en) | 1992-01-30 |
| JPH02300225A (en) | 1990-12-12 |
| BR9001868A (en) | 1991-06-18 |
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