CA2339737A1 - Method for producing vinyl compounds - Google Patents
Method for producing vinyl compounds Download PDFInfo
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- CA2339737A1 CA2339737A1 CA002339737A CA2339737A CA2339737A1 CA 2339737 A1 CA2339737 A1 CA 2339737A1 CA 002339737 A CA002339737 A CA 002339737A CA 2339737 A CA2339737 A CA 2339737A CA 2339737 A1 CA2339737 A1 CA 2339737A1
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- vinyl
- compound
- compounds
- aminovinyl
- groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
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- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Epoxy Resins (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention relates to a method for producing vinyl compounds, especially vinyl ether compounds, whereby amino vinyl compounds are reacted, while retaining their vinyl groups, with substances that react with said amino vinyl compounds. The invention also relates to vinyl compounds that can be produced according to said method, preparations containing said vinyl compounds, the use of said compounds and the use of amino vinyl compounds in the production of vinyl compounds.
Description
METHOD FOR PRODUCING VINYL COMPOUNDS
The invention relates to a process for preparing vinyl compounds, especially vinyl ether compounds, to vinyl compounds preparable by this process, to formulations comprising them and to their use.
Compounds containing vinyl groups have developed into important, key products in industrial chemistry owing to their particular reactivity and diverse possibilities for use. Consequently, there exists a large number of processes for preparing substances and mixtures of substances which contain vinyl groups.
Because of the diverse possibilities for use of vinyl-containing compounds there is great interest in new kinds of vinyl compounds which can be used to give products having new and/or improved properties.
It is an object of the present invention to provide a Process for preparing novel vinyl compounds, vinyl compounds preparable by such a process, formulations comprising such vinyl compounds, and for the use of these vinyl compounds or of formulations comprising them.
We have found that this object is achieved by a process for preparing vinyl compounds where aminovinyl compounds are reacted, but maintain their vinyl groups, with substances reactive with the aminovinyl compounds.
By aminovinyl compounds here are meant compounds containin at least one nitro en-basic g g group and at least one vinyl group in the molecule . The vinyl group in these compounds is generally not linked directly to the amino group.
The vinyl compounds preparable by the process of the invention feature extremely high sensitivity to W
light. When compounds of the invention or formulations comprising them are cured there is no oxygen inhibition of the surface.
The reaction of the aminovinyl compounds with substances reactive with them takes place at the amino group or groups. This means that the aminovinyl compounds are able to react singly or multiply with substances reactive with the nitrogen-basic group of the aminovinyl compounds. The resultant bonds may be ionic bonds, covalent bonds or forms intermediate between ionic and covalent bonds. The formation of covalent bonds is preferred.
The aminovinyl compounds may have further reactive groups. The reaction with substances reactive with the aminovinyl compounds may therefore take place at the amino group or groups and/or at the reactive groups.
It is therefore possible to obtain compounds which may carry numerous functional groups and may be employed in a large number of industrial fields.
The aminovinyl compounds employed in the process of the invention are preferably aminovinyl ether compounds.
Such compounds may contain one or more vinyl ether groups.
The vinyl ether compounds are compounds which in addition to at least one nitrogen-basic group have at least one vinyl ether group in the molecule. In general they include vinyl ethers of primary, secondary and tertiary alkanolamines, of cycloalkanolamines, of arylalkanolamines and open-chain and cyclic amides.
The invention relates to a process for preparing vinyl compounds, especially vinyl ether compounds, to vinyl compounds preparable by this process, to formulations comprising them and to their use.
Compounds containing vinyl groups have developed into important, key products in industrial chemistry owing to their particular reactivity and diverse possibilities for use. Consequently, there exists a large number of processes for preparing substances and mixtures of substances which contain vinyl groups.
Because of the diverse possibilities for use of vinyl-containing compounds there is great interest in new kinds of vinyl compounds which can be used to give products having new and/or improved properties.
It is an object of the present invention to provide a Process for preparing novel vinyl compounds, vinyl compounds preparable by such a process, formulations comprising such vinyl compounds, and for the use of these vinyl compounds or of formulations comprising them.
We have found that this object is achieved by a process for preparing vinyl compounds where aminovinyl compounds are reacted, but maintain their vinyl groups, with substances reactive with the aminovinyl compounds.
By aminovinyl compounds here are meant compounds containin at least one nitro en-basic g g group and at least one vinyl group in the molecule . The vinyl group in these compounds is generally not linked directly to the amino group.
The vinyl compounds preparable by the process of the invention feature extremely high sensitivity to W
light. When compounds of the invention or formulations comprising them are cured there is no oxygen inhibition of the surface.
The reaction of the aminovinyl compounds with substances reactive with them takes place at the amino group or groups. This means that the aminovinyl compounds are able to react singly or multiply with substances reactive with the nitrogen-basic group of the aminovinyl compounds. The resultant bonds may be ionic bonds, covalent bonds or forms intermediate between ionic and covalent bonds. The formation of covalent bonds is preferred.
The aminovinyl compounds may have further reactive groups. The reaction with substances reactive with the aminovinyl compounds may therefore take place at the amino group or groups and/or at the reactive groups.
It is therefore possible to obtain compounds which may carry numerous functional groups and may be employed in a large number of industrial fields.
The aminovinyl compounds employed in the process of the invention are preferably aminovinyl ether compounds.
Such compounds may contain one or more vinyl ether groups.
The vinyl ether compounds are compounds which in addition to at least one nitrogen-basic group have at least one vinyl ether group in the molecule. In general they include vinyl ethers of primary, secondary and tertiary alkanolamines, of cycloalkanolamines, of arylalkanolamines and open-chain and cyclic amides.
Particular preference is given to the use of aminopropyl vinyl ether, and ethyleneurea monovinyl ether and very particular preference to the use of diethanolamine divinyl ether.
Through the process of the invention the vinyl compounds can be prepared in the form of monomers, oligomers, polymers or mixtures thereof. As a result it is possible to prepare suitable vinyl compounds in accordance with the field of use.
Preferably, the aminovinyl compounds are reacted with substances containing functional groups selected from epoxide groups, isocyanate groups, carboxyl groups, carbonyl groups, halogens and groups able to enter into a Michael reaction with the amino groups.
These substances may be in monomeric or polymeric form and one or more functional groups may be present.
Preferred epoxy substances are known and commercially available epoxy monomers and epoxy resins such as, for example, of the bisphenyl A type (e. g. Araldite, Epicote) and copolymers incorporating glycidyl (meth)acrylate monomers.
In the reaction of the aminovinyl compounds with the epoxy compounds it is possible in order to establish desired properties to allow further substances, such as carboxyl compounds, amino compounds without vinyl groups, aromatic and/or aliphatic hydroxy compounds, to react as well. The sequence of the reaction is open in such cases and in specific cases must be decided on in accordance with rules known to the skilled worker. For example, if carboxyl compounds are to be reacted, it is judicious to react the carboxyl compound first with the epoxy compound in order to avoid the formation of salts between carboxyl and aminovinyl compounds and in order to avoid acid-catalyzed polmerizations.
Through the process of the invention the vinyl compounds can be prepared in the form of monomers, oligomers, polymers or mixtures thereof. As a result it is possible to prepare suitable vinyl compounds in accordance with the field of use.
Preferably, the aminovinyl compounds are reacted with substances containing functional groups selected from epoxide groups, isocyanate groups, carboxyl groups, carbonyl groups, halogens and groups able to enter into a Michael reaction with the amino groups.
These substances may be in monomeric or polymeric form and one or more functional groups may be present.
Preferred epoxy substances are known and commercially available epoxy monomers and epoxy resins such as, for example, of the bisphenyl A type (e. g. Araldite, Epicote) and copolymers incorporating glycidyl (meth)acrylate monomers.
In the reaction of the aminovinyl compounds with the epoxy compounds it is possible in order to establish desired properties to allow further substances, such as carboxyl compounds, amino compounds without vinyl groups, aromatic and/or aliphatic hydroxy compounds, to react as well. The sequence of the reaction is open in such cases and in specific cases must be decided on in accordance with rules known to the skilled worker. For example, if carboxyl compounds are to be reacted, it is judicious to react the carboxyl compound first with the epoxy compound in order to avoid the formation of salts between carboxyl and aminovinyl compounds and in order to avoid acid-catalyzed polmerizations.
Preferred isocyanate substances are known and commercially available polyfunctional isocyanates.
In these cases too, it is possible in addition to add substances reactive with the isocyanates. Examples are mono- and polyfunctional hydroxyl compounds and/or their alkoxylation products, and mono- and polyfunctional amino compounds. As a result it is possible to utilize the known polyurethane chemistry in order to obtain novel, highly reactive vinylurethane compounds.
Preferred carboxyl substances are monofunctional and polyfunctional monomeric and polymeric carboxylic acids or their anhyrides. They are, for example, linear, branched substituted and unsubstituted aromatic and cycloaliphatic carboxylic acids or anhyrides thereof, and various fatty acids deriving from natural oils and fats, such as linseed oil fatty acid, polymerized linseed oil fatty acid, oleic acid and tall oil fatty acid.
Substances of particular industrial interest are those which are derived from acidic polyesters and can be functionalized with aminovinyl compounds. In this way it is possible to obtain highly reactive, vinyl-modified substances. The synthesis of suitable polyesters, and the control of the basic properties, are known to the skilled worker. In this context, the aminovinyl compounds can be added to the polyesters right at the beginning of the polycondensation. It is preferred first to carry out the polycondensation to give the acidic polyesters and then to react the aminovinyl compounds with said polyesters.
It is also possible to employ polycarboxylic acids, such as (meth)acrylate polymers with fractions of polymerizable carboxylic acids, such as (meth)acrylic acid, malefic acid, et cetera. In this way, polyacrylate binders of extremely high UV activity can be obtained.
In the case of the reactions of aminovinyl compounds, 5 especially aminovinyl ethers, with carboxyl substances it is preferred to initially introduce the aminovinyl ether compound and then to add the acidic carboxyl substance in a stoichiometric amount.
By initial introduction of the aminovinyl ether compound is meant that the total amount of the aminovinyl ether compound to be reacted is introduced before the beginning of the reaction (= initially introduced) into an appropriate apparatus. The carboxyl substance is added gradually to the total amount of aminovinyl ether compound. This procedure, and the addition of a stoichimetric amount of the carboxyl substance, prevents acid-catalyzed polymerization of the aminovinyl ether compound.
The carboxyl groups can be attached to the aminovinyl compounds by way of a condensation reaction (amide groups) and/or by way of an ionic bond (by protonation).
Carbonyl substances employed with preference are derived from polyfunctional keto compounds. Examples of these are copolymers of carbon monoxide and ethylene, or acrylate polymers with carbonyl comonomers, such as diacetoneacrylamide. Primary or secondary aminovinyl compounds can be added on to these keto polymers to form ketals.
If the aminovinyl compounds are reacted with substances containing halogens as reactive groups, then the attachment of the halogen substances to the aminovinyl compounds can take place by way of a covalent bond and/or by way of an ionic bond.
In these cases too, it is possible in addition to add substances reactive with the isocyanates. Examples are mono- and polyfunctional hydroxyl compounds and/or their alkoxylation products, and mono- and polyfunctional amino compounds. As a result it is possible to utilize the known polyurethane chemistry in order to obtain novel, highly reactive vinylurethane compounds.
Preferred carboxyl substances are monofunctional and polyfunctional monomeric and polymeric carboxylic acids or their anhyrides. They are, for example, linear, branched substituted and unsubstituted aromatic and cycloaliphatic carboxylic acids or anhyrides thereof, and various fatty acids deriving from natural oils and fats, such as linseed oil fatty acid, polymerized linseed oil fatty acid, oleic acid and tall oil fatty acid.
Substances of particular industrial interest are those which are derived from acidic polyesters and can be functionalized with aminovinyl compounds. In this way it is possible to obtain highly reactive, vinyl-modified substances. The synthesis of suitable polyesters, and the control of the basic properties, are known to the skilled worker. In this context, the aminovinyl compounds can be added to the polyesters right at the beginning of the polycondensation. It is preferred first to carry out the polycondensation to give the acidic polyesters and then to react the aminovinyl compounds with said polyesters.
It is also possible to employ polycarboxylic acids, such as (meth)acrylate polymers with fractions of polymerizable carboxylic acids, such as (meth)acrylic acid, malefic acid, et cetera. In this way, polyacrylate binders of extremely high UV activity can be obtained.
In the case of the reactions of aminovinyl compounds, 5 especially aminovinyl ethers, with carboxyl substances it is preferred to initially introduce the aminovinyl ether compound and then to add the acidic carboxyl substance in a stoichiometric amount.
By initial introduction of the aminovinyl ether compound is meant that the total amount of the aminovinyl ether compound to be reacted is introduced before the beginning of the reaction (= initially introduced) into an appropriate apparatus. The carboxyl substance is added gradually to the total amount of aminovinyl ether compound. This procedure, and the addition of a stoichimetric amount of the carboxyl substance, prevents acid-catalyzed polymerization of the aminovinyl ether compound.
The carboxyl groups can be attached to the aminovinyl compounds by way of a condensation reaction (amide groups) and/or by way of an ionic bond (by protonation).
Carbonyl substances employed with preference are derived from polyfunctional keto compounds. Examples of these are copolymers of carbon monoxide and ethylene, or acrylate polymers with carbonyl comonomers, such as diacetoneacrylamide. Primary or secondary aminovinyl compounds can be added on to these keto polymers to form ketals.
If the aminovinyl compounds are reacted with substances containing halogens as reactive groups, then the attachment of the halogen substances to the aminovinyl compounds can take place by way of a covalent bond and/or by way of an ionic bond.
The reaction of the aminovinyl compounds with substances reactive with them takes place preferably by adding the aminovinyl compound to the corresponding reactive substances or mixtures of substances at a temperature of in general from 25 to 250°C, preferably from 50 to 150°C and, with particular preference, from 60 to 90°C.
Following the addition of the aminovinyl compound stirring is continued at a temperature of in general from 25 to 250°C, preferably from 50 to 200°C, with particular preference from 80 to 100°C and, with very particular preference, at 100°C for in general from 2 to 20 hours, preferably from 4 to 8 hours and, with particular preference, from 5 to 6 hours.
It is a further object of the present invention to provide compounds preparable by the process of the invention and formulations comprising them.
The present invention therefore additionally provides vinyl compounds preparable by the process described, using aminovinyl compounds, and formulations which comprise at least one such vinyl compound.
The vinyl substances of the invention are curable by cationic polymerization and/or, if further copolymerizable double bonds are present, by free-radical polymerization with the addition of appropriate initiators. For the purposes of this invention curing means the crosslinking of the vinyl substances of the invention.
The present invention therefore additionally provides formulations which in addition to the vinyl compounds of the invention comprise further ionic and/or free-radically co-reactive substances selected from monomeric, oligomeric and/or polymeric epoxy, allyl, (meth)acrylic and/or vinyl ether compounds.
Following the addition of the aminovinyl compound stirring is continued at a temperature of in general from 25 to 250°C, preferably from 50 to 200°C, with particular preference from 80 to 100°C and, with very particular preference, at 100°C for in general from 2 to 20 hours, preferably from 4 to 8 hours and, with particular preference, from 5 to 6 hours.
It is a further object of the present invention to provide compounds preparable by the process of the invention and formulations comprising them.
The present invention therefore additionally provides vinyl compounds preparable by the process described, using aminovinyl compounds, and formulations which comprise at least one such vinyl compound.
The vinyl substances of the invention are curable by cationic polymerization and/or, if further copolymerizable double bonds are present, by free-radical polymerization with the addition of appropriate initiators. For the purposes of this invention curing means the crosslinking of the vinyl substances of the invention.
The present invention therefore additionally provides formulations which in addition to the vinyl compounds of the invention comprise further ionic and/or free-radically co-reactive substances selected from monomeric, oligomeric and/or polymeric epoxy, allyl, (meth)acrylic and/or vinyl ether compounds.
The present invention provides, furthermore, for the use of the vinyl compounds or formulations of the invention for free-radically and/or sonically initiated crosslinking or curing.
Cationic polymerization is also possible in combination with free epoxy groups. The cationic initiators can be added to multi-component systems or, preferably, to single-component systems. Particular preference is given to single-component systems in which the cations required for crosslinking are released with the aid of the admixed initiators by means of heat and/or high-energy radiation, e.g. W light.
Free-radical polymerization is possible with substances having copolymerizable double bonds, such as acrylic, allyl, malefic, fumaric and/or itaconic groups.
Particular preference is given to unsaturated polyester resins functionalized with vinyl groups in the manner of the invention. Depending on the polyester components selected and degree of condensation established, these resins can be either in liquid form or in solid form, and constitute outstanding binders, for example, for coating materials including powder coating materials.
Particular preference is given to the free-radical polymerization of the vinyl compounds of the invention in combination with free-radically co-crosslinkable substances. Co-crosslinkable substances employed with preference are unsaturated polyester resins, monofunctionally and polyfunctionally, acrylically or vinylically unsaturated monomers and/or polymers, monofunctional and polyfunctional allyl esters, allyl ethers and vinyl esters.
Preferred free-radical initiators are those employed for thermal and/or UV curing. Suitable initiators for thermal curing are peroxides, azo compounds and C-C-labile substances, of the pinacole type, for example. Suitable initiators for UV curing are photoinitiators of Norrish types I and II.
Furthermore, it is also possible to employ two-stage curing systems in which cationic and free-radical curing are combined.
The substances of the invention are extremely sensitive to UV light, and on irradiation with UV light there is no oxygen inhibition of the surface. After curing they prove to be highly resistant to organic solvents, such as acetone, and exhibit a hard, tack-free surface layer.
The present invention therefore additionally provides for the use of the vinyl compounds of the invention, or of formulations comprising at least one vinyl compound of the invention, in coating materials, adhesives, printing inks and UV-curable or daylight-curable exterior paints, and also in coatings, in potting compounds, casting compositions and impregnants for electronics and electrical engineering, and in fiber-reinforced materials and prepregs.
Preference is given here to 100 systems, which in order to regulate the viscosity, reactivity or properties of the cured substances may include further co-reactive substances, such as reactive diluents, examples being styrene, vinyl toluene, vinyl ethers, vinyl esters, acrylates, allyl ethers and allyl esters.
Also provided by the present invention are sheetlike and/or shaped articles produced using the vinyl compounds of the invention or formulations comprising at least one such vinyl compound.
The following examples additionally illustrate the invention.
Cationic polymerization is also possible in combination with free epoxy groups. The cationic initiators can be added to multi-component systems or, preferably, to single-component systems. Particular preference is given to single-component systems in which the cations required for crosslinking are released with the aid of the admixed initiators by means of heat and/or high-energy radiation, e.g. W light.
Free-radical polymerization is possible with substances having copolymerizable double bonds, such as acrylic, allyl, malefic, fumaric and/or itaconic groups.
Particular preference is given to unsaturated polyester resins functionalized with vinyl groups in the manner of the invention. Depending on the polyester components selected and degree of condensation established, these resins can be either in liquid form or in solid form, and constitute outstanding binders, for example, for coating materials including powder coating materials.
Particular preference is given to the free-radical polymerization of the vinyl compounds of the invention in combination with free-radically co-crosslinkable substances. Co-crosslinkable substances employed with preference are unsaturated polyester resins, monofunctionally and polyfunctionally, acrylically or vinylically unsaturated monomers and/or polymers, monofunctional and polyfunctional allyl esters, allyl ethers and vinyl esters.
Preferred free-radical initiators are those employed for thermal and/or UV curing. Suitable initiators for thermal curing are peroxides, azo compounds and C-C-labile substances, of the pinacole type, for example. Suitable initiators for UV curing are photoinitiators of Norrish types I and II.
Furthermore, it is also possible to employ two-stage curing systems in which cationic and free-radical curing are combined.
The substances of the invention are extremely sensitive to UV light, and on irradiation with UV light there is no oxygen inhibition of the surface. After curing they prove to be highly resistant to organic solvents, such as acetone, and exhibit a hard, tack-free surface layer.
The present invention therefore additionally provides for the use of the vinyl compounds of the invention, or of formulations comprising at least one vinyl compound of the invention, in coating materials, adhesives, printing inks and UV-curable or daylight-curable exterior paints, and also in coatings, in potting compounds, casting compositions and impregnants for electronics and electrical engineering, and in fiber-reinforced materials and prepregs.
Preference is given here to 100 systems, which in order to regulate the viscosity, reactivity or properties of the cured substances may include further co-reactive substances, such as reactive diluents, examples being styrene, vinyl toluene, vinyl ethers, vinyl esters, acrylates, allyl ethers and allyl esters.
Also provided by the present invention are sheetlike and/or shaped articles produced using the vinyl compounds of the invention or formulations comprising at least one such vinyl compound.
The following examples additionally illustrate the invention.
Example 1 Substance of the invention based on epoxy resins.
380 g of bisphenol A glycidol ether (Araldite GY 2600) having an epoxide equivalent weight of 190 are initially introduced into a stirred flask with feed vessel and heating bath and this initial charge is heated to 90°C under a gentle stream of nitrogen. Then 314 g of diethanolamine divinyl ether are added dropwise over one hour and stirring is continued at 100°C for 5 hours. The result of cooling is a viscose yellowish resin.
Example 2 Vinyl compound based on a polyacrylate.
A flask with heating bath, reflux condenser stirred and two feed vessels is charged with 200 g of butyl acetate 50 g of methyl methacrylate g of glycidyl methacrylate 25 20 g ethylhexyl acrylate 1 g of mercaptoethanol (regulator) 2 g of tert-butyl peroctoate (initiator) and this initial charge is heated with stirring to 30 115°C. Then the following feeds are run in simultaneously over one hour.
Feed I: a mixture of 150 g of methyl methacrylate 90 g of glycidyl methacrylate 60 g of ethylhexyl acrylate 3 g of mercapto ethanol (regulator) Feed II: a mixture of 6 g of tert-butyl peroctoate (initiator) 66 g of butyl acetate The mixture is subsequently stirred at 120°C for 3 hours and then cooled to 60°C, after which 5 132 g of diethanolamine divinyl ether 0.8 g of tert-butylcresole 0.8 g of hydroquinone monomethyl ether 0.1 g of phenothiazine are added.
The mixture is then stirred at 100°C for 6 hours. The result is a viscose yellowish resin solution.
Testing of the vinyl compounds:
A 100 g of Laromer PO 33 F (unsaturated acrylate resin from BASF) 30 g of resin of Example 1 3.9 g of benzil dimethyl ketal B 100 g of Laromer PO 33 F (unsaturated acrylate resin from BASF) g of resin of Example 2 3.9 g of benzil dimethyl ketal C Comparative Example 100 g of Laromer PO 33 F (unsaturated acrylate resin from BASF) 3 g of benzil dimethyl ketal The test coating materials were prepared and the test panels produced in a UV-protected laboratory. The components of the test coating materials were premixed in glass flasks with a stirring spatula and these mixtures were stored in a drying cabinet at 50°C for 1 hour and stirred thoroughly again. Cooling to room temperature resulted in all cases in clear, viscose solutions.
The solutions were then drawn down onto degreased bright steel panels using a coater bar having a gap height of 60 mm. The test panels were then irradiated under a mercury vapor W lamp having an emission maximum at about 365 nm and an energy output of 19 mJ/cm2 in the exposure plane until the films were not attacked by 10 minutes of exposure to a cotton pad wetted with acetone. If surface inhibition of the films was observed, a non-crosslinked, acetone-soluble layer present was first of all wiped off and the swellability of the underlying layer was assessed. Surface inhibition means that the layers are acetone-insolubly crosslinked beneath a tacky or tack-free surface layer which remains uncrosslinked and acetone-soluble.
Results:
Coating Result after UV irradiation Material A 2 s: acetone-resistant, hard, no surface inhibition 5 s: acetone-resistant, hard, no surface inhibition 10 s: acetone-resistant, hard, no surface inhibition B 2 s: acetone-resistant, hard, no surface inhibition 5 s: acetone-resistant, hard, no surface inhibition 10 s: acetone-resistant, hard, no surface inhibition C 5 s: slightly tacky, acetone-resistant below detachable layer (surface inhibition) s: tack-free, soft, acetone-resistant below detachable layer (surface inhibition) s: tack-free, hard, acetone-resistant below detachable layer (surface inhibition) These examples show that the examples in accordance with the invention achieve extremely high sensitivity 5 to UV light and avoid oxygen inhibition of the surface.
380 g of bisphenol A glycidol ether (Araldite GY 2600) having an epoxide equivalent weight of 190 are initially introduced into a stirred flask with feed vessel and heating bath and this initial charge is heated to 90°C under a gentle stream of nitrogen. Then 314 g of diethanolamine divinyl ether are added dropwise over one hour and stirring is continued at 100°C for 5 hours. The result of cooling is a viscose yellowish resin.
Example 2 Vinyl compound based on a polyacrylate.
A flask with heating bath, reflux condenser stirred and two feed vessels is charged with 200 g of butyl acetate 50 g of methyl methacrylate g of glycidyl methacrylate 25 20 g ethylhexyl acrylate 1 g of mercaptoethanol (regulator) 2 g of tert-butyl peroctoate (initiator) and this initial charge is heated with stirring to 30 115°C. Then the following feeds are run in simultaneously over one hour.
Feed I: a mixture of 150 g of methyl methacrylate 90 g of glycidyl methacrylate 60 g of ethylhexyl acrylate 3 g of mercapto ethanol (regulator) Feed II: a mixture of 6 g of tert-butyl peroctoate (initiator) 66 g of butyl acetate The mixture is subsequently stirred at 120°C for 3 hours and then cooled to 60°C, after which 5 132 g of diethanolamine divinyl ether 0.8 g of tert-butylcresole 0.8 g of hydroquinone monomethyl ether 0.1 g of phenothiazine are added.
The mixture is then stirred at 100°C for 6 hours. The result is a viscose yellowish resin solution.
Testing of the vinyl compounds:
A 100 g of Laromer PO 33 F (unsaturated acrylate resin from BASF) 30 g of resin of Example 1 3.9 g of benzil dimethyl ketal B 100 g of Laromer PO 33 F (unsaturated acrylate resin from BASF) g of resin of Example 2 3.9 g of benzil dimethyl ketal C Comparative Example 100 g of Laromer PO 33 F (unsaturated acrylate resin from BASF) 3 g of benzil dimethyl ketal The test coating materials were prepared and the test panels produced in a UV-protected laboratory. The components of the test coating materials were premixed in glass flasks with a stirring spatula and these mixtures were stored in a drying cabinet at 50°C for 1 hour and stirred thoroughly again. Cooling to room temperature resulted in all cases in clear, viscose solutions.
The solutions were then drawn down onto degreased bright steel panels using a coater bar having a gap height of 60 mm. The test panels were then irradiated under a mercury vapor W lamp having an emission maximum at about 365 nm and an energy output of 19 mJ/cm2 in the exposure plane until the films were not attacked by 10 minutes of exposure to a cotton pad wetted with acetone. If surface inhibition of the films was observed, a non-crosslinked, acetone-soluble layer present was first of all wiped off and the swellability of the underlying layer was assessed. Surface inhibition means that the layers are acetone-insolubly crosslinked beneath a tacky or tack-free surface layer which remains uncrosslinked and acetone-soluble.
Results:
Coating Result after UV irradiation Material A 2 s: acetone-resistant, hard, no surface inhibition 5 s: acetone-resistant, hard, no surface inhibition 10 s: acetone-resistant, hard, no surface inhibition B 2 s: acetone-resistant, hard, no surface inhibition 5 s: acetone-resistant, hard, no surface inhibition 10 s: acetone-resistant, hard, no surface inhibition C 5 s: slightly tacky, acetone-resistant below detachable layer (surface inhibition) s: tack-free, soft, acetone-resistant below detachable layer (surface inhibition) s: tack-free, hard, acetone-resistant below detachable layer (surface inhibition) These examples show that the examples in accordance with the invention achieve extremely high sensitivity 5 to UV light and avoid oxygen inhibition of the surface.
Claims (16)
1.A process for preparing a vinyl compound, which comprises reacting an aminovinyl compound, which retains its vinyl groups, with a substance containing epoxy groups and selected from epoxy resins and copolymers incorporating glycidyl methacrylate monomers.
2. A process as claimed in claim 1, wherein the reaction takes place at the amino group or groups.
3. A process as claimed in claim l, wherein said aminovinyl compound has further reactive groups and the reaction takes place at the amino group or groups and/or at the reactive groups.
4. A process as claimed in any of claims 1 to 3, wherein the aminovinyl compound reacted is an aminovinyl ether compound.
5. A process as claimed in claim 4, wherein said aminovinyl ether compound contains the vinyl ether group singly or multiply.
6. A process as claimed in any of claims 1 to 5, wherein said vinyl compound is prepared in the form of a monomer, oligomer, polymer or mixture thereof.
7. A process as claimed in claim 1, wherein said substance contains epoxy groups and one or more of said epoxy groups may be present.
8. A vinyl compound obtainable by a process as claimed in any of claims 1 to 7.
9. A formulation comprising at least one vinyl compound as claimed in claim 8.
10. A formulation as claimed in claim 9, which additionally comprises further ionic and/or free-radically co-reactive substances selected from monomeric, oligomeric and/or polymeric epoxy, allyl, (meth)acrylic and/or vinyl ether compounds.
11. The use of a vinyl compound as claimed in claim 8 or formulation as claimed in claim 9 or 10 for free-radically and/or ionically initiated curing.
12. The use of an aminovinyl compound to prepare a vinyl compound as claimed in claim 8.
13. The use of a vinyl compound as claimed in claim 8 or formulation as claimed in claim 9 or 10 in coating materials, adhesives, printing inks and UV-curable or daylight curable exterior paints.
14. The use of a vinyl compound as claimed in claim 8 or formulation as claimed in claim 9 or 10 in coatings.
15. The use of a vinyl compound as claimed in claim 8 or formulation as claimed in claim 9 or 10 in potting compounds, casting compositions and impregnants for electronics and electrical engineering.
16. The use of a vinyl compound as claimed in claim 8 or formulation as claimed in either of claims 9 and 10 in fiber-reinforced materials and prepregs.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19835906.3 | 1998-08-07 | ||
| DE19835906A DE19835906A1 (en) | 1998-08-07 | 1998-08-07 | Process for the production of vinyl compounds |
| PCT/EP1999/005553 WO2000008085A1 (en) | 1998-08-07 | 1999-08-02 | Method for producing vinyl compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2339737A1 true CA2339737A1 (en) | 2000-02-17 |
Family
ID=7876881
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002339737A Abandoned CA2339737A1 (en) | 1998-08-07 | 1999-08-02 | Method for producing vinyl compounds |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1102801A1 (en) |
| JP (1) | JP2002522583A (en) |
| KR (1) | KR20010071082A (en) |
| CN (1) | CN1322219A (en) |
| CA (1) | CA2339737A1 (en) |
| DE (1) | DE19835906A1 (en) |
| WO (1) | WO2000008085A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7745400B2 (en) | 2005-10-14 | 2010-06-29 | Gregg Feinerman | Prevention and treatment of ocular side effects with a cyclosporin |
| US9839667B2 (en) | 2005-10-14 | 2017-12-12 | Allergan, Inc. | Prevention and treatment of ocular side effects with a cyclosporin |
| TWI730037B (en) * | 2016-01-26 | 2021-06-11 | 日商富士軟片和光純藥股份有限公司 | Photocuring method, compound and composition used therefor |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU672859A1 (en) * | 1977-07-12 | 1990-04-23 | Иркутский институт органической химии СО АН СССР | Oligomers of 2-aminoethylvinyl ester as hardener for epoxy resins and method of producing same |
| JPS6026022A (en) * | 1983-07-20 | 1985-02-08 | Sanyo Chem Ind Ltd | Polyurethane |
| DE19602071A1 (en) * | 1995-02-11 | 1996-06-13 | Basf Ag | Michael adducts of (meth)acrylic cpds. with amino-alkenyl ether cpds. |
| DE19535161A1 (en) * | 1995-09-22 | 1997-03-27 | Basf Ag | Radiation-curable compositions containing surface-active, blocked amino compounds |
-
1998
- 1998-08-07 DE DE19835906A patent/DE19835906A1/en not_active Withdrawn
-
1999
- 1999-08-02 KR KR1020017001620A patent/KR20010071082A/en not_active Application Discontinuation
- 1999-08-02 CN CN99811854A patent/CN1322219A/en active Pending
- 1999-08-02 WO PCT/EP1999/005553 patent/WO2000008085A1/en not_active Application Discontinuation
- 1999-08-02 EP EP99939782A patent/EP1102801A1/en not_active Withdrawn
- 1999-08-02 CA CA002339737A patent/CA2339737A1/en not_active Abandoned
- 1999-08-02 JP JP2000563716A patent/JP2002522583A/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| CN1322219A (en) | 2001-11-14 |
| DE19835906A1 (en) | 2000-02-10 |
| KR20010071082A (en) | 2001-07-28 |
| EP1102801A1 (en) | 2001-05-30 |
| WO2000008085A1 (en) | 2000-02-17 |
| JP2002522583A (en) | 2002-07-23 |
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