Patent Application
20160194341
The present invention relates to silylated polyisocyanates containing allophanate groups, to processes for preparing them, to their use, and to coating compositions comprising them.
Pigmented paints and transparent varnishes composed or based on polyurethanes have been known for a number of decades.
More recent times have seen polyisocyanates containing isocyanate groups partly substituted by alkoxysilyl groups, giving the resulting product not only curing of the free isocyanate groups but also, with the formation of siloxane, a further curing mechanism. For a polyisocyanate architecture of this kind, it is common to use the readily commercially available 3-(trialkoxysilyl)propylamine or N-alkylated derivatives thereof—see, for example, in WO2008/074489.
A disadvantage of this reaction regime is that said reaction of isocyanate groups with 3-(trialkoxysilyl)propylamine produces urea groups, which diminish the solubility of the resultant products.
It would be desirable, for example, to attach alkoxysilyl groups via urethane groups. To do so, however, requires the use of a compound which has not only alkoxysilyl groups but also a free hydroxyl group for attachment to the isocyanate group. Such a situation is mutually exclusive, however, since the free hydroxyl group would react instantly with the alkoxysilyl group.
There is additionally a need for low-viscosity polyisocyanates which can be used in polyurethane coating compositions. In order to formulate a coating composition to a desired application viscosity, it is often necessary to add solvent. By reducing the viscosity of the starting components, the solvent demand can be reduced.
It was an object of the present invention to develop a process with which alkoxysilyl groups can be attached to polyisocyanates without the products exhibiting the poor solubility of polyisocyanates containing urea groups. In addition, the viscosity of the products should be as low as possible.
The object has been achieved by means of a process for preparing polyisocyanates carrying silyl groups and containing allophanate groups, which comprises
As a result of the specific two-step synthesis of the compounds, silylated polyisocyanates obtained in accordance with the invention do not contain the abovementioned disruptive urea groups. The polyisocyanates obtainable exhibit more ready solubility in common solvents and/or a lower melting point than the analogous polyisocyanates containing urea groups.
As a result of the binding the silyl groups to the polyisocyanates of the invention via allophanate groups, the viscosity of the products may additionally be lowered.
The di- or polyisocyanate (A) is a compound which has at least 2 free isocyanate groups. The compounds in question may be monomeric di- or polyisocyanates, or polyisocyanates obtainable by reaction of at least one diisocyanate. Preferably they are monomeric diisocyanates.
The diisocyanates and the monomeric isocyanates used for preparing the polyisocyanates may be aromatic, aliphatic, or cycloaliphatic diisocyanates, preferably aliphatic or cycloaliphatic, which is referred to for short in this text as (cyclo)aliphatic; aliphatic isocyanates are particularly preferred.
Aromatic isocyanates are those which comprise at least one aromatic ring system, in other words not only purely aromatic compounds but also araliphatic compounds. The aromatic isocyanates naturally display a greater reactivity, which can be boosted still further through the use of catalysts.
Cycloaliphatic isocyanates are those which comprise at least one cycloaliphatic ring system.
Aliphatic isocyanates are those which comprise exclusively linear or branched chains, i.e., acyclic compounds.
The monomeric isocyanates are preferably diisocyanates, which carry precisely two isocyanate groups.
In principle, higher isocyanates having on average more than 2 isocyanate groups are also possible. Suitability therefor is possessed for example by triisocyanates, such as triisocyanatononane, 2′-isocyanatoethyl 2,6-diisocyanatohexanoate, 2,4,6-triiso-cyanatotoluene, triphenylmethane triisocyanate or 2,4,4′-triisocyanatodiphenyl ether, or the mixtures of diisocyanates, triisocyanates, and higher polyisocyanates that are obtained, for example, by phosgenation of corresponding aniline/formaldehyde condensates and represent methylene-bridged polyphenyl polyisocyanates.
These monomeric isocyanates do not contain substantially any products of reaction of the isocyanate groups with themselves.
The monomeric isocyanates are preferably isocyanates having 4 to 20 C atoms. Examples of typical diisocyanates are aliphatic diisocyanates such as tetramethylene diisocyanate, pentamethylene 1,5-diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, derivatives of lysine diisocyanate (e.g., methyl 2,6-diisocyanatohexanoate or ethyl 2,6-diisocyanatohexanoate), trimethylhexane diisocyanate or tetramethylhexane diisocyanate, cycloaliphatic diisocyanates such as 1,4-, 1,3- or 1,2-diisocyanatocyclohexane, 4,4′- or 2,4′-di(isocyanatocyclohexyl)methane, 1-isocyanato-3,3,5-trimethyl-5-(isocyanato-methyl)cyclohexane (isophorone diisocyanate), 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane or 2,4-, or 2,6-diisocyanato-1-methylcyclohexane, and also 3 (or 4), 8 (or 9)-bis(isocyanatomethyl)tricyclo[5.2.1.02,6]decane isomer mixtures, and also aromatic diisocyanates such as tolylene 2,4- or 2,6-diisocyanate and the isomer mixtures thereof, m- or p-xylylene diisocyanate, 2,4′- or 4,4′-diisocyanatodiphenylmethane and the isomer mixtures thereof, phenylene 1,3- or 1,4-diisocyanate, 1-chlorophenylene 2,4-diisocyanate, naphthylene 1,5-diisocyanate, diphenylene 4,4′-diisocyanate, 4,4′-diisocyanato-3,3′-dimethylbiphenyl, 3-methyldiphenylmethane 4,4′-diisocyanate, tetramethylxylylene diisocyanate, 1,4-diisocyanatobenzene or diphenyl ether 4,4′-diisocyanate.
Particular preference is given to hexamethylene 1,6-diisocyanate, 1,3-bis(isocyanato-methyl)cyclohexane, isophorone diisocyanate, and 4,4′- or 2,4′-di(isocyanato-cyclohexyl)methane, very particular preference to isophorone diisocyanate and hexamethylene 1,6-diisocyanate, and especial preference to hexamethylene 1,6-diisocyanate.
Mixtures of said isocyanates may also be present.
Isophorone diisocyanate is usually in the form of a mixture, specifically a mixture of the cis and trans isomers, generally in a proportion of about 60:40 to 90:10 (w/w), preferably of 70:30-90:10.
Dicyclohexylmethane 4,4′-diisocyanate may likewise be in the form of a mixture of the different cis and trans isomers.
For the present invention it is possible to use not only those diisocyanates obtained by phosgenating the corresponding amines but also those prepared without the use of phosgene, i.e., by phosgene-free processes. According to EP-A-0 126 299 (U.S. Pat. No. 4,596,678), EP-A-126 300 (U.S. Pat. No. 4,596,679), and EP-A-355 443 (U.S. Pat. No. 5,087,739), for example, (cyclo)aliphatic diisocyanates, such as hexamethylene 1,6-diisocyanate (HDI), isomeric aliphatic diisocyanates having 6 carbon atoms in the alkylene radical, 4,4′- or 2,4′-di(isocyanatocyclohexyl)methane, and 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane (isophorone diisocyanate or IPDI) can be prepared by reacting the (cyclo)aliphatic diamines with, for example, urea and alcohols to give (cyclo)aliphatic biscarbamic esters and subjecting said esters to thermal cleavage into the corresponding diisocyanates and alcohols. The synthesis takes place usually continuously in a circulation process and in the presence, if desired, of N-unsubstituted carbamic esters, dialkyl carbonates, and other by-products recycled from the reaction process. Diisocyanates obtained in this way generally contain a very low or even unmeasurable fraction of chlorinated compounds, which is advantageous, for example, in applications in the electronics industry.
In one embodiment of the present invention the isocyanates used have a total hydrolyzable chlorine content of less than 100 ppm, very preferably less than 30 ppm, in particular less than 20 ppm, and especially less than 10 ppm. This can be measured by means, for example, of ASTM specification D4663-98. The amounts of total chlorine are, for example, below 1000 ppm, preferably below 800 ppm, and more preferably below 500 ppm (determined by argentometric titration after hydrolysis).
It will be appreciated that it is also possible to employ mixtures of those monomeric isocyanates which have been obtained by reacting the (cyclo)aliphatic diamines with, for example, urea and alcohols and cleaving the resulting (cyclo)aliphatic biscarbamic esters, with those diisocyanates which have been obtained by phosgenating the corresponding amines.
Compared to the monomeric diisocyanates, polyisocyanates (A) to which the monomeric isocyanates can be oligomerized, are less preferred, although still conceivable. These are generally characterized as follows:
The average NCO functionality of such compounds is in general at least 1.8 and can be up to 8, preferably 2 to 5, and more preferably 2.4 to 4.
The isocyanate group content after oligomerization, calculated as NCO=42 g/mol, is generally from 5% to 25% by weight unless otherwise specified.
The polyisocyanates (A) are preferably compounds as follows:
In one possible embodiment of the present invention the polyisocyanate (A) is selected from the group consisting of isocyanurates, biurets, urethanes, and allophanates, preferably from the group consisting of isocyanurates, urethanes, and allophanates; more preferably it is a polyisocyanate containing isocyanurate groups.
In another possible embodiment the polyisocyanate (A) encompasses polyisocyanates comprising isocyanurate groups and obtained from 1,6-hexamethylene diisocyanate.
For example, the polyisocyanate (A) may be a mixture comprising low-viscosity polyisocyanates, preferably polyisocyanates comprising isocyanurate groups, with a viscosity of 200-1500 mPa*s, preferably 400-1300, low-viscosity urethanes and/or allophanates having a viscosity of 200-1600 mPa*s, more particularly 600-1500 mPa*s, and/or polyisocyanates comprising iminooxadiazinedione groups.
In this specification, unless noted otherwise, the viscosity is reported at 23° C. in accordance with DIN EN ISO 3219/A.3 in a cone/plate system with a shear rate of 1000 s−1.
The silylated polyisocyanates of the invention are for example obtainable, preferably obtained, by two-step reaction of the corresponding diisocyanates or, less preferably, of the polyisocyanates. In the first step this compound is reacted with an unsaturated monoalcohol (B), preferably allyl alcohol, under reaction conditions under which essentially at least some, preferably most, allophanate groups are very preferably formed. To the double bond bonded in this manner, a compound (C) of the formula (V) is added in the next step by means of transition metal-catalyzed, preferably platinum-catalyzed, hydrosilylation
In this formula, R9-R11 independently of one another are
Alkyl for the purposes of the present specification is straight-chain or branched alkyl groups having one to 20 carbon atoms, preferably C1-C8 alkyl groups, i.e., for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 2-butyl, tert-butyl, 1-pentyl, 2-pentyl, isoamyl, n-hexyl, n-octyl, or 2-ethylhexyl.
By C1-C4 alkyl in this specification is meant methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 2-butyl, or tert-butyl.
R9 to R11 are independently of one another alkyl, a radical of the formula —O—R12, preferably a radical of the formula —OR12, more preferably with R12 as alkyl, very preferably methyl or ethyl, and more particularly ethyl.
This platinum-catalyzed hydrosilylation is frequently carried out in the following way: The reaction product containing allophanate groups of the di- or polyisocyanate (A) used with the unsaturated monoalcohol (B) is admixed with the silicon hydride (V), in solution in an anhydrous inert solvent, at ambient temperature in a reaction vessel which is equipped with means for maintaining an inert gas blanket, preferably of nitrogen or argon, the admixing taking place with inert gas blanketing. Added with stirring is a catalyst, such as a transition metal, for example, preferably a noble metal from transition group VIII, more preferably nickel, nickel salts, iridium salts, and very preferably chloroplatinic acid or Karstedt catalyst (platinum-divinyltetramethyldisiloxane). The temperature is raised to about 60° C. under inert gas blanketing. The reaction can be monitored by NMR spectroscopy for the disappearance of the multiplet of the vinylic methine proton (—CH=5.9 ppm in CDCl3) of the allyl group.
The di- or polyisocyanate used may comprise at least one solvent which is not reactive toward isocyanate groups, examples being esters, ethers, ketones, or aromatic hydrocarbons, such as toluene or xylene-isomer mixtures, for example.
The compound (B) comprises at least one, preferably precisely one, unsaturated alcohol (B), which carries at least one, preferably precisely one, C═C double bond and at least one, preferably precisely one, hydroxyl group.
The C═C double bonds in accordance with the invention are nonactivated double bonds, which means that they are C═C double bonds or conjugated double bond systems which are not connected directly, i.e., are not directly adjacent, to any groups other than hydrogen and sp3-hybridized carbon atoms. Such sp3-hybridized carbon atoms may comprise, for example, alkyl groups, unsubstituted methylene groups, monosubstituted alkylene groups (1,1-alkylene groups) or disubstituted alkylene groups (n,n-alkylene groups).
In the case of conjugated double bond systems, the C═C double bond is conjugated with one or more further C═C double bonds and/or with an aromatic system, the bonds and/or system in question being preferably one to three, more preferably one to two, and very preferably precisely one further C═C double bond(s) and/or preferably precisely one carbocyclic aromatic ring system. Important in accordance with the invention is that in this case the conjugated double bond system is not connected directly to any groups other than hydrogen and sp3-hybridized carbon atoms. The aromatic ring system is a carbocyclic ring system; heteroaromatic systems are excluded by the invention.
The C═C double bonds are preferably isolated double bonds; alcohols (B) with conjugated double bond systems are less preferred.
Excluded, on the other hand, are those C═C double bonds which are electronically activated—that is, for example, vinyl ether groups, acrylate groups or methacrylate groups.
Located between the C═C double bonds and hydroxyl groups there is at least one sp3-hybridized carbon atom, preferably one to ten, more preferably one to five, very preferably one to three, more particularly one to two, and especially one.
Examples of compounds (B) of these kinds are allyl alcohol (2-propen-1-ol), methallyl alcohol (2-methyl-2-propen-1-ol), homoallyl alcohol (3-buten-1-ol), 1-buten-3-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-buten-2-ol, 1-octen-3-ol, 2-hexen-1-ol, 1-penten-3-ol, and also, in addition, phytol, farnesol, and linalool.
Examples of compounds (B) having a plurality of C═C double bonds are 1,4-pentadien-3-ol, 1,4-hexadien-3-ol, and 5-methyl-1,4-hexadien-3-ol. Compounds having a plurality of C═C double bonds are less preferred, however.
One example of compounds (B) with C═C double bonds which are conjugated to a carbocyclic aromatic ring system is cinnamyl alcohol. Compounds with C═C double bonds conjugated to aromatics are less preferred, however.
Preference is given to allyl alcohol, methallyl alcohol, and homoallyl alcohol, particular preference to allyl alcohol.
The compound (C) is preferably a compound of the formula (V):
where R9-R11 have the definition given above.
In this formula, R9 to R11 independently of one another are preferably
More preferably R9 to R11 are selected from the group consisting of methyl, ethyl, isopropyl, n-butyl, tert-butyl, methoxy, ethoxy, tert-butyloxy, and phenoxy, very preferably from the group consisting of methyl, ethyl, methoxy, and ethoxy.
The silanes (C) used are preferably tris(alkyloxy)silanes or alkyl bis(alkyloxy)silanes, more preferably tris(C1-C4-alkyloxy)silanes or C1-C4-alkyl-bis(C1-C4-alkyloxy)silanes.
The silanes (C) used are very preferably triethylsilane, triisopropylsilane, dimethylphenylsilane, diethoxymethylsilane, dimethoxymethylsilane, ethoxydimethylsilane, phenoxydimethylsilane, triethoxysilane, trimethoxysilane, bistrimethylsiloxymethylsilane, or mixtures thereof.
The stoichiometry of unsaturated alcohol (B) to the isocyanate groups in the di- or polyisocyanate (A) is generally from 1:0.1 to 0.1:1, preferably 1:0.2 to 0.2:1, more preferably 1:0.3 to 0.3:1, very preferably 1:0.5 to 0.5:1, and more particularly 1:0.66 to 0.66:1.
The stoichiometry of silane (C) according to formula (V) to double bonds in the polyisocyanate containing allophanate groups, obtained by reaction with an unsaturated alcohol, is generally from 0.1:1 to 1.0:1, preferably from 0.5:1 to 1.0:1, more preferably from 0.6:1 to 1.0:1, and very preferably from 0.8:1 to 1.0:1.
Also conceivable is the use of compounds (C) which carry more than one Si—H bond, as for example at least two, preferably two to four, more preferably two or three, and very preferably two.
Examples thereof are siloxane-bridged compounds (C1) of the formula
or their higher homologs with n=2 to 5
in which R9 and R10 may have the above definitions.
Examples of such are tetramethylsiloxane, tetraethylsiloxane, and tetraphenylsiloxane.
The reaction to the silylated polyisocyanates of the invention may take place in the first stage preferably between 40 and 120° C., more preferably between 60 and 110° C., and very preferably between 80 and 100° C., and in the second stage preferably between 40 and 80° C., more preferably between 50 and 70° C., and very preferably at 60° C.
It is essential to the invention that the reaction in the first stage takes place with formation of allophanate groups, with at least some of the unsaturated alcohol (B) being bonded via allophanate groups.
A reaction of this kind is known from U.S. Pat. No. 5,739,251.
It is also possible to bond some of the unsaturated alcohol (B) via allophanate groups and some of the unsaturated alcohol (B) via urethane groups.
The ratio of alcohol (B) bonded via allophanate groups to alcohol (B) bonded by urethane groups may be from 1:0 to 1:2, preferably 1:0.1 to 1:1.5, more preferably from 1:0.3 to 1:1, and very preferably from 1:0.5 to 1:1.
The reaction may be carried out in bulk, but preferably in an inert, anhydrous solvent.
The reaction of the di- or polyisocyanate used with the unsaturated alcohol preferably takes place with catalysis and with or without addition of an azeotrope former, such as toluene, for example.
The unsaturated alcohol is used in the ratio indicated above, according to the desired degree of substitution.
In one preferred embodiment of the present invention the ratio of alcohol (B) to di- or polyisocyanate (A) is to be selected such that the resultant polyisocyanate containing allophanate groups has an average functionality of alcohol (B) of preferably at least 1, more preferably 1 to 3, very preferably 1 to 2, and especially preferably 1. If necessary, a product which carries only a few alcohol groups (B) may be reacted further by addition of further alcohol (B).
The addition of the silane (C) to the double bond of the unsaturated alcohol (B) takes place with transition metal catalysis. Transition metals contemplated are preferably those from transition group eight, more preferably platinum, rhodium, palladium, cobalt, and nickel, metallically or in the form of the complexes. One preferred catalyst is, for example, the catalyst known as Karstedt catalyst (platinum-divinyltetramethyldisiloxane) or hexachloroplatinic acid hydrate, also for example in the form of Speier catalyst, in other words in the form of the solution in isopropanol, and also platinum on activated carbon.
The reaction in the first stage is generally carried out by introducing the unsaturated alcohol used, optionally together with the catalyst, bringing this initial charge to the desired temperature, and slowly adding the di- or polyisocyanate, optionally in solution in a suitable solvent.
The reaction with the unsaturated alcohol may preferably take place in the presence of at least one catalyst. Preferred catalysts are selected from the group consisting of compounds of lead, tin, iron, titanium, aluminum, manganese, nickel, zinc, cobalt, zirconium and bismuth, being preferably compounds of titanium, aluminum, zinc, zirconium or bismuth, more preferably compounds of titanium, zinc, or bismuth, very preferably compounds of titanium or bismuth, and more particularly bismuth compounds.
Possible for example are metal complexes such as acetylacetonates of iron, of titanium, of aluminum, of zirconium, of manganese, of nickel, of zinc, and of cobalt.
Examples of compounds used as zirconium, bismuth, titanium, and aluminum compounds include the following: zirconium tetraacetylacetonate (e.g., K-KAT® 4205 from King Industries); zirconium dionates (e.g., K-KAT® XC-9213; XC-A 209 and XC-6212 from King Industries); and aluminum dionate (e.g., K-KAT® 5218 from King Industries).
Zinc compounds contemplated in this context are those in which the following anions are used: F−, Cl−, ClO−, ClO3−, ClO4−, Br−, I−, IO3−, CN−, OCN−, NO2−, NO3−, HCO3−, CO32−, S2−, SH−, HSO3−, SO32−, HSO4−, SO42−, S2O22−, S2O42−, S2O52−, S2O62−, S2O72−, S2O82−, H2PO2−, H2PO4−, HPO42−, PO43−, P2O74−, (OCnH2n+1)−, (CnH2n−1O2)−, (CnH2n−3O2)−, and (Cn+1H2n−2O4)2−, where n stands for the numbers 1 to 20. Preferred here are the carboxylates where the anion conforms to the formulae (CnH2n−1O2)− and also (Cn+1H2n−2O4)2− with n being 1 to 20. Particularly preferred salts have monocarboxylate anions of the general formula (CnH2n−1O2)− where n stands for the numbers 1 to 20. Especially noteworthy in this context are formate, acetate, propionate, hexanoate, neodecanoate, and 2-ethylhexanoate.
Among the zinc catalysts the zinc carboxylates are preferred, more preferably those of carboxylates having at least six carbon atoms, very preferably at least eight carbon atoms, more particularly zinc(II) diacetate, zinc(II) dioctoate, or zinc(II) neodecanoate. Examples of commercial catalysts include Borchi® K at 22 from OMG Borchers GmbH, Langenfeld, Germany.
Among the titanium compounds the titanium tetraalcoholates Ti(OR)4 are preferred, more preferably those of alcohols ROH having 1 to 8 carbon atoms, examples being methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-hexanol, n-heptanol, and n-octanol, preferably methanol, ethanol, isopropanol, n-propanol, n-butanol, or tert-butanol, more preferably isopropanol and n-butanol.
As catalyst, preference is given to using at least one bismuth compound, as for example one to three, preferably one or two, and more preferably precisely one compound of bismuth in the +3 oxidation state.
Bismuth compounds contemplated in this context are compounds of bismuth with the following anions: F−, Cl−, ClO−, ClO3−, ClO4−, Br−, I−, IO3−, CN−, OCN−, NO2−, NO3−, HCO3−, CO32−, S2−, SH−, HSO3−, SO32−, HSO4−, SO42−, S2O22−, S2O42−, S2O52−, S2O62−, S2O72−, S2O82−, H2PO2−, H2PO4−, HPO42−, PO43−, P2O74−, (OCxH2x+1)−, (CxH2x−1O2)−, (CxH2x−3O2)−, and (Cx+1H2x−2O4)2−, where x stands for the numbers 1 to 20. Preferred here are the carboxylates where the anion conforms to the formulae (CxH2x−1O2)− and also (Cx+1H2x−2O4)2− with x being 1 to 20. Particularly preferred salts have monocarboxylate anions of the general formula (CxH2x−1O2)− where x stands for the numbers 1 to 20, preferably 1 to 10. Especially noteworthy in this context are formate, acetate, propionate, hexanoate, neodecanoate, and 2-ethylhexanoate.
Preferred among the bismuth catalysts are the bismuth carboxylates, more preferably those of carboxylates which have at least six carbon atoms, more particularly bismuth octoates, ethylhexanoates, neodecanoates, or pivalates; examples are K-KAT 348, XC-B221; XC-C227, XC 8203, and XK-601 from King Industries, TIB KAT 716, 716LA, 716XLA, 718, 720, and 789 from TIB Chemicals, and those from Shepherd Lausanne, and also, for example, Borchi® Kat 24, 315, and 320 from OMG Borchers GmbH, Langenfeld, Germany.
Mixtures of different metals may also be relevant in this context, such as, for example, in Borchi® Kat 0245 from OMG Borchers GmbH, Langenfeld, Germany.
Particularly preferred, however, are bismuth neodecanoate, bismuth 2-ethylhexanoate, and zinc 2-ethyl hexanoate.
It is possible to boost the effect of the catalysts additionally through the presence of acids, as for example through acids having a pKa of <2.5, as described in EP 2316867 A1, or with a pKa of between 2.8 and 4.5, as described in WO 04/029121 A1. Preferred is the use of acids with a pKa of not more than 4.8, more preferably of not more than 2.5.
In one preferred embodiment of the present invention, the catalysis takes place with formation of allophanate groups through reaction of the monomeric diisocyanate in the present of quaternary ammonium salts, preferably quaternary ammonium carboxylates, carbonates, phenoxides, or hydroxides.
Particularly suitable as catalysts for the process are quaternary ammonium salts corresponding to the formula
where
Ye=carboxylate (R8COO−), fluoride (F−), carbonate (R8O(CO)O−) or hydroxide (OH−), as described for Y−═OH− in U.S. Pat. No. 4,324,879 and in German Laid-Open Specifications 2,806,731 and 2,901,479.
The radical Ye is preferably a carboxylate, carbonate or hydroxide and more preferably a carboxylate or hydroxide, very preferably a carboxylate.
R8 therein is hydrogen, C1 to C20 alkyl, C6 to C12 aryl or C7 to C12 arylalkyl, each of which may optionally be substituted.
Preferably R8 is hydrogen or C1 to C8 alkyl.
Preferred quaternary ammonium salts are those in which the radicals R4 to R7 are like or different alkyl groups having 1 to 20, preferably 1 to 4, carbon atoms, which are optionally substituted by hydroxyl or phenyl groups.
Two of the radicals R4 to R7 may also combine with the nitrogen atom and, if desired, with a further nitrogen or oxygen atom to form a heterocyclic five-, six- or seven-membered ring. The radicals R4 to R7 may in each case also be ethylene radicals, which combine with the quaternary nitrogen atom and with a further, tertiary nitrogen atom to form a bicyclic triethylenediamine structure, subject to the proviso that the radical R7 is then a hydroxyalkyl group having 2 to 4 carbon atoms, in which the hydroxyl group is located preferably in the 2-position relative to the quaternary nitrogen atom. The hydroxy-substituted radical or the hydroxy-substituted radicals may also contain other substituents, examples being C1 to C4 alkyloxy substituents.
The ammonium ions may also be part of a single-membered or multi-membered ring system, derived, for example, from piperazine, morpholine, piperidine, pyrrolidine, quinuclidine or diazabicyclo[2.2.2]octane.
Examples of groups R4 to R7 having 1 to 20 carbon atoms are, independently of one another, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3,3-tetramethylbutyl, benzyl, 1-phenylethyl, 2-phenylethyl, α,α-dimethylbenzyl, benzhydryl, p-tolylmethyl, 1-(p-butylphenyl)ethyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, methoxybenzyl, 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1,2-di(methoxycarbonyl)ethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, chloromethyl, 2-chloroethyl, trichloromethyl, trifluoromethyl, 1,1-dimethyl-2-chloroethyl, 2-methoxyisopropyl, 2-ethoxyethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, 2-hydroxy-2,2-dimethylethyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl, 6-ethoxyhexyl, phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, norbornyl or norbornenyl.
Independently of one another, the radicals R4 to R7 are preferably C1 to C4 alkyl. R7 may additionally be benzyl or a radical of the formula
in which R′ and R″ independently of one another may be hydrogen or C1 to C4 alkyl.
Particularly preferred radicals R4 to R7 are, independently of one another, methyl, ethyl, and n-butyl, and for R7 additionally benzyl, 2-hydroxyethyl, and 2-hydroxypropyl.
For the process of the invention it is possible with preference to use the following catalysts:
Quaternary ammonium hydroxides, preferably N,N,N-trimethyl-N-benzylammonium hydroxide and N,N,N-trimethyl-N-(2-hydroxypropyl)ammonium hydroxide.
For certain of the aforementioned catalysts, as for example the recited ammonium salts, in general a portion of the diisocyanate is reacted to give a polyisocyanate which contains isocyanurate groups and which in turn is able to react with the unsaturated alcohol (B) to form urethane groups and/or allophanate groups, and another portion is reacted to give the desired polyisocyanate containing allophanate groups.
The weight ratio of polyisocyanate containing isocyanurate groups and desired polyisocyanate containing allophanate groups, without isocyanurate groups, is dependent on the reaction conditions and may for example be 10:90 to 90:10, preferably 20:80 to 80:20, more preferably 30:70 to 70:30, and very preferably 40:60 to 60:40.
In a preferred embodiment a catalyst is used with which predominantly polyisocyanates containing allophanate groups, without isocyanurate groups, are obtained. In the reaction mixture, with particular preference, the fraction of polyisocyanates with functional groups other than allophanate groups is less than 50 wt %, very preferably not more than 40, more particularly not more than 30, especially not more than 20, and even not more than 10 wt %.
By polyisocyanates with functional groups other than allophanate groups are meant in this context, more particularly, polyisocyanates containing isocyanurate groups, but also polyisocyanates containing urethane groups and/or polyisocyanates containing uretdione groups, the latter being less preferable.
The reaction product obtained can be purified by column chromatography on silica gel (Silicagel Si 60, 40-63 μm, Merck) with an eluent mixture of ethyl acetate and pentane in a ratio of 1:2. In general, however, the level of impurities in the crude product is minimal, and it can be used in the subsequent synthesis without further purification.
The second reaction stage is generally carried out by introducing the preliminary product from the first reaction stage, preferably under an inert atmosphere, together with the corresponding silane, in an anhydrous, inert solvent, and adding—with vigorous stirring—a solution of the transition metal catalyst in the same solvent. The reaction mixture is stirred at the abovementioned temperature for 30 minutes to 3 hours, preferably 1 to 2 hours, and subsequently, optionally, is freed from solvent under reduced pressure. There is no need for the product to be worked up and so preferably it is not.
The silylated polyisocyanate obtained has a viscosity at 23° C. in accordance with ISO 3219/B of preferably between 100 and 20 000 mPas, more preferably between 500 and 10 000 mPas.
The shear rate in this case ought preferably to be 250 s−1.
The number-average molar weight Mn of the silylated polyisocyanates containing allophanate groups obtained, is generally less than 3500 g/mol, preferably less than 3000 g/mol, and more preferably less than 2500 (as determined by gel permeation chromatography using tetrahydrofuran and polystyrene as standard, DIN 55672, part 1).
In one preferred embodiment, the silylated polyisocyanate containing allophanate groups is a polyisocyanate of the following idealized formula
in which
R2 represents a radical as formed by conceptual abstraction of two isocyanate groups from a diisocyanate,
R3 denotes a divalent aliphatic hydrocarbon radical having 1 to 12 carbon atoms, and R9 to R11 are as defined above.
Preferred radicals R2 are selected from the group consisting of 1,5-pentylene,
1,6-hexylene, and
The radical R2 is preferably 1,6-hexylene or
and more preferably 1,6-hexylene.
In one preferred embodiment R3 has 1 to 8, more preferably 1 to 4, very preferably 1 to 2 and more particularly precisely one carbon atom.
Examples of R3 are methylene, 1,2-ethylene, 1,1,-dimethyl-1,2-ethylene, 1,2-propylene, 1,3-propylene, 2-methyl-1,3-propylene, 2-ethyl-1,3-propylene, 2-butyl-2-ethyl-1,3-propylene, 2,2-dimethyl-1,3-propylene, 1,2-butylene, 1,3-butylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 2-ethyl-1,3-hexylene, 1,8-octylene, 2,4-diethyl-1,3-octylene or 1,10-decylene, preferably methylene, 1,2-ethylene, 1,2-propylene, 1,3-propylene, or 1,4-butylene, more preferably methylene.
Also conceivable, furthermore are the higher homologues of this idealized formula, in which, by addition reaction of two or more diisocyanates, two or more allophanate groups are formed—for example up to three, preferably up to two, allophanate groups. The silylated polyisocyanate containing allophanate groups preferably has an NCO content of 12 to 24, preferably 14 to 22, and more preferably 15 to 21 wt %.
The silylated polyisocyanate obtained in accordance with the invention may subsequently be mixed with commonplace solvents.
Examples of such solvents are aromatic and/or (cyclo)aliphatic hydrocarbons and mixtures thereof, halogenated hydrocarbons, esters, ethers, and alcohols.
Preference is given to aromatic hydrocarbons, (cyclo)aliphatic hydrocarbons, alkanoic acid alkyl esters, alkoxylated alkanoic acid alkyl esters, and mixtures thereof.
Particular preference is given to mono- or polyalkylated benzenes and naphthalenes, alkanoic acid alkyl esters and alkoxylated alkanoic acid alkyl esters, and mixtures thereof.
Preferred aromatic hydrocarbon mixtures are those which comprise predominantly aromatic C7 to C14 hydrocarbons and which span a boiling range from 110 to 300° C.; particular preference is given to toluene, o-, m- or p-xylene, trimethylbenzene isomers, tetramethylbenzene isomers, ethylbenzene, cumene, tetrahydronaphthalene, and mixtures comprising them.
Examples thereof are the Solvesso® grades from ExxonMobil Chemical, especially Solvesso® 100 (CAS No. 64742-95-6, predominantly C9 and C10 aromatics, boiling range about 154-178° C.), 150 (boiling range about 182-207° C.), and 200 (CAS No. 64742-94-5), and also the Shellsol® grades from Shell. Hydrocarbon mixtures of paraffins, cycloparaffins, and aromatics are also available commercially under the Kristalloel names (for example, Kristalloel 30, boiling range about 158-198° C. or Kristalloel 60: CAS No. 64742-82-1), white spirit (for example likewise CAS No. 64742-82-1) or solvent naphtha (light: boiling range about 155-180° C., heavy: boiling range about 225-300° C.). The aromatics content of hydrocarbon mixtures of this type is generally more than 90%, preferably more than 95%, more preferably more than 98%, and very preferably more than 99%, by weight. It may be sensible to use hydrocarbon mixtures having a particularly reduced naphthalene content.
The density at 20° C. to DIN 51757 of the hydrocarbons can be less than 1 g/cm3, preferably less than 0.95 and more preferably less than 0.9 g/cm3.
The aliphatic hydrocarbons content is generally less than 5%, preferably less than 2.5%, and more preferably less than 1%, by weight.
Halogenated hydrocarbons are for example chlorobenzene and dichlorobenzene or its isomer mixtures.
Esters are for example n-butyl acetate, ethyl acetate, 1-methoxyprop-2-yl acetate, and 2-methoxyethyl acetate, and also the monoacetyl and diacetyl esters of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol or tripropylene glycol, such as, for example, butylglycol acetate. Further examples are also carbonates, such as preferably 1,2-ethylene carbonate, 1,2-propylene carbonate or 1,3-propylene carbonate.
Ethers are for example tetrahydrofuran (THF), dioxane, and also the dimethyl, diethyl or di-n-butyl ethers of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol or tripropylene glycol.
(Cyclo)aliphatic hydrocarbons are for example decalin, alkylated decalin, and isomer mixtures of linear or branched alkanes and/or cycloalkanes.
Of further preference are n-butyl acetate, ethyl acetate, 1-methoxyprop-2-yl acetate, 2-methoxyethyl acetate, and also mixtures thereof, especially with the aromatic hydrocarbon mixtures set out above.
Mixtures of this kind may be produced in a volume ratio of 10:1 to 1:10, preferably in a volume ratio of 5:1 to 1:5, and more preferably in a volume ratio of 1:1.
Preferred examples are butyl acetate/xylene, 1:1 methoxypropyl acetate/xylene, 1:1 butyl acetate/solvent naphtha 100, 1:2 butyl acetate/Solvesso® 100, and 3:1 Kristalloel 30/Shellsol® A.
Alcohols are for example methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, pentanol isomer mixtures, hexanol isomer mixtures, 2-ethylhexanol or octanol.
It is an advantage of the silylated polyisocyanates of the invention that, in coating materials, they exhibit hardness and gloss properties that are comparable with or even an improvement on those of the unsilylated polyisocyanates. In addition, they have a further crosslinking mechanism, via the silyl groups that are present.
In addition, they have a lower viscosity than polyisocyanate having the same molar weight and the same functionality, to the extent that in coating compositions there is less need for solvent in order to achieve the application viscosity.
Curing is generally accomplished by drying the coatings—following application of the coating of the substrates with the coating compositions or formulations comprising the polyisocyanates of the invention, optionally admixed with further, typical coatings additives and thermally curable resins—if desired at a temperature below 80° C., preferably room temperature to 60° C., and more preferably room temperature to 40° C., for a time of up to 72 hours, preferably up to 48 hours, more preferably up to 24 hours, very preferably up to 12 hours, and in particular up to 6 hours, and subjecting them to thermal treatment (curing) under an oxygen-containing atmosphere, preferably air, or under inert gas at temperatures between 80 and 270° C., preferably between 100 and 240° C., and more preferably between 120 and 180° C. Curing of the coating takes place, as a function of the amount of coating material applied and of the crosslinking energy introduced, via high-energy radiation, heat transfer from heated surfaces, or via convection of gaseous media, over a period of from seconds, for example, in the case of coil coating in combination with NIR drying, up to 5 hours, for example, high-build systems on temperature-sensitive materials, usually not less than 10 minutes, preferably not less than 15 minutes, more preferably not less than 30 minutes, and very preferably not less than 45 minutes. Drying essentially comprises removal of existing solvent, and in addition there may also even at this stage be reaction with the binder, whereas curing essentially comprises reaction with the binder.
Instead of or in addition to thermal curing, curing may also take place by means of IR and NIR radiation, with NIR radiation here denoting electromagnetic radiation in the wavelength range from 760 nm to 2.5 μm, preferably from 900 to 1500 nm.
Curing takes place in a time of 1 second to 60 minutes, preferably of 1 minute to 45 minutes.
The present invention further provides coating compositions comprising at least one silylated polyisocyanate of the invention.
As binders, coating compositions of this kind comprise at least one binder comprising groups that are reactive toward isocyanate. These are, generally, selected from the group consisting of hydroxyl-containing binders and amino-containing binders.
The hydroxyl-containing binder preferably comprises polyetherols, polyesterols, polyacrylate polyols, polycarbonate polyols, alkyd resins or epoxy resins. Polyesterols and polyacrylate polyols are particularly preferred, very particular preference being given to polyacrylate polyols.
The binders have on average per molecule at least two, preferably two to ten, more preferably three to ten, and very preferably three to eight hydroxyl groups.
The OH number, measured to DIN 53240-2, is generally from 10 to 200 mg KOH/g, preferably from 30 to 140.
The binders may additionally have an acid number to DIN EN ISO 3682 of 0 to 200 mg KOH/g, preferably 0-100, and more preferably 0 to 10 mg KOH/g.
The polyacrylate polyols are, for example, those which are copolymers of (meth)acrylic esters with at least one compound having at least one, preferably precisely one, hydroxyl group and at least one, preferably precisely one, (meth)acrylate group.
The latter may be, for example, monoesters of α,β-unsaturated carboxylic acids, such as acrylic acid, methacrylic acid (referred to in this text for short as “(meth)acrylic acid”), with diols or polyols which have preferably 2 to 20 carbon atoms and at least two hydroxyl groups, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,1-dimethyl-1,2-ethanediol, dipropylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, tripropylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, neopentyl glycol hydroxypivalate, 2-ethyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,6-hexanediol, 2-methyl-1,5-pentanediol, 2-ethyl-1,4-butanediol, 2-ethyl-1,3-hexanediol, 2,4-diethyloctane-1,3-diol, 2,2-bis(4-hydroxycyclohexyl)propane, 1,1-, 1,2-, 1,3-, and 1,4-bis(hydroxymethyl)cyclohexane, 1,2-, 1,3- or 1,4-cyclohexanediol, glycerol, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, diglycerol, threitol, erythritol, adonitol (ribitol), arabitol (lyxitol), xylitol, dulcitol (galactitol), maltitol, isomalt, poly-THF having a molar weight between 162 and 2000, poly-1,3-propanediol or polypropylene glycol having a molar weight between 134 and 2000, or polyethylene glycol having a molar weight between 238 and 2000.
Preference is given to 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2- or 3-hydroxypropyl acrylate, 1,4-butanediol monoacrylate or 3-(acryloyloxy)-2-hydroxypropyl acrylate, and particular preference to 2-hydroxyethyl acrylate and/or 2-hydroxyethyl methacrylate.
The hydroxyl-bearing monomers are employed in the copolymerization in mixture with other polymerizable, preferably free-radically polymerizable, monomers, preferably those composed of more than 50% by weight of C1-C20 alkyl (meth)acrylate, vinylaromatics having up to 20 carbon atoms, vinyl esters of carboxylic acids comprising up to 20 carbon atoms, vinyl halides, nonaromatic hydrocarbons having 4 to 8 carbon atoms and 1 or 2 double bonds, unsaturated nitriles, and mixtures thereof. Particular preference is given to the polymers composed of more than 60% by weight of C1-C10 alkyl (meth)acrylates, styrene or mixtures thereof.
The polymers may further comprise hydroxyl-functional monomers in keeping with the above hydroxyl group content, and, if desired, further monomers, examples being ethylenically unsaturated acids, especially carboxylic acids, acid anhydrides or acid amides.
Further binders are polyesterols, such as are obtainable by condensing polycarboxylic acids, especially dicarboxylic acids, with polyols, especially diols.
Polyester polyols are known for example from Ullmanns Encyklopädie der technischen Chemie, 4th edition, volume 19, pp. 62 to 65. It is preferred to use polyester polyols obtained by reacting dihydric alcohols with dibasic carboxylic acids. In lieu of the free polycarboxylic acids it is also possible to use the corresponding polycarboxylic anhydrides or corresponding polycarboxylic esters of lower alcohols, or mixtures thereof, to prepare the polyester polyols. The polycarboxylic acids may be aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic and may be optionally substituted, by halogen atoms for example, and/or unsaturated. Examples thereof that may be mentioned include the following:
Oxalic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, o-phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, azelaic acid, 1,4-cyclohexanedicarboxylic acid or tetrahydrophthalic acid, suberic acid, azelaic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic anhydride, dimeric fatty acids, isomers thereof, hydrogenation products thereof, and esterifiable derivatives thereof, such as anhydrides or dialkyl esters, such as C1-C4 alkyl esters, preferably methyl, ethyl or n-butyl esters, of the stated acids. Preference is given to dicarboxylic acids of the general formula HOOC—(CH2)y—COOH, in which y is a number from 1 to 20, preferably an even number from 2 to 20; particular preference is given to succinic acid, adipic acid, sebacic acid, and dodecanedicarboxylic acid.
Suitable polyhydric alcohols for preparing the polyesterols include 1,2-propanediol, ethylene glycol, 2,2-dimethyl-1,2-ethanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 3-methylpentane-1,5-diol, 2-ethylhexane-1,3-diol, 2,4-diethyloctane-1,3-diol, 1,6-hexanediol, polyTHF having a molar mass between 162 and 2000, poly-1,3-propanediol having a molar mass between 134 and 1178, poly-1,2-propanediol having a molar mass between 134 and 898, polyethylene glycol having a molar mass between 106 and 458, neopentyl glycol, neopentyl glycol hydroxypivalate, 2-ethyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-bis(4-hydroxycyclohexyl)propane, 1,1-, 1,2-, 1,3-, and 1,4-cyclohexanedimethanol, 1,2-, 1,3- or 1,4-cyclohexanediol, trimethylolbutane, trimethylolpropane, trimethylolethane, neopentyl glycol, pentaerythritol, glycerol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, diglycerol, threitol, erythritol, adonitol (ribitol), arabitol (lyxitol), xylitol, dulcitol (galactitol), maltitol or isomalt, which optionally may be alkoxylated as described above.
Preference is given to alcohols of the general formula HO—(CH2)x—OH, in which x is a number from 1 to 20, preferably an even number from 2 to 20. Preference is given to ethylene glycol, butane-1,4-diol, hexane-1,6-diol, octane-1,8-diol and dodecane-1,12-diol. Preference is further given to neopentyl glycol.
Also suitable are polycarbonate diols, such as may be obtained, for example, by reacting phosgene with an excess of the low molecular mass alcohols as specified as synthesis components for the polyester polyols.
Also suitable are lactone-based polyester diols, which are homopolymers or copolymers of lactones, preferably hydroxy-terminal addition products of lactones with suitable difunctional starter molecules. Suitable lactones are preferably those derived from compounds of the general formula HO—(CH2)z—COOH, in which z is a number from 1 to 20 and one hydrogen atom of a methylene unit may also be substituted by a C1 to C4 alkyl radical. Examples are ε-caprolactone, β-propiolactone, gamma-butyrolactone and/or methyl-ε-caprolactone, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid or pivalolactone, and mixtures thereof. Suitable starter components are, for example, the low molecular mass dihydric alcohols specified above as a synthesis component for the polyester polyols. The corresponding polymers of c-caprolactone are particularly preferred. Lower polyester diols or polyether diols as well can be used as starters for preparing the lactone polymers. In lieu of the polymers of lactones it is also possible to use the corresponding, chemically equivalent polycondensates of the hydroxycarboxylic acids corresponding to the lactones.
Further suitable polymers are polyetherols, which are prepared by addition reaction of ethylene oxide, propylene oxide or butylene oxide with H-active components. Polycondensates of butanediol are suitable as well.
The polymers can of course also be compounds having primary or secondary amino groups.
Suitability is further possessed by polycarbonate polyols, such as may be obtained, for example, by reacting phosgene with an excess of the low molecular mass alcohols specified as synthesis components for the polyester polyols.
Alkyd resins are polycondensation resins made from polyols, polybasic carboxylic acids, and fatty oils, or free natural and/or synthetic fatty acids; at least one polyol must have a functionality of three or more.
As polyols and polybasic carboxylic acids it is possible for example to employ the components specified above in connection with the polyesterols.
Preferred polyhydric alcohols are glycerol, pentaerythritol, trimethylolethane, trimethylolpropane, various diols such as ethane-/propanediol, diethylene glycol, neopentyl glycol.
Preferred polybasic carboxylic acids are phthalic acid (anhydride) (PAA), isophthalic acid, terephthalic acid, trimellitic anhydride, adipic acid, azelaic acid, sebacic acid.
Examples of suitable oil components and/or fatty acids include drying oils, such as linseed oil, oiticica oil or tung oil, semidrying oils, such as soybean oil, sunflower oil, safflower oil, ricinene oil or tall oil, nondrying oils, such as castor oil, coconut oil or peanut oil, or free fatty acids of above oils, or synthetic monocarboxylic acids.
The molar mass of typical alkyd resins is between 1500 and 20 000, preferably between 3500 and 6000. The acid number is preferably 2 to 30 mg KOH/g, or 35-65 mg KOH/g in the case of water-thinnable resins. The OH number is generally up to 300, preferably up to 100 mg KOH/g.
Polyacrylate polyols, polyesterols and/or polyetherols of this kind have a molecular weight Mn of preferably at least 1000, more preferably at least 2000, and very preferably at least 5000 g/mol. The molecular weight Mn can be for example up to 200,000, preferably up to 100,000, more preferably up to 80,000, and very preferably up to 50,000 g/mol.
Furthermore, the polyisocyanates of the invention may also be used together with noncrosslinkable binders, i.e., those without groups that are reactive toward isocyanate. In this case the polyisocyanates of the invention crosslink by condensation of their silane groups with one another.
The crosslinking is accelerated generally by addition of acids.
Weak acids for the purposes of this text are monobasic or polybasic, organic or inorganic, preferably organic, acids having a pKa of between 1.6 and 5.2, preferably between 1.6 and 3.8.
Examples thereof are carbonic acid, phosphoric acid, formic acid, acetic acid, and maleic acid, glyoxylic acid, bromoacetic acid, chloroacetic acid, thioglycolic acid, glycine, cyanoacetic acid, acrylic acid, malonic acid, hydroxypropanedioic acid, propionic acid, lactic acid, 3-hydroxypropionic acid, glyceric acid, alanine, sarcosine, fumaric acid, acetoacetic acid, succinic acid, isobutyric acid, pentanoic acid, ascorbic acid, citric acid, nitrilotriacetic acid, cyclopentanecarboxylic acid, 3-methylglutaric acid, adipic acid, hexanoic acid, benzoic acid, cyclohexanecarboxylic acid, heptanedioic acid, heptanoic acid, phthalic acid, isophthalic acid, terephthalic acid, tolylic acid, phenylacetic acid, phenoxyacetic acid, mandelic acid or sebacic acid.
Preference is given to organic acids, preferably monobasic or polybasic carboxylic acids. Particular preference is given to formic acid, acetic acid, maleic acid or fumaric acid.
Strong acids for the purposes of this text are monobasic or polybasic, organic or inorganic, preferably organic acids having a pKa of less than 1.6 and more preferably less than 1.
Examples thereof are sulfuric acid, pyrophosphoric acid, sulfurous acid, and tetrafluoroboric acid, trichloroacetic acid, dichloroacetic acid, oxalic acid, and nitroacetic acid. Preference is given to organic acids, preferably organic sulfonic acids. Particular preference is given to methanesulfonic acid, para-toluenesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, cyclododecanesulfonic acid, and camphorsulfonic acid.
The acids are used in amounts in general of up to 10% by weight, preferably 0.1% to 8%, more preferably 0.3% to 6%, very preferably 0.5% to 5%, and in particular from 1% to 3% by weight, based on the polyurethane employed.
The acids may also be used as free acids or in blocked form.
Examples of further, typical coatings additives used can be antioxidants, stabilizers, activators (accelerants), fillers, pigments, dyes, antistatic agents, flame retardants, thickeners, thixotropic agents, surface-active agents, viscosity modifiers, plasticizers or chelating agents.
Suitable thickeners, in addition to free-radically (co)polymerized (co)polymers, include customary organic and inorganic thickeners such as hydroxymethylcellulose or bentonite.
Chelating agents which can be used include, for example, ethylenediamineacetic acid and its salts, and also β-diketones.
Suitable fillers comprise silicates, examples being silicates obtainable by silicon tetrachloride hydrolysis, such as Aerosil® from Evonik, siliceous earth, talc, aluminum silicates, magnesium silicates, calcium carbonates, etc.
Suitable stabilizers comprise typical UV absorbers such as oxanilides, triazines, and benzotriazole (the latter available as Tinuvin® grades from BASF SE, Ludwigshafen), and benzophenones. They can be used alone or together with suitable free-radical scavengers, examples being sterically hindered amines such as 2,2,6,6-tetramethylpiperidine, 2,6-di-tert-butylpiperidine or derivatives thereof, e.g., bis(2,2,6,6-tetramethyl-4-piperidyl) sebacinate. Stabilizers are used usually in amounts of 0.1% to 5.0% by weight, based on the solid components comprised in the preparation.
Pigments may likewise be comprised. Pigments, according to CD Römpp Chemie Lexikon—Version 1.0, Stuttgart/New York: Georg Thieme Verlag 1995, with reference to DIN 55943, are particulate, “organic or inorganic, chromatic or achromatic colorants which are virtually insoluble in the application medium”.
Virtually insoluble here means a solubility at 25° C. of below 1 g/1000 g of application medium, preferably below 0.5 g, more preferably below 0.25 g, very preferably below 0.1 g, and in particular below 0.05 g/1000 g of application medium.
Examples of pigments comprise any desired systems of absorption pigments and/or effect pigments, preferably absorption pigments. There are no restrictions whatsoever governing the number and selection of the pigment components. They can be adapted as desired to the particular requirements, such as the desired color impression, for example.
By effect pigments are meant all pigments which exhibit a platelet-shaped construction and impart specific decorative color effects to a surface coating. The effect pigments comprise, for example, all of the effect-imparting pigments which can be employed commonly in vehicle finishing and industrial coating. Examples of effect pigments of this kind are pure metal pigments, such as aluminum, iron or copper pigments; interference pigments, such as titanium-dioxide-coated mica, iron-oxide-coated mica, mixed-oxide-coated mica (e.g., with titanium dioxide and Fe2O3 or titanium dioxide and Cr2O3), metal-oxide-coated aluminum, or liquid-crystal pigments.
The color-imparting absorption pigments are, for example, customary organic or inorganic absorption pigments which can be used in the coatings industry. Examples of organic absorption pigments are azo pigments, phthalocyanine pigments, quinacridone pigments, and pyrrolopyrrole pigments. Examples of inorganic absorption pigments are iron oxide pigments, titanium dioxide, and carbon black.
The coating compositions of the invention, accordingly, are constituted as follows:
The substrates are coated with the coating compositions of the invention in accordance with conventional techniques which are known to the skilled person, and which involve applying at least one coating composition or formulation of the invention to the target substrate in the desired thickness, and removing the volatile constituents of the coating composition, with heating if desired (drying). This operation may if desired be repeated one or more times. Application to the substrate may be made in a known way, as for example by spraying, troweling, knife coating, brushing, rolling, roller-coating or pouring. The coating thickness is generally in a range from about 3 to 1000 g/m2 and preferably 10 to 200 g/m2.
Curing may then be carried out as described above.
Examples of suitable substrates for the coating compositions of the invention include thermoplastic polymers, particularly polymethyl methacrylates, polybutyl methacrylates, polyethylene terephthalates, polybutylene terephthalates, polyvinylidene fluorides, polyvinyl chlorides, polyesters, polyolefins, acrylonitrile-ethylene-propylene-diene-styrene copolymers (A-EPDM), polyether imides, polyether ketones, polyphenylene sulfides, polyphenylene ethers or mixtures thereof.
Mention may further be made of polyethylene, polypropylene, polystyrene, polybutadiene, polyesters, polyamides, polyethers, polycarbonate, polyvinylacetal, polyacrylonitrile, polyacetal, polyvinyl alcohol, polyvinyl acetate, phenolic resins, urea resins, melamine resins, alkyd resins, epoxy resins or polyurethanes, block or graft copolymers thereof, and blends of these.
Mention may preferably be made of ABS, AES, AMMA, ASA, EP, EPS, EVA, EVAL, HDPE, LDPE, MABS, MBS, MF, PA, PA6, PA66, PAN, PB, PBT, PBTP, PC, PE, PEC, PEEK, PEI, PEK, PEP, PES, PET, PETP, PF, PI, PIB, PMMA, POM, PP, PPS, PS, PSU, PUR, PVAC, PVAL, PVC, PVDC, PVP, SAN, SB, SMS, UF, UP plastics (abbreviated names in accordance with DIN 7728), and aliphatic polyketones.
Particularly preferred substrates are polyolefins, such as PP (polypropylene), which optionally may be isotactic, syndiotactic or atactic and optionally may be unoriented or may have been oriented by uniaxial or biaxial stretching, SAN (styrene-acrylonitrile copolymers), PC (polycarbonates), PVC (polyvinyl chlorides), PMMA (polymethyl methacrylates), PBT (poly(butylene terephthalate)s), PA (polyamides), ASA (acrylonitrile-styrene-acrylate copolymers) and ABS (acrylonitrile-butadiene-styrene copolymers), and also their physical mixtures (blends). Particular preference is given to PP, SAN, ABS, ASA and also blends of ABS or ASA with PA or PBT or PC. Very particular preference is given to polyolefins, PMMA, and PVC.
ASA is especially preferred, particularly in accordance with DE 196 51 350, and the ASA/PC blend. Preference is likewise given to polymethyl methacrylate (PMMA) or impact-modified PMMA.
A further-preferred substrate for coating with the coating compositions of the invention are metals, which, if desired, may have been pretreated with a primer.
As far as the type of metal is concerned, suitable metals may in principle be any desired metals. In particular, however, they are metals or alloys of the kind customarily employed as metallic materials of construction, requiring protection against corrosion.
The surfaces in question are in particular those of iron, steel, Zn, Zn alloys, Al or Al alloys. These are the surfaces of elements composed entirely of the metals or alloys in question. Alternatively, the elements may have been only coated with these metals and may themselves be composed of materials of other kinds, such as other metals, alloys, polymers or composite materials. They may be the surfaces of castings made from galvanized iron or steel. In one preferred embodiment of the present invention the surfaces are steel surfaces.
Zn alloys or Al alloys are known to the skilled person. The skilled person selects the nature and amount of alloying constituents in accordance with the desired end-use application. Typical constituents of zinc alloys comprise, in particular, Al, Pb, Si, Mg, Sn, Cu or Cd. Typical constituents of aluminum alloys comprise, in particular, Mg, Mn, Si, Zn, Cr, Zr, Cu or Ti. The alloys may also be Al/Zn alloys in which Al and Zn are present in an approximately equal amount. Steel coated with alloys of these kinds is available commercially. The steel may comprise the customary alloying components known to the skilled person.
Also conceivable is the use of the coating compositions of the invention for treating tin-plated iron/steel (tinplate).
The coating compositions and formulations of the invention are additionally suitable for coating substrates such as wood, paper, textile, leather, nonwoven, plastics surfaces, glass, ceramic, mineral building materials, such as cement moldings and fiber-cement slabs, or coated or uncoated metals, preferably plastics or metals, particularly in the form of sheets, more preferably metals.
The polyisocyanates, coating compositions or coating formulations of the invention are suitable as or in exterior coatings, i.e., applications where they are exposed to daylight, preferably parts of buildings, interior coatings, and coatings on vehicles and aircraft. In particular the polyisocyanates and coating compositions of the invention are used as or in automotive clearcoat and topcoat material(s). Further preferred applications are in can coating and coil coating.
They are particularly suitable for use as primers, surfacers, pigmented topcoat materials, and clearcoat materials in the segments of industrial, wood, automotive, especially OEM, coating, or decorative coating. The coating compositions are especially suitable for applications where there is a need for particularly high application reliability, external weathering resistance, optical qualities, solvent resistance and/or chemical resistance.
Additionally it has been found that polyisocyanates of the invention which carry silyl groups are capable of forming a gradient within a coating (also referred to as stratification), with which hardness and elasticity in the coating can be improved simultaneously.
Hardness and elasticity are often mutually contradictory properties—that is, as the hardness of a coating goes up, its elasticity often goes down, and vice versa.
This hardness is required on the outside of a coating, in order to improve the scratch resistance, for example, while the elasticity of a coating is necessary within the coating in order to improve, for example, the resistance to stone chipping. This has hitherto been achieved by application of at least two different coating compositions each exhibiting the desired properties, in separate coating and drying and/or curing steps. Through the use of the silyl group-bearing polyisocyanates of the invention, this is now possible in one application in polyurethane paints as well.
The examples which follow are intended to illustrate the properties of the invention but without restricting it.
Parts in this text, unless indicated otherwise, are by weight.
Preparation of a Polyisocyanate Containing Allophanate Groups from 1,6-Hexamethylene Diisocyanate (HDI) and Allyl Alcohol
336 g of hexamethylene diisocyanate (2.0 mol) were admixed with 11.6 g of allyl alcohol (0.2 mol) and heated to 80° C. Added to the clear solution were 200 ppm of (2-hydroxypropyl)-N,N,N-trimethylammonium 2-ethylhexanoate solution (DABCO® TMR from AirProducts). The mixture was held at 80° C. for 30 minutes. The NCO content was 40.8%. The mixture was admixed with 0.2 ml of diethylhexyl phosphate. Unreacted monomer was removed in a thin-film evaporator under 5 mbar with an external temperature of 165° C. The product showed an NCO content of 20.8% and a viscosity of 260 mPas. The weight ratio of polyisocyanate containing isocyanurate groups (not shown in the reaction scheme) to polyisocyanate containing allophanate groups was 1.6 (according to GPC analysis).
The product was characterized by IR (
The reactions were carried out as indicated and the products were characterized by IR and 1H-NMR spectroscopy.
The polyisocyanate containing allophanate groups, and also the products VF 49, VF 52 and 56 are oils of low viscosity, whereas the triply functionalized compound is a high-viscosity oil.
The surface tensions determined were as follows:
polyisocyanate containing allophanate groups 41.84±0.80 mN/m
VF 52: 42.14±0.99 mN/m
VF 49: 29.49±0.78 mN/m
VF 56: 31.36 mN/m
It is seen that the introduction of silyl groups lowers the surface tension.
5 g of the above-prepared polyisocyanate containing allophanate groups were dissolved in 20 mL of dry THF, 2.6 mL of triethoxysilane from ABCR were added, the solution was heated to 65° C., and, with vigorous stirring, 50 μl of a solution of Pt-divinyltetramethyldisiloxane (2.1% Pt) in xylene from ABCR Gelest were added. The progress of the reaction was monitored via 1H-NMR spectroscopy. After a reaction time of 3 hours, a further 50 μl of the catalyst solution were added. After a reaction time of 17 hours, the solvents were distilled off under reduced pressure at 40° C. This gave the product VF 49 as a pale yellow oil.
The product was characterized by IR (
10 g of the above-prepared polyisocyanate containing allophanate groups were reacted for 24 hours in 50 mL of toluene at 80° C. with 1.7 mL of allyl alcohol from Aldrich, giving, following distillative removal of the solvents, a product VF 52 having on average two allyl groups. 5 g of this product were dissolved in 15 ml of absolute THF. 4.1 mL of HSi(OEt)3 from ABCR were added and the solution was heated to 65° C. With vigorous stirring, 100 μl of a solution of Pt-divinyltetramethyldisiloxane (2.1% Pt) in xylene from ABCR Gelest were added. After 3 hours, the solvents were distilled off under reduced pressure at 40° C. This gave the product VF 56 as a pale yellow oil.
10 g of the above-prepared polyisocyanate containing allophanate groups were reacted for 24 hours in 50 mL of toluene at 80° C. with 3.5 mL of allyl alcohol from Aldrich, giving, following distillative removal of the solvents, a product VF 53 having on average three allyl groups. 5 g of this product were dissolved in 15 ml of absolute THF. 5.4 mL of HSi(OEt)3 from ABCR were added and the solution was heated to 65° C. With vigorous stirring, 100 μl of a solution of Pt-divinyltetramethyldisiloxane (2.1% Pt) in xylene from ABCR Gelest were added. After 3 hours, the solvents were distilled off under reduced pressure at 40° C. This gave the product VF 57 as a viscous, pale yellow oil.
2 g of the product VF 52 from Example 2, having on average two allyl groups, were dissolved in 10 ml of THF. 1.1 mL of HSI(OEt)3 from Aldrich were added and the solution was heated to 65° C. With vigorous stirring, 50 μl of a solution of Pt-divinyltetramethyldisiloxane (2.1% Pt) in xylene from ABCR Gelest were added. After 3 hours, the solvents were distilled off under reduced pressure at 40° C. This gave the product VF 66 as a viscous, pale yellow oil.
| Number | Date | Country | Kind |
|---|---|---|---|
| 13177260.0 | Jul 2013 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP14/64689 | 7/9/2014 | WO | 00 |
