Patent Grant
11286335
This application is a 35 U.S.C. § 119 patent application which claims the benefit of European Application No. 18172951.8 filed May 17, 2018, which is incorporated herein by reference in its entirety.
The present invention provides compositions comprising at least one epoxy resin, at least one cyclic amine and a salt of a very strong Brønsted acid.
Epoxy resins, especially those that are prepared from bisphenol A and epichlorohydrin, are known raw materials for the production of high-quality casting resins, coating compositions, composites and adhesives. Aromatic epoxy resins cured with polyamines have not only good chemical and solvent resistance but also good bond strength on many substrates.
The curing of epoxy-amine coating systems can be accelerated using catalysts (U.S. Pat. Nos. 3,492,269 A, 5,470,896 A, GB 1,105,772 A).
EP 0 083 813 A1, EP 2 957 584 A1, U.S. Pat. Nos. 5,441,000 A, 5,629,380 A, WO 96/09352 A1 disclose the catalysed curing of epoxy resins with various amines.
Cyclic amines show advantages in epoxy curing. U.S. Pat. No. 8,951,619 B2 and U.S. Pat. No. 9,006,385 B2 disclose, inter alia, the catalyst-free curing of epoxy resins with N-substituted piperazines.
CN 106905816 A, CN 106833261 A, JP H08-113876 A, DE 1 954 701 A1, CA 2 165 585 A1 and U.S. Pat. No. 3,055,901 A disclose the catalyst-free curing of epoxy resins with aminoethylpiperazine.
U.S. Pat. No. 8,980,979 B2 discloses the curing of an epoxy resin with, inter alia, a cyclic diamine selected from piperazine and homopiperazine, optionally in the presence of a catalyst.
EP 0 969 030 A1 discloses epoxy/amine coating systems wherein the amine component is an aliphatic amine. The compositions may include a catalyst. In the examples, the hardener used is aminoethylpiperazine.
U.S. Pat. No. 4,775,734 A discloses the curing of epoxy resins with aminoethylpiperazine using catalytic amounts of tetrafluoroborate or hexafluorophosphate salts of various amines. Also disclosed in comparative examples (Example 2) is an attempt to cure epoxy resins with aminoethylpiperazine in the presence of lithium tetrafluoroborate. However, there is no reaction at the ratio of epoxy groups:NH groups used. In addition, in a comparative example (in Example 9), epoxy resin is cured with aminoethylpiperazine in the presence of imidazoline. However, the imidazoline used has the disadvantage that it is not storage-stable in the presence of moist materials and has a tendency to yellow.
EP 3 255 078 A1 discloses epoxy resin compositions comprising at least one epoxy compound, 2-(2,2,6,6-tetramethylpiperidin-4-yl)propane-1,3-diamine, and optionally a catalyst which may be an inorganic salt inter alia.
WO 2017/074810 A1 discloses compositions comprising an epoxy resin, a polyetheramine and a further amine hardener which may be an imidazole or imidazoline inter alia, and a metal triflate catalyst.
A common factor in the prior art compositions is that they cure too slowly or only at high temperatures.
For many applications, however, it is important that surface curing or complete through-curing proceeds particularly rapidly or else at low temperatures. Firstly, productivity can be increased or else the next processing step can be accelerated. The latter is important particularly in cold regions in order, for example, to provide ships or pipelines with a corrosion protection coating, such that continued operation is possible there in winter as well.
The problem addressed in the present context is thus that of providing epoxy systems that react much more quickly under the same conditions than the formulations known to date. Another problem addressed was that of providing epoxy formulations that partly or fully cure more quickly than is possible to date at temperatures well below room temperature.
These present problems are solved by the compositions according to the invention comprising
Preferably, the ratio of the epoxy groups in the epoxy resin to the sum total of all NH groups in all amines is 0.5:1 to 1.5:1, preferably 0.8:1 to 1.2:1, most preferably 0.9:1 to 1.1:1. “All amines” are understood here to mean cyclic amines of the formula (I) and amines d) not covered by formula (I) that are described hereinafter. A corresponding reaction has the advantage that this increases the crosslinking density and the molar mass, and hence improves mechanical properties, chemical stability and scratch resistance. Moreover, no unreacted constituents remain in the coating, which can either enter into unwanted side reactions, migrate out of the coating or else at least lower heat distortion resistance as plasticizer.
Component a) is at least one epoxy resin. All epoxy compounds are suitable in principle for this purpose.
Suitable epoxy compounds are described, for example, in EP 675 185 A2. Useful compounds are a multitude of the known compounds containing more than one epoxy group, preferably two epoxy groups, per molecule. These epoxy compounds may be either saturated or unsaturated and aliphatic, cycloaliphatic, aromatic or heterocyclic and may also have hydroxyl groups. They may additionally contain such substituents that do not cause any troublesome side reactions under the mixing or reaction conditions, for example alkyl or aryl substituents or ether moieties.
Preferred epoxy compounds here are glycidyl ethers which derive from polyhydric phenols, especially bisphenols and novolaks, and which have molar masses based on the number of epoxy groups ME (“epoxy equivalent weights”, “EV value”) between 100 and 1500 g/eq, but especially between 150 and 250 g/eq.
Particularly preferred epoxy compounds derive from resorcinol, hydroquinone, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), isomer mixtures of dihydroxydiphenylmethane (bisphenol F), 4,4′-dihydroxydiphenylcyclohexane, 4,4′-dihydroxy-3,3′-dimethyldiphenylpropane, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxybenzophenone, bis(4-hydroxyphenyl)-1,1-ethane, bis(4-hydroxyphenyl)-1,1-isobutane, 2,2-bis(4-hydroxy-tert-butylphenyl)propane, bis(2-hydroxynaphthyl)methane, 1,5-dihydroxynaphthalene, tris(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl) ether, bis(4-hydroxyphenyl) sulfone, and the chlorination and bromination products of the aforementioned compounds (for example tetrabromobisphenol A).
Very particular preference is given to using liquid diglycidyl ethers based on bisphenol A and bisphenol F having an epoxy equivalent weight of 150 to 200 g/eq.
It is also possible with preference to use polyglycidyl ethers of polyalcohols, for example ethane-1,2-diol diglycidyl ether, propane-1,2-diol diglycidyl ether, propane-1,3-diol diglycidyl ether, butanediol diglycidyl ether, pentanediol diglycidyl ether (including neopentyl glycol diglycidyl ether), hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, higher polyoxyalkylene glycol diglycidyl ethers, for example higher polyoxyethylene glycol diglycidyl ethers and polyoxypropylene glycol diglycidyl ethers, co-polyoxyethylene-propylene glycol diglycidyl ethers, polyoxytetramethylene glycol diglycidyl ethers, polyglycidyl ethers of glycerol, of hexane-1,2,6-triol, of trimethylolpropane, of trimethylolethane, of pentaerythritol or of sorbitol, polyglycidyl ethers of oxyalkylated polyols (for example of glycerol, trimethylolpropane, pentaerythritol, inter alia), diglycidyl ethers of cyclohexanedimethanol, of bis(4-hydroxycyclohexyl)methane and of 2,2-bis(4-hydroxycyclohexyl)propane, polyglycidyl ethers of castor oil, triglycidyl tris(2-hydroxyethyl)isocyanurate.
Further useful components A preferably include: poly(N-glycidyl) compounds obtainable by dehydrohalogenation of the reaction products of epichlorohydrin and amines such as aniline, n-butylamine, bis(4-aminophenyl)methane, m-xylylenediamine or bis(4-methylaminophenyl)methane. However, the poly(N-glycidyl) compounds also include triglycidyl isocyanurate, triglycidylurazole and oligomers thereof, N,N′-diglycidyl derivatives of cycloalkyleneureas and diglycidyl derivatives of hydantoins.
In addition, it is also possible with preference to use polyglycidyl esters of polycarboxylic acids which are obtained by the reaction of epichlorohydrin or similar epoxy compounds with an aliphatic, cycloaliphatic or aromatic polycarboxylic acid such as oxalic acid, succinic acid, adipic acid, glutaric acid, phthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, naphthalene-2,6-dicarboxylic acid and higher diglycidyl dicarboxylates, for example dimerized or trimerized linolenic acid. Examples are diglycidyl adipate, diglycidyl phthalate and diglycidyl hexahydrophthalate.
Also preferred are glycidyl esters of unsaturated carboxylic acids and epoxidized esters of unsaturated alcohols or unsaturated carboxylic acids. In addition to the polyglycidyl ethers, it is possible to use small amounts of monoepoxides, for example methyl glycidyl ether, butyl glycidyl ether, allyl glycidyl ether, ethylhexyl glycidyl ether, long-chain aliphatic glycidyl ethers, for example cetyl glycidyl ether and stearyl glycidyl ether, monoglycidyl ethers of a higher isomeric alcohol mixture, glycidyl ethers of a mixture of C12 to C13 alcohols, phenyl glycidyl ether, cresyl glycidyl ether, p-tert-butylphenyl glycidyl ether, p-octylphenyl glycidyl ether, p-phenylphenyl glycidyl ether, glycidyl ethers of an alkoxylated lauryl alcohol, and also monoepoxides such as epoxidized monounsaturated hydrocarbons (butylene oxide, cyclohexene oxide, styrene oxide), in proportions by mass of up to 30% by weight, preferably 10% to 20% by weight, based on the mass of the polyglycidyl ethers.
A detailed enumeration of the suitable epoxy compounds can be found in the handbook “Epoxidverbindungen and Epoxidharze” [Epoxy Compounds and Epoxy Resins] by A. M. Paquin, Springer Verlag, Berlin 1958, Chapter IV, and in Lee Neville “Handbook of Epoxy Resins”, 1967, Chapter 2.
Useful epoxy compounds preferably include glycidyl ethers and glycidyl esters, aliphatic epoxides, diglycidyl ethers based on bisphenol A and/or bisphenol F, and glycidyl methacrylates. Other examples of such epoxides are triglycidyl isocyanurate (TGIC, trade name: ARALDIT 810, Huntsman), mixtures of diglycidyl terephthalate and triglycidyl trimellitate (trade name: ARALDIT PT 910 and 912, Huntsman), glycidyl esters of Versatic acid (trade name: CARDURA E10, Shell), 3,4-epoxycyclohexylmethyl 3′,4′-epoxycyclohexanecarboxylate (ECC), ethylhexyl glycidyl ether, butyl glycidyl ether, pentaerythrityl tetraglycidyl ether (trade name: POLYPDX R 16, UPPC AG), and other Polypox products having free epoxy groups. It is also possible to use mixtures of the epoxy compounds mentioned.
Particularly preferred epoxy resins are polyepoxides based on bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, 4,4′-methylenebis[N,N-bis(2,3-epoxypropyl)aniline], hexanediol diglycidyl ether, butanediol diglycidyl ether, trimethylolpropane triglycidyl ether, propane-1,2,3-triol triglycidyl ether, pentaerythritol tetraglycidyl ether and diglycidyl hexahydrophthalate.
Preference is given to using mixtures of the aforementioned epoxy compounds as component A).
Useful cyclic amines b) in principle include any compounds which, as NH carrier, have exactly one cyclic, i.e. ring-attached, NH group and at least one non-ring-attached primary or secondary amino group. In addition, however, the amines used in accordance with the invention may also have tertiary amino groups that are unreactive.
The amines b) have the formula (I)
The cyclic amines are saturated or partly unsaturated in relation to the ring shown in formula (I). Corresponding amines react more quickly than corresponding aromatic amines and imidazolines. Further rings optionally present in the cyclic amine may be not only saturated or unsaturated, but also aromatic.
Preferred cyclic amines are saturated in relation to the ring shown in formula (I).
Preferably, at least one of the R1, R2, R3 and R4 radicals=H. In that case, the carbon atoms adjacent to the ring-attached amino group, since at least one of the R1, R2, R3 and R4 radicals=H, are unsubstituted at at least one site overall. Corresponding amines react more quickly than amines in which all four R1, R2, R3 and R4 radicals≠H. Further preferably at least two, even further preferably at least three and more preferably all of the R1, R2, R3 and R4 radicals=H.
In the X radical, if present, A1, A2 and A3 are independently alkylene or alkenylene radicals. These may in turn bear organic radicals. If the alkylene and/or alkenylene radicals themselves have one or more organic radicals, any two organic radicals are selected from the organic radicals in the alkylene and/or alkenylene radicals may also form one or more further rings with one another or with any organic R1 to R5 radicals present.
Preferably, A1, A2 and A3, if present, each independently have the formula (III))
—(CR7R8)x—(CR9═CR10)y—(CR11R12)z— (III)
in which, independently of one another,
The indices x, y and z, in accordance with their pertinence to the A1, A2 and A3 radical, may preferably also be referred to as indices x1, y1 and z1, as x2, y2 and z2 and as x3, y3 and z3.
Preferably, X has a chain length of 2 to 15 atoms. Preferably, the sum total of all x, ½·y and z and of m, o, q and s has a value from 2 to 15, further preferably a value from 2 to 8, even further preferably a value from 2 to 5 and most preferably a value from 2 to 4. In other words, preferably, 2≤m+o+q+s+x1+1/2·y1+z1+x2+½·y2+z2+x3+1/2·y3+z3≤15. Further preferably 2≤m+o+q+s+x1+1/2·y1+z1+x2+½·y2+z2+x3+1/2·y3+z3≤8, further preferably 2≤m+o+q+s+x1+1/2·y1+z1+x2+½·y2+z2+x3+1/2·y3+z3≤5, most preferably 2≤m+o+q+s+x1+1/2·y1+z1+x2+½·y2+z2+x3+1/2·y3+z3≤4.
The amines of the formula (I) are (optionally bi/poly)cyclic compounds since both carbon atoms adjacent to the amino group are attached on either side to the substituted (hetero)alkylene radical of the formula (II).
Further preferably, formula (I), as well as the nitrogen atom of the ring-attached NH group, has not more than one further heteroatom in the cycle, i.e. X preferably has the formula (Ha)
X═—(CR7R8)x—(Y)o—(CR11R12)z— (IIa)
with
Correspondingly, in formula (I), any two organic radicals selected from R1 to R8, R11 and R12 may also form one or more further rings, with the proviso that at least one of the radicals selected from R1 to R8, R11 and R12 present is substituted by at least one —NHR6 or —NH2 group, where R6=organic radical.
In the preferred case that x=2-4 and 0 and z=0, the resulting compounds are saturated heteroalkyl ring systems having one NH group. Preferred compounds are pyrrolidines, piperidines and azepanes. In the preferred case that x=1-3, o=1 and z=0-2, the compounds are saturated heteroalkyl ring systems having one NH group and a further heteroatom in the cycle that is not part of a further cyclic NH group. Preferred compounds are singly N-substituted pyrazolidines, singly N-substituted imidazolidines, oxazolidines, thiazolidines, singly N-substituted piperazines, morpholines, thiomorpholines, singly N-substituted diazepanes, oxazepanes and thiazepanes. It is thus preferable, in formula (IIa), that x=1-4, o=0 or 1 and z=0-2.
However, it is also possible to use compounds having three heteroatoms in the cycle. Preference is given especially to the group of the triazinanes and the triazepanes. Especially these compounds may be in bridged form, as, for example, in the case of a particularly preferred group of compounds of the 1,3,6-triazabicyclo[4.2.1]nonanes.
The R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11 and R12 radicals may be organic radicals. Preferred organic radicals are alkyl, alkenyl, alkynyl, aryl or aralkyl radicals. These may be heteroatom-substituted within their chain and/or their substituents. Preferred organic radicals are alkyl, alkenyl, alkynyl, aryl or aralkyl radicals which may bear one or more ether, carboxyl, amino, amido, urea, carbamate, carbonate, amidino or guanidino groups within the chain. In addition, preferred organic radicals may bear one or more substituents selected from organic radicals optionally having ether, carboxyl, amino, amido, urea, carbamate, carbonate, amidino or guanidino groups that may optionally also be substituted by hydroxyl, nitrile or halogen radicals or may themselves be hydroxyl, nitrile or halogen radicals.
Preferred compounds of the formula (I) are aminoethylpiperazine (AEP, 1-(2-aminoethyl)piperazine), 1-(3-aminopropyl)piperazine, 1-imidazolidinoethanamine, imidazolidino-N-propanamine, α-methyl-1-piperazinethanamine, 2,6-dimethyl-1-piperazinoethanamine, 2-amino-1-(piperazin-1-yl)ethanone, 4-(2-aminoethyl)piperidine, 3-(2-aminoethyl)piperidine and 2-(2-aminoethyl)piperidine.
The compounds of the formula (I) may also be used in a mixture.
The compositions according to the invention further comprise at least one salt of a very strong Brønsted acid with a counterion selected from metal ions, metal-containing ions, phosphonium ions and unsubstituted ammonium ions. Corresponding salts serve as catalyst. Such a very strong acid in the present context is understood to mean a salt having a pKa (or in the case of polyprotic acids having a pKa of the first protolysis stage) of not more than −9.01. Preferably, the pKa of the very strong acid is between −9.5 and −25, more preferably between −9.9 and −21.
The pKa is defined as the negative decadic logarithm of the equilibrium constant Ka and is considered to be a measure of the strength of an acid. The smaller a pKa, the stronger the acid. The pKA is determined as disclosed in F. G. Bordwell, “Equilibrium Acidities in Dimethylsulfoxide Solution”, Acc. Chem. Res. 1988, 21, 456-463.
Preferred salts are the corresponding salts of the very strong acids collated in the first column in Table 1 below:
The counterions of these very strong acids are selected from metal ions, metal-containing ions, phosphonium ions and unsubstituted ammonium ions. Preferred metal ions are alkaline earth metal cations, especially beryllium, magnesium, calcium, strontium and barium ions, and lithium, aluminium, bismuth, zinc and europium ions.
Metal-containing ions are ions that contain at least one metal but are not pure metal ions. They are preferably metal compound ions, for example tetraphenylstibonium ions.
The counterions may also be ammonium ions (NH4−) or optionally alkylated and/or arylated phosphonium ions. Very particular preference is given to ammonium ions.
Preferred salts of very strong acids are calcium triflate, europium triflate, barium triflate, aluminium triflate, bismuth triflate, lithium triflate, lithium perchlorate, barium perchlorate, lithium hexafluorophosphate and zinc perchlorate. Very particular preference is given to calcium triflate, europium triflate, lithium hexafluorophosphate and lithium perchlorate.
Preference is given to salts having good solubility in organic media (e.g. benzyl alcohol), i.e. salts having a solubility of at least 10 g/1 in benzyl alcohol at 20° C.
Preferably, the compositions according to the invention may further include d) amines not covered by the formula (I) and/or e) further auxiliaries or additives.
Amines d) not covered by the formula (I) are preferably di- or polyamines. These may be monomeric, oligomeric and/or polymeric compounds. Preferred monomeric and oligomeric compounds are selected from the group consisting of diamines, triamines and tetramines. The amine group of the di- or polyamines d) may be attached to a primary, secondary or tertiary carbon atom, preferably to a primary or secondary carbon atom. It is also possible to use mixtures of di- and/or polyamines as component d).
Components d) used may be the following amines, alone or in mixtures:
It is also possible to use mixtures of the aforementioned di- or polyamines as component d).
Preferred further auxiliaries and admixtures e) may be the compounds customary in epoxy chemistry. Preferred auxiliaries and admixtures e) are pigments, solvents, levelling agents, modifiers, for example benzyl alcohol or nonylphenol, degassing agents, flatting agents, reactive diluents, and conventional catalysts such as salicylic acid, bisphenol A, 2,4,6-tris(dimethylaminomethyl)phenol and phenol derivatives.
In a preferred embodiment, no further amines d) not covered by the formula (I) are used. In a preferred embodiment, no further conventional catalysts are used, meaning that the possible auxiliaries and admixtures are limited to pigments, solvents, levelling agents, modifiers, degassing agents, flatting agents and reactive diluents.
The composition of components a) to e) in the composition according to the invention is preferably the following proportions by weight, based on the total mass of the composition:
Preferably, in addition, the proportion by weight of the amines b) based on the total mass of the amines b) and d) is at least 10% by weight, more preferably at least 30% by weight, even more preferably at least 50% by weight and more preferably still at least 70% by weight.
The invention further provides a process for producing a composition according to the invention, in which at least one epoxy resin a), at least one cyclic amine b) and at least one salt of a very strong acid c) are mixed with one another.
The invention further provides for the use of the compositions according to the invention as a casting resin, coating composition, composite or adhesive or as a constituent thereof.
To demonstrate the particular reactivity of the catalysts claimed, model experiments are first compared with one another. For this purpose, 0.025 mol (3.75 g) of 1,2-epoxy-3-phenoxypropane is added to a mixture of 22.68 g of toluene (solvent) and 2.08 g of tetradecane (internal standard). To this are added 0.025 mol (2.13 g) of piperidine, and 0.06 g of the particular catalyst. Immediately after the mixing, a GC is taken and the content of 1,2-epoxy-3-phenoxypropane is compared with the content of tetradecane. After 4 h at room temperature, by means of GC analysis, the residual content of 1,2-epoxy-3-phenoxypropane (EP) is ascertained (calibrated by the internal tetradecane standard). This gives the following results:
Comparison of the Catalysts
To demonstrate the particular reactivity of the amines claimed, model experiments are first compared with one another. For this purpose, 0.025 mol (3.75 g) of 1,2-epoxy-3-phenoxypropane is added to a mixture of 22.68 g of toluene (solvent) and 2.08 g of tetradecane (internal standard). To this are added 0.025 NH equivalent of an amine and 0.06 g of calcium triflate. Immediately after the mixing, a GC is taken and the content of 1,2-epoxy-3-phenoxypropane is compared with the content of tetradecane. After 4 h at room temperature, by means of GC analysis, the residual content of 1,2-epoxy-3-phenoxypropane (EP) is ascertained (calibrated by the internal tetradecane standard). This gives the following results:
It is clearly apparent from the model experiments that the compositions claimed are much more reactive than conventional systems.
100 parts aminoethylpiperazine (AEP, Aldrich) are intimately mixed with 446 parts Epikote 828 (epoxy equivalent 190, Hexion) and a DSC is taken immediately thereafter.
0.5 part calcium triflate (Aldrich) is dissolved in 100 parts aminoethylpiperazine (AEP, Aldrich) and this mixture is intimately mixed with 446 parts Epikote 828 (epoxy equivalent 190, Hexion) and a DSC is taken immediately thereafter.
In the inventive experiment, the exothermic peak is 23° C. lower, and the onset of this exothermic peak is 29° C. lower. The reactive composition according to the invention is thus much more reactive.
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| Number | Date | Country | |
|---|---|---|---|
| 20190352450 A1 | Nov 2019 | US |
