TW200911866A - Catalyst for curing epoxides - Google Patents

Abstract

The use of 1, 3-substituted imidazolium salts of the formula l in which R1 and R3 independently of one another are an organic radical having 1 to 20 C atoms, R2, R4, and R5 independently of one another are an H atom or an organic radical having 1 to 20 C atoms, it also being possible for R4 and R5 together to form an aliphatic or aromatic ring, X is a carboxylate or thiocarboxylate, and n is 1, 2 or 3, with the exception as imidazolium salts of 1-ethyl-2, 3-dimethylimidazolium acetate and 1-ethyl-2, 3-dimethylimidazolium acetate-acetic acid complex, as latent catalysts for curing compositions comprising epoxy compounds.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the use of a 1,3-substituted imidazole rust salt of the formula I as a latent catalyst for curing a composition comprising an epoxy compound,

Wherein: R1 and R3 are independently from each other having 1 to 20 (: atomic organic groups; R2, R4 and R5 are independently H atoms or have 1 to 2 ( (: atomic organic groups, R4 and R5- It is also possible to form an aliphatic or aromatic ring; X is a tickate or thiorexate; and η is 1, 2 or 3, wherein 1-ethyl-2,3-dimethylimidazolium acetate and ethyl acetate Except for the imidazolium salt of the 2,3-dimethylimidazolium-acetic acid complex. [Prior Art] Epoxy compounds are used to produce coatings, and are used for a number of other purposes. In liquid form during H ( In the absence of a solvent system in a suitable solvent). Epoxy 4 畺. In use, it is a cured coating used as an adhesive to create a shaped article. In such applications, it is usually in a processing agent. The solution form or liquid, 1% by weight of the epoxy compound usually has a low molecular weight cured. There are many known for curing, which are cured. For solidity, epoxy with at least two epoxy groups. The compound begins with an epoxy compound having at least two amine groups or at least a group, It is possible to combine at least one amine group of an acid anhydride group. 131923.doc 200911866 * The acid anhydride compound is cured by addition polymerization (chain extension) via Α h A p + , usually until the desired curing. The amine-based compound or anhydride compound having reactivity is not added. Therefore, the system in question is referred to as a two-component (2K) system. It is also possible to use a homopolymerization or copolymerization of an epoxy compound. Catalysts have been used to include catalysts that are only active toward temperature (potentially sensitive media). _ Latent (4) has the advantages of the material component (10) system, and the ring is replaced by the ring. Oxygen compounds can contain latent catalysts without any unnecessary early fixation. Ocean 5, commercially available latent catalysts include trifluoride and amine adducts. (BF3. monoethylamine), a fourth scale compound, and cyanide (dicy).

Journal of P〇lymer Science: P〇lymer Letters Edition, Vol. 21, 633. 638 (1983) describes the use of ls3_dialkyl octagonal rust salts for this purpose. Its decomposition at above 175 ° C releases the 丨-alkylimidazole, which in turn leads to the solidification of the 1-alkylimidazole. The structure of the cation has been changed, and halide ions (milk ions and ion-filling ions) have been used as anions. U DE-A 24 16408 discloses imidazolium borate such as imidazolium tetraphenylborate or tetraammonium butyl acid. US 3 63 5 894 describes a latent catalyst as an epoxy compound, a 3 -dialkylimidazolium rust salt whose anion is selected from the group consisting of chloride, bromide and ruthenium ions.

Kowalczyk and Spychaj, Polimery (Warsaw, Poland) (2003), 48(11/12), 833-835 describe i-butyl-3-methylimidazole rust as tetrafluoroborate as a latent catalyst for epoxy compounds use. The catalyst does not open until 1 90 °C. 131923.doc 200911866 is active.

Sun, Zhang and Wong, Journal of Adhesion Science and

Technology (2004), 18(1), 109-121 discloses the use of ethyl _3_methylimidazole hexafluorophosphate as a latent catalyst. It is only active at 196 °c. JP 2004217859 uses imidazolium tetraalkylborate or imidazole rust of dialkyldithiocarbamate. It is activated by exposure to high energy light. EP 0 458 502 discloses a number of extremely different catalysts for epoxy compounds.

The list includes 1-ethyl-2,3-dimethylimidazolium acetate (in the formula!

Rl = ethyl, R2 = fluorenyl, and R3 = methyl) and ethyl dimethyl imidazolium-acetate complex. The potential of cockroaches should be observed. 热u hot-mixing is stable for as long as possible under standard storage conditions at room temperature, so it is suitable for storage in 1K systems. However, in use ^. The temperature required for curing should be too high, and particularly preferably should be lower than 2 ° C ° lower curing temperature so that energy costs can be saved and unnecessary = secondary reactions can be avoided. Although lower curing temperatures are required, the mechanical and performance characteristics of the cured system should not be compromised as much as possible. Hardness, flexibility, strong bond, etc.) 4 characteristics (example is good. Xiliangliang and right may even more [invention] The imidazole rust salt of the medium and the 咋乍 is π-containing. Tungsten salt and epoxidation Therefore, it has been found that the paper of the formula I is fine. The use of the bismuth-containing catalyst and the use of the chelating agent and the illuminating composition of the latent catalyst. Strontium salt The present invention uses the 1,3_substituted imidazolium salt of the formula I: broad-R5

R1 Χπ—where:

R1 and R3 independently of each other are from 1 to 20 c atoms having from 1 to 2 fluorene atoms, and it is also possible to form the lipids R2, R4 and R5 independently of each other as a ruthenium atom or having from 1 to 10 C atoms. The organic group, with "a family or an aromatic ring; X is a tickate or thiorexate; and η is 1, 2 or 3. The list of ΕΡ 〇 458 5G2 is revealed as the „ rice rust salt Ethyl _ 2,3-dimethylimidazolium (in the formula β ' = ethyl, methyl, and ^ methyl) and 1-ethyl-2,3-dimethyl succinate And for this reason 'except for it has been excluded herein. Preferably, 'R1 and R3, independently of each other, have an i-c atomic group. The organic group may also contain other heteroatoms, more specifically, a hydroxyl group, an ether group, an ester group or a carbonyl group. Specifically, R1 and R3 are each independently a hydrocarbon group, and may further contain, in addition to carbon and hydrogen, a via group, an energy group or a record. Preferably, RUR3 are, independently of each other, a hydrocarbyl group having from 1 to 20 C atoms, more specifically 1 to C atoms, which does not contain other heteroatoms such as oxygen or nitrogen. ). The hydrocarbyl group may be aliphatic (in this case, also includes an unsaturated aliphatic group) or an aromatic group, or may contain both an aromatic group and an aliphatic group. Mention may be made; examples of the J:k group include a phenyl group, a benzyl group, a phenyl group or a benzyl group substituted by a plurality of c 1 to C 4 alkyl groups, or a decyl group and a dilute group. Allyl. In particular, R1 and R3 are independently of each other (: 1 to (:: 1 〇 alkyl, allyl or indoylhydrazine. More preferably, the alkyl group is .1 to .6 alkyl, and in one In a particular embodiment, 'alkyl is C1 to C4 alkyl. Rarely, R1 and R3 are, independently of each other, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl or third Butyl, allyl or benzyl, especially methyl, ethyl, n-propyl and n-butyl. In a particular embodiment: R1 and R3 are methyl; R1 and R3 are ethyl R1 is methyl and R3 is ethyl; R1 is methyl and R3 is n-propyl; R1 is methyl and R3 is n-butyl; R1 is methyl and R3 is allyl; R1 is ethyl and R3 Is an allyl group; R1 is a methyl group and R3 is a benzyl group; R1 is an ethyl group and R3 is a benzyl group. R2, R4 and R5 are each independently a ruthenium atom or a 131923 having 1 to 2 c c atoms. Doc -11 - 200911866 T base, R4 and R5 may also form an aliphatic or aromatic ring. In addition to carbon and " stack base may also contain heteroatoms (such as nitrogen or oxygen); preferably, it can Contains oxygen, more specifically, thiol, 3-position, ether or silk Oxygen is present in the form. More specifically, R2, R4 and R5 are each independently a halogen atom or a hydrocarbon group, and the hydrocarbon group may further contain, in addition to carbon and hydrogen, a minus, a base, or a base. The grounds 'R2, R4 and R5 are, independently of each other, a hydrogen atom or a hydrocarbon group having 丨 to 2 c c atoms, more specifically 1JL1_c atom, which does not contain other hetero atoms (for example, oxygen or nitrogen). An aliphatic (in this case also comprising an unsaturated aliphatic group) or an aromatic group, or may comprise both an aromatic and an aliphatic group, in which case, ... can also be shaped & aromatic or fat If the family ring is 't', the aromatic or aliphatic hydrocarbon ring may be substituted by other aromatic or aliphatic nicotinic groups (the number of ruthenium atoms (including substituents) of the unsubstituted or substituted hydrocarbon ring in this case Preferably, it may not exceed 4 Å, especially not more than 2 Å, and particularly preferably not more than 15 Å or not more than 1 〇. Examples of hydrocarbon groups which may be mentioned include phenyl, benzyl, one or more C4 alkyl substituted phenyl or benzyl, or alkyl, alkenyl, and if formed with R5 (formed by 114 and 115) The aromatic 5 or 6 membered ring or cyclohexene or % pentene)' is highly likely to be substituted by one or more C 丨 to C 1 〇, more specifically C 1 to C 4 alkyl groups. R2, R4 and R5 are each independently H atom, mountain to alkyl, C1-C8 alkenyl (such as allyl) or phenyl or benzyl. Rather, R2, R4 and R5 are mutually Independently H atom or methyl, B 131923.doc 12 200911866 base, n-propyl, isopropyl, n-butyl, t-butyl or tert-butyl, methyl 'ethyl, n-propyl and n-Butyl is especially important. In a particular embodiment, R2 is a deuterium atom independent of the other groups R4 and R5 and the remaining groups R1 and R3. The imidazole rust salt of the formula I (wherein r2 is an η atom) is particularly advantageous in the present invention; it has excellent/glutenability and latent catalyst activity in an epoxy compound. In a particular embodiment, if the anion is acetate, then R2 is a deuterium atom. In a particular embodiment:

R2, R4 and R5 are a halogen atom; R2 is a halogen atom or a C1 to C4 alkyl group, and each of R4 and r5 is an η atom or a (^ to C4 alkyl group. Specific examples of the cation of the compound of the formula I which may be mentioned include the following Each: 1-butyl-3-methylimidazolium (R1 = butyl, R3 = methyl); 1'butyl-3-ethylimidazolium (R1 = butyl, R3 = ethyl); '3--methyl pm ° sitting (Rl = methyl, R3 = methyl); 1-ethyl-3-methylimidazolium (R1 = ethyl, R3 = mercapto); 1-ethyl -2,3-dimethylimidazolium (R1 = ethyl, R2 = methyl, phantom = methyl). In formula I, η is 丨, 2 or 3; correspondingly, 'anion has one, two in salt There are one, two or three micro or three negative charges and thus a oxazolium cation. Preferably, η is 1 or 2 is a monovalent. More preferably, η is 1; therefore, the anion is preferably X Phytate or thiodecanoate. 131923.doc • 13- 200911866 For the purposes of the present invention, a carboxylic acid ester is a compound of a carboxylate group; a phase, furnace, two or three carboxyl or three thio a compound of a carboxylate group, preferably two to one, preferably one or In other words, the carboxylic acid ester comprises an organic compound having from 1 to 2 C atoms of a C atom, which contains one to three 'more preferably one carboxylate group. White in: 3⁄4: 炷I ^ π a compound of a human or a compound at the beginning of the mouth, a compound of a compound. Where appropriate, the 'aliphatic or aromatic compound may contain other functional groups as a substituent, examples being a transradical, a few or a ketone group; or other hetero atom, More specifically, it is usually a fluorine-containing gas, such as fluorine, gas or bromine, preferably fluorine. In the acid-containing vinegar containing a functional element (preferably fluorine), one or more hydrogens are replaced by dentate or fluorine. The purpose of the discussion is preferably that the aliphatic group contains the o-reductive m oxygen atom and the _ atom (four), and the acid vinegar does not contain other hetero atoms. The carboxylic acid containing _ (preferably fluorine) is brewed. Preferred package: 1 to 10 C atoms, and preferably each contains H9 elemental atoms or fluorine atoms (halo or fluoro group). In other words, the carboxylic acid ester having other functional groups includes a carboxylate having a hydroxyl group, a carbonyl group or an ether group other than the group, and the carboxylate group does not contain other functional groups or other hetero atoms. An aliphatic or aromatic compound other than the oxygen atom of the ester group that does not contain other functional groups or heteroatoms. Compounds having two carboxylate groups include, for example, anions of phthalic acid; anions of isophthalic acid And the negative ion of the dicarboxylic acid 131923.doc 200911866 sub-such as the anion of oxalic acid (pKb in the first stage is 12.77; the second stage is 9.8 丨), the anion of malonic acid (the second stage of the first stage is 8.31), anion of succinic acid (9.81 in the first stage; 8.52 in the second stage), anion in glutaric acid (pKb in the first stage is 9.66; first stage is 8.59) and adipic acid The anion (pKb in the first stage is 9-58; the second stage is 8 59). The compound having a carboxylate group includes an aromatic, aliphatic, saturated or unsaturated C1 to C20 carboxylic acid, more specifically an alkanoic acid, an alkenecarboxylic acid, an alkynecarboxylic acid, a diene retarding acid, a triene. The anion of a carboxylic acid, a hydroxycarboxylic acid or a ketocarboxylic acid, an alkanecarboxylic acid, an alkenecarboxylic acid and a dienecarboxylic acid are also known in the form of a fatty acid. Mention may in particular be made of the anion of benzoic acid (pKb 9 8); the anion of phenylacetic acid (pKb 99.69); the anion of formic acid (formate, pKb 1〇23); the anion of acetic acid (acetate, pKb 9.24), which is limited The condition is that it is not covered by the exception of "monthly item 1; an anion of acetoxyacetic acid (pL 1〇·42); or an anion of lactic acid (pKb=1〇22). Examples of the transcarboxylic acid or ketocarboxylic acid include glycolic acid (pKb ι〇 i8) or acetaldehyde (pKb 10.68). An example of a carboxylic acid containing a halogen (more specifically, containing fluorine) is a tri-acetylated core: ^(a) and trifluoroacetate]^^?). Examples of other carboxylic acids are thioether carboxylic acids such as methyl thioglycolic acid (pKb 10.28). In a preferred embodiment, the carboxylate anion in question has a pKb of less than 13, preferably less than 12, more preferably less than u, and is preferably less than 1〇.5 of 131923.doc •15- 200911866 citrate anion. Sub-destination 'in the case of 1 bar, in water or dimethyl water as a solvent, according to the present invention, the anion sufficiently has a corresponding PKb at or in. Especially when the anion is not soluble... use dimethyl hydrazine. Literature on both solvents can be found in W. In the case of (4) reacting with water in two or more stages to form a corresponding polyprotonic acid, one (four) pKb.

PKb is the negative logarithm of the basement constant Kb with the base ten, and Kb is the dissociation constant of the following reaction: Χ +Η20-^ΗΧ+〇η· The dissociation constant of the reverse reaction is the acidity constant Ka, and the corresponding ten is the bottom. The negative logarithm is pKa. If the literature references pKa, pKb can be calculated by the following simple relationship: pKa + pKb: 14 文献 The literature on pKb values and/or corresponding pKa values is found in standard commercial reference works and below the Internet. The site also found an extremely comprehensive compilation of the ruler Williams: http://research.chem.psu.edu/brpgroup/pKa__compilation.pdf The map compiled in the list is taken from the original references including:

Brown, H.C., et al., in Braude, E.A. and F.C. Nachod, determination of Organic Structures by Physical Methods, Academic Press, New York, 1955 (two oxonic acid);

Dawson, R.M.C., et al, data for Biochemical Research, Oxford, Clarendon Press, 1959 (rebel); 131923.doc -16- 200911866

Dippy, Hughes, S.R-C. Rozanski, A J. Chem Soc. 1959, 2492 (substituted acetic acid). All of the above statements regarding carboxylate have also been modified as necessary to apply to thiosulphonate. In the thiocarboxylate (-cso), the carbonyl oxygen atom of the phthalate group is only replaced by a sulfur atom. A preferred thiocarboxylate is thioacetate. Isozolium rust salts of formula I are commercially available, for example, from BASF, Sigma Aldrich or Merck. If desired, the anion of the commercially available salt can be readily displaced by other anions by means of ion exchange. The soil oxygen curable composition comprises an epoxy compound. Particularly suitable epoxy compounds are epoxides having from 1 to 10 epoxy groups, preferably having at least 2 epoxy groups. The J-curable composition particularly preferably comprises an epoxy compound having a lower of Μ _ _, and especially having 2 epoxy groups. The mono-epoxy group is, in particular, a diglycidyl group of the kind formed in the reaction of an alcohol group with epichlorohydrin. The epoxy compound may be a low molecular weight compound having an average molar weight of 10 〇〇g/mol 'compound (polymer)... is a compound having a higher molecular weight or containing an aromatic group: (including cycloaliphatic compounds) 5's 'epoxy compound or its oligomer. ~, ® aromatic or aliphatic 6-member ring can be made by making epichlorohydrin and | /, to 乂The combination of two reactive ruthenium atoms 131,923.doc 200911866 'More specifically, the epoxy compound obtained by reacting with a polyol is of importance in the art. It can be made by including epigas alcohol with at least two ( Preferably, two epoxy compounds obtained by reacting a compound with two aromatic or aliphatic 6-membered rings are of particular importance in the art; compounds such as Xiao include, in particular, double-aged bis and bisphenol F' And hydrogenated bisphenol a and bisphenol f. The reaction product of epichlorohydrin and (iv) is also suitable, such as a cresol-aldehyde adduct, such as a phenol-furfural resin, a resin (a). More special varnish Type (4) Of course, epoxy compounds which are not derived from epichlorohydrin epoxy compounds are also suitable. Suitable examples include the following epoxy compounds: those containing an epoxy group obtained by reaction with glycidyl enoate (for example, radical copolymerization with (meth) propyl terephthalate, glycerol). +Incoming A can also refer to ERL-4221 from Dow (CAS No. 2386-87-0):

The U compound is more liquid in the range of 2 Torr to the temperature, and is suitable for the epoxidization of the composition at 100 ° C, more preferably 20 to 4 (TC, excellent 2 (TC processed epoxy) Other Components of the Compositions The compositions of the present invention may also comprise other ingredients in addition to the latent catalyst and epoxy compound. 131923.doc -18- 200911866 The composition is suitable for a 1 κ system, or Applicable as a storable component of a 2-foot system. In the case of a 2 Κ system, 'the second highly reactive component is added only shortly before use; after adding the second component, the resulting mixture no longer has storage stability, Since the crosslinking reaction or curing has started and the viscosity is increased. 1 The κ system already contains all the necessary components and has storage stability.

Unless otherwise stated, the following statements regarding the composition apply to the 1 κ and 2 κ systems. ~ The composition may also contain other reactive or non-reversal compounds. Peripheral examples include a variegated resin; here, the resin is a condensation product of a derivative such as o-, m- or p-cresol) with an aldehyde or a ketone (more specifically, formaldehyde). Particularly suitable phenolic resins are resole phenolic resins and more specifically varnish-type (four) resins, varnish-type (four) trees, more specifically, molar excess of morden condensation: two... resins. The varnish type (4) resin is preferably soluble in alcohol or propionate crosslinker, such as phthalic acid liver, needle, diphenyl hydrazine, tetracarboxylic dianhydride, tetra phthalic acid ~ A:: Dicarboxylic anhydride, 4_f-based tetrahydro-o-phenylene, phthalic anhydride, 4-f-hexahydro-o-benzene- _ soil tetra-t-phthalic anhydride. The present invention is a cross-linking of a phthalic anhydride or a W-based hexahydro-o-xylene-based I-based resin and an acid anhydride curing agent with an epoxy compound by addition polymerization 131923.doc -19- 200911866. The addition polymerization reaction (more specifically, the addition polymerization reaction of the epoxy compound with the expectant resin) is also accelerated by the imidazolium salt of the formula I. Thus, a particularly suitable composition of the present invention also includes a composition comprising at least one test resin (preferably a varnish-type wake-up resin) in addition to the π-salt salt of the formula I and the epoxy compound. Non-reactive ingredients include resins that do not enter any other crosslinking reaction, as well as inorganic fillers or pigments.

The composition may also contain a solvent. If appropriate, the organic solvent has applicability to set the desired viscosity. In a preferred embodiment, the composition contains only a small amount of bathing agent (less than 2 parts by weight per 100 parts by weight of the epoxy compound, more specifically less than 10 parts by weight) or even low, even if it contains a solvent. 5 parts by weight), and particularly preferably no solvent (1 〇〇 / system). Preferred compositions comprise to +q η _^ counties. / / ο 3 main weight %, preferably at least 5% by weight, excellently at least 70 weights / n p p g A / % of the compound (plus any solvent used) 〇

^ 1 part epoxy compound 0.01 to 1 part by weight, more preferably at least 1). 1 heavy wound, especially at least 重量 5 parts by weight, and excellently per i weight to the lining % rolling compound at least 1 part by weight; the amount is preferably not more than 8 parts by weight per 100 parts by weight of the compound, especially not to 6 parts by weight, and the detail θ can also be, for example, every 100 parts by weight. % oxygen compound 1-6 or 3-5 parts by weight. Except for the ρ meter of formula I. The rust _ _ _ _ _ _ ' composition can of course also contain other latent catalysts known to date, 眚 - a case of boron trifluoride and amine adducts (Bf3_ 131923.doc -20. 200911866 single B Base amine), fourth oxime compound & s σ or cyanogenic guanidine (DICY). The nitrogen-containing component as a curing agent means an aromatic and aliphatic polyamine such as ν_aminoethyl (tetra), polyvinylamine', more specifically aromatic and aliphatic diamines, such as isophorone II. Amine, toluenediamine, xylene diamine (more specifically, meta-xylene diamine) 4,4'-methylenediphenylamine, ethyl-xanthene, ethylamine, 1,2-propylenediamine, 1, 3_propylenediamine, piperazine, 4,4'-diaminodicyclohexylmethyl, 3,3,-dimethyldiaminodicyclohexylcarbamate, neopentylamine, 2,2,_ Oxy bis(ethylamine), hexylamine, octylamine, hydrazine, 12-diaminotetradecyl, 1,1 fluorene diamine decane, norbornane diamine, menthane diamine,丨, 2_diaminocyclohexane, hydrazine, 3-bis(amino-methyl)% hexanyl, 1·methyl-2,4-diaminocyclohexane; polyetheramine, Ethylene oxide, butylene oxide, pentene oxide or a mixture of such alkylene oxides with propylene oxide and ammonia (4,7,1〇_trioxatridecane-丨^-diamine, 4,7,10 -Dioxa·ι,13•13-decanediamine, XTJ-568 from Huntsman, 1,8-diamino-3,6-dioxaoctane (from Hunt Sman's XTJ 504), 1,1 〇-diamino-4,7-dioxa-decane (from Huntsmani XTJ 5 90), 4,9-dioxadodecanediamine (from BASF), 4 , 7,10-trioxatridecane-13-diamine (from basf), XTJ 566 from Huntsman) 'Polyether amines based on ammonia, propylene oxide and ethylene oxide (such as

Huntsman's XTJ 500, XTJ 501, XTJ 511), polyetheramine based on poly(1,4-butanediol) and/or poly(THF), propylene oxide and ammonia: XTJ 542, XTJ 559 from Huntsman, poly Ether amine T403, polyether amine T5000 'except for diethyltriamine, tri-ethylidene tetraamine and polyetheramine based on propylene oxide and ammonia. Selected examples of other nitrogen-containing components are substituted imidazoles such as 1-mercapto 131923.doc • 21 - 200911866 imidazole, 2-phenylimidazole, hydrazine-cyanoethylimidazole; imidazolines such as fluorenylphenyl Imidazoline; third amine, such as N,N-dimethylbenzylamine, % (2,4,6-gin(dimethylaminomethyl)phenol), DABC〇(14_diaza Bicyclo [2.2.2]octane); ketimine, such as Qiu _ (:: 1^35〇2; polyamidoamine, such as Versamid® 140 from Cognis; uron, such as 3_ (4 chlorobenyl)-1,1-monomethylurea (monuron), 3-(3,4~dichlorobenzene-yldimethylurea (diuron), 3-benzene Base_1,1_dimethylmethane (non-cedar, fenuron), 3_(3_gas_4_methylphenyl^dimethylurea (green Γ; 麦隆, chioroioluron), tolyl-2 , 4-bis(indole, Ν·dimethyl carbamide), Amicure UR2T (Air Products); tetraalkyl hydrazine, such as N, N, N', N,-tetramethyl hydrazine; reaction of DICY with amine The product (so-called biguanide) 'such as HT 2844 from Vantico. The composition is preferably from 20 to 100. (:, more preferably from 20 to 40. (:, excellently 20. The liquid at the processing temperature is a liquid. The viscosity of the composition without a latent catalyst at 21 ° C and 1 bar is carried out at a temperature of up to 50 ° C for a period of 1 hour, especially at 1 Torr. After 〇 hours of U (starting with the addition of latent catalyst), the viscosity of the entire composition increases by less than 20% 'more preferably less than 10%, very preferably less than 5%, more specifically less than. 2〇/〇. The above composition is suitable for the 1 K system. It is also suitable for the storable component of the 2 K system. In the case of the 2 K system, the highly reactive group injury is added only before use [such as the conventional Southern reaction Amine curing agent or reactive anhydride curing agent; thereafter, curing begins and becomes apparent due to increased viscosity. 131923.doc •22- 200911866 α / Crosslinking of epoxy compounds in makeup or poly systems. Suitable examples of a family of polyamines such as two include reactive polyamines or xenon, which are commonly used as 2 κ

The ethyltriamine, the three known amine crosslinkers are amines of propylene oxide and ammonia (polyetheramine, oxime-ethyltetramine; or based on 400). For example, D 23 〇, D 2 〇〇〇, D curing and use The composition of the imidazole salt containing the formula is easy to dissolve in epoxidation = storage stability. 〗 〖Mi

. The rust salt is used as a latent catalyst in the composition: the polymerization or crosslinking of the compound is excellent. - At a typical storage temperature below 40 °C, more specifically at a temperature below 30 C, it is observed that the viscosity of the composition is little or no increase. Therefore, these I humans are suitable for use as a howling system without the need to add a second group prior to use: to cause curing or crosslinking. These compositions are of course also suitable as storable components of the 2 κ system (see above). Curing of the composition (in the form of a 1 Κ system or a 2 Κ system) can be carried out at temperatures below the potential use temperatures of the latent imidazole rust catalysts known to date. Curing can be carried out at atmospheric pressure and at temperatures below 250X: especially at temperatures below 200 ° C, preferably below 175 ° C, more preferably below 150 ° C And preferably carried out at temperatures below 125 ° C and even below 10 (rc). Curing may also be carried out at temperatures below 80 ° C. Curing is especially possible at 40 to 175 ° C, more specifically 60 to 150 ° C or 60 to 125. (: in the temperature range. 131923.doc • 23- 200911866 The composition of the present invention is suitable for use as a coating or impregnating composition, suitable for use as an adhesive, composite 'used to produce shaped articles, or suitable for use as a casting compound to embed, join or solidify shaped articles. This statement and the following statements apply to both 1 K systems and 2 K systems; the preferred system for all of the applications is 1 K system. Examples of coating compositions include coatings and varnishes. The use of the combination of the invention (1 ft or 2 K) is especially desirable in any material made, for example, of metal, plastic or wood based materials. A scratch-resistant protective coating is obtained on the substrate. These groups of p-products are also suitable for electronic applications. Insulating coatings, such as insulative coatings for wiring and electrical winding. It may also be mentioned for its use in the production of photoresists. In particular, it is also suitable for use as a re-grinding σ JL coating material, including with (for example) It is a combination of repairing the official road (site cure cipp restoration) without disassembling the pipe. In addition, it is also suitable for sealing the floor. It is a 1 K or 2 K structural adhesive. The agent is used to permanently connect the molded parts to each other. The molded part can be made of any desired material: suitable materials include plastic, metal, wood, leather, ceramics, etc. The J phase adhesive can also be hot melt. Adhesive, which is fluid and can only be processed at relatively high temperatures. It can also be a floor adhesive. These compositions are also suitable for producing printed circuit boards by at least the S Μ T method (surface mount technology). Adhesives for electronic circuits. In composites, different materials such as plastics and reinforcing materials (fibers, carbon fibers) are joined to each other. 4 ° mysterious composition is suitable for producing pre-impregnated fibers (eg prepreg) and Suitable for use One-step processing into a composite. i31923.doc •24- 200911866 The method of producing a composite includes curing m ^ j. pre/re, fiber or woven fiber. The mouth (such as prepreg) is solidified, or extruded. Pressing and pulling a resin transfer molding (rtm) called resin impregnation technique (R1). In detail, the composition of the present invention can be impregnated with fibers, and thereafter cured at an ancient temperature. During the impregnation process and any During subsequent storage, no: curing begins or only a small amount of curing. Khan as a casting compound for inlaying, joining or solidifying shaped articles,

Such compositions can be used, for example, in electronic applications. It is suitable for use as a flip chip underfill or as an electrocast resin for infusion, wash and (dome, gl〇b) packages. [Examples] Examples Starting materials The epoxy compound used was bisphenol A diglycidyl ether (abbreviated as DGEBA), which was commercially available from Nan Ya under the name NPEL 127H. Compositions studied In each case, 5 parts by weight of a mixture of an imidazolium salt or an imidazole rust salt was mixed with a 100-weight epoxy compound. The table lists the compositions and results. In the case of lx and lxx, mixtures containing other ingredients are also tested (see footnotes in Table 2 below). Measurement Method The start and process of curing were investigated by means of differential scanning calorimetry (Dsc). For this purpose, the composition was heated to a 15 mg composition at a constant rate of 10 ° C/min in a DSC calorimeter (DSC 822, Mettler Toledo). 131923.doc -25- 200911866 The measured parameter is τ〇 (start of exothermic polymerization, starting temperature),

Tmax (the maximum temperature of the exothermic peak, corresponding to the maximum acceleration of the reaction) and ΔΗ (the integral of the DSC curve, corresponding to the total amount of heat released from the polymerization). Further, the glass transition temperature (Tg) of the cured, sufficiently reacted sample was measured by means of DSC as follows: The g uncured composition was introduced into the aluminum boat at a film thickness of 3 to 4 mm and each at 40. 〇, 60 ° C, 80. (:, 100 〇C, 120 ° C and 140 ° C for 30 minutes. Determine the Tg of the cured sample by DSC measurement at a heating rate of 30 ° C / min, which is three independent measurements Average. Test storage stability (applicable period) by measuring relative viscosity (gelnorm®-rvn viscometer). Time at different temperatures (25 ° C, 8 CTC, 100. < 3 and 120 ° C) The measurement (in days (d) or minutes). The reported time is the time after which the mixture can still be washed. Table 1: Imidazolium salt, physical properties Salt imidazole rust cationic anion anion at 25. (: pKb 1 1-ethyl-3-methylimidazolium rust acetate in water 9.2 — 2 1-butyl-3-ethylimidazolium acetate 92 ~- 3 1,3-dimethylimidazolium acetate 9.2 ~ 4 1-butyl-3-mercaptoimidyl rust formate 10.2 - C1 butyl-3-mercaptoimidazole rust ion 14~~ ~~~~ C2 Tethyl-3-methylimidazolium rust sulfonate 14-- 131923.doc -26- 200911866 Table 2: Results of DSC measurement and storage stability Salt To (°C) Tmax (°C) AH (J/g) Tg (°C) Storage stability, at 25 (C) storage stability Storage stability at 80 ° C (min), at 120 ° C (min) 1 73 114 495 133 2 11 2 98 117 479 141 2 14 3 96 119 475 nd 1 9 4 94 124 423 138 2 20 lx 123 162 334 156 15.8 |XX 146 162 294 157 18.3 Cl 192 245 518 104 >20 >300 C2 280 315 418 ndnd >300 lx The mixture tested also contains the anhydride curing agent MHHPA (mercaptohexahydrophthalic acid) Anhydride); epoxide: anhydride molar ratio of 1:0.9; 1 part by weight of imidazole rust salt per 100 parts by weight of epoxide; curing conditions: 3 hours at 100 ° C and 2 hours at 150 ° C. The mixture tested by lxx also contained varnish type phenolic resin PHS 6000 IZ04 from Hexion Specialty GmbH; the epoxide: hydroxyl molar ratio was 1:0.9; 1 part by weight of imidazole per 100 parts by weight of epoxide + varnish type phenolic resin Barium salt; curing conditions: 2 hours at 140 ° C and 2 hours at 100 ° C. A mixture of EMIL acetate and DICY in a ratio of up to 10:9 is a liquid and homogeneous solution, so it can be easily metered into the epoxy resin. 131923.doc -27- 200911866 Table 3 and Table 4: (lactate pKb = 10.1) Composition (weight fraction) DSC data under 80 C [min] To rc] Tmax rci ΔΗ Tg rci DGEBA/EMIM lactate ( 5) 100/5 95 132 457 133 30'

Table 5: Solidification of DGEBA composition with EMIM acetate (1)/DICY mixture (weight fraction) DSC data stored under 80C '[sec] To [°C] Tmax re] ΔΗ [J/g] Tg rci DGEBA /1 100/5 73 114 495 133 660-720 ~~ DGEBA/1/DIC Y 100/3.75/1.25 116 153 485 140 2040-2440 '— DGEBA/l/DICY 100/2.5/2.5 130 140 532 152 5140- 6010 ~~ DGEBA/l/DICY 100/1.25/3.75 112 127 509 160 7080-9120 ^~ DGEBA/l/DICY 100/5/5 130 140 529 133 3380-4150 ~ Each at 60 ° C, 80 ° C, l 〇〇 ° C, 120 ° C, 140 ° C for 30 min, at 160 ° C for 4 匕 3.5 h. The storage stability was about 11 minutes with DGEBA cured with 5% EMIM acetate. Surprisingly, the addition of DICY results in increased storage stability of the system and, in the case of cured epoxy resins, produces comparable or increased glass transition temperatures. The EMIM acetate (1) and DICY mixture are liquid and therefore can be especially easily mixed with epoxy resins. 131923.doc •28-

Claims (1)

200911866 X. Patent application scope: 1. A formula I, a latent catalyst of a 3-substituted imidazole composition, a cerium salt as a curing inclusion, epoxy compound Χη· Where: Ri and R3 are each independently an organic group having an atom; R2, R4 and R5 are each independently an H atom or an organic group having 丨 to 2 = = atom, and R4 and R5 may also form an aliphatic or aromatic group. Ring; X is tickrate or thiowarate; and n is 1, 2 or 3, wherein 1-ethyl-2,3-dimethylimidazole rust and cesium acetate-ethyl-2,3-dimethyl Except for the rice bran salt of the quinone-acetic acid complex. 2. The use of claim 1 wherein the phantoms are independently of each other (7) alkyl, allyl or benzoinyl. 3. The use of claim 1 or 2, wherein R2, R4&R5 are, independently of each other, H atom or Cl to C8 alkyl, Cl to C8 alkenyl, more specifically allyyl, phenyl or phenyl base. 4. The use of claim 1 or 2, wherein if the anion X is acetate, R2 is a deuterium atom. 5. The use of claim 1 or 2, wherein R2 is a deuterium atom. 6. The use of claim 1 or 2, wherein η is 1. 131923.doc 200911866 7. The use of claim 1 or 2 wherein the carboxylate has a pKb lower than i3 (measured in water or dimethyl sulfoxide at 25 C, 1 bar). 8. The use according to claim 2, wherein the curable composition comprises an epoxy compound having at least 2 epoxy groups. 9. The use of claim 2 or 2, wherein the curable composition comprises an epoxy compound having an average of 2 epoxy groups. ', 10. The use of the item 丨 or 2, wherein the composition comprises an epoxy compound obtained by reacting an alcohol with an alcohol. 11. The use of the item 1 or 2, wherein the group of materials contains at least 3 ounces of water in addition to water and organic solvents. /. Preferably, at least $ 〇 by weight of the epoxy compound. 12. The use of claim (4), wherein the composition further comprises other components, examples being anhydride curing agents or phenolic resins, more specifically varnish-type resins (nov〇lak). 13. The use of the item 丨 or 2, wherein the amount of the latent catalyst is from 0.01 to 10 parts by weight per part of the weight of the epoxy compound. 14. A curable composition comprising an epoxy compound and a 1,3_substituted imidazole rust salt of the formula I as claimed in claim 1 as a latent catalyst. 15. The curable composition of claim 14 which comprises a mcYA/ or an amine crosslinker. The curable composition according to any one of claims 14 and 15, which comprises a nitrogen-containing component as a curing agent. 17. The curable composition of claim 16, which comprises a mixture of _CY in the ferric salts of said sulphate. The mixture is homogeneous and liquid at room temperature. The curable composition of any one of claims 14 and 15 which, in addition to the 7 solvent, also comprises at least 3% by weight of epoxidized character oxime and organic 19. A cure as claimed in item 14 The composition of any one of 17 is to be cured at less than 2 Torr. It is carried out at a temperature of 〇. ''20. The use of the curable composition of any one of claims 14 to 17, which is used as a coating or impregnating composition, as an adhesive, in a composite material, for The shaped article is produced or used as a casting compound to insert or solidify the shaped article. Use of a curable composition according to any one of claims 14-17 for curing by pre-impregnating fibers or woven fabrics or by extrusion, drawing, coiling or resin transfer molding or The resin impregnation technique produces a composite. 131923.doc 200911866 VII. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbol of the symbol of the representative figure is simple: 8. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: 131923.doc -6-