GB2247237A - 1-(N'-cyanoguanyl) derivatives of N-containing five-membered ring heterocycles - Google Patents
1-(N'-cyanoguanyl) derivatives of N-containing five-membered ring heterocycles Download PDFInfo
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- GB2247237A GB2247237A GB9117979A GB9117979A GB2247237A GB 2247237 A GB2247237 A GB 2247237A GB 9117979 A GB9117979 A GB 9117979A GB 9117979 A GB9117979 A GB 9117979A GB 2247237 A GB2247237 A GB 2247237A
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- epoxy resin
- cyanoguanyl
- membered ring
- derivatives
- compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/325—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals directly attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
1-(N'-Cyanoguanyl) derivatives of N-containing five-membered ring heterocycles of the general formula: <IMAGE> where X = N, CR3 Y = N, CR4 R1 - R4 = H, alkyl of from 1 to 4 carbon atoms @or phenyl, are highly reactive and very stable in storage, and are also particularly highly suitable for use as accelerants in the curing of epoxy resin compositions.
Description
2.--: '1 -7:2.-- -,, 1-(NI-Cv4noguanvl) derivatives of N-containing
fivemembered ring heterocycles The present invention relates to derivatives of Ncontaining five-membered ring heterocycles, the preparation thereof, and the use thereof in the curing of epoxy resins. 5 As will be known, storable epoxy resin mixtures involve the use of urones (monurone, diurone, fenurone, etc.) combined for example with dicyandiamide (cf. US 3 562 215 and US 3 956 237). Urones have the disadvantages of involving the use of isocyanates in their preparation and the fact that some gaseous dimethylamine is evolved in the process of curing.
Alternatively, imidazoles can be prepared for example as described in GB1050679, but they have only a limited shelf life, which presents many application problems.
To meet this problem, various imidazole derivatives have been put forward, for example imidazolides (Nacylimidazoles) (cf. DE-A-32 46 072) and also isocyanateblocked imidazoles. Both compound types are very expensive to produce, by reaction with specific acid chlorides (releasing HC1) or with isocyanates.
Finally, DE-A-39 19 431 discloses additives for heat-curable epoxy resin compositions which represent adducts or reaction products of substituted or unsub- stituted imidazoles with aromatic hydroxyacids, for 2 - example salicylic acid. These products likewise only have a limited shelf life.
it is an object of the present invention to develop novel compounds which are relatively simple and inexpensive to prepare and can be used as reactive-and stable additives for heat-curable epoxy resin compo'Sitions.
The present invention provides a 1-(NI-cyanoguanyl) derivative of an Ncontaining five-membered ring heterocycle, of the general formula:
/ R1 NH J===Y "-- R2 ..I N - C - NH - W where X = N, CR3 Y = N, CR4 R, R4 = H, alkyl of from 1 to 4 carbon atoms or phenyl.
It has been found, surprisingly, that owing to their high reactivity and good stability, these compounds are highly suitable for use as accelerants in the curing of epoxy resin compositions.
The above compounds consist of an NI-cyanoguanyl radical whose N-atom forms part of a five-membered ring heterocycle. In a preferred aspect of the present 1 1 1 i 1 1 i 1 1 invention, the five-membered ring heterocycle is an imidazole, a pyrrole or a 1,2,4-triazole ring. The fivemembered ring heterocycle may be completely unsubstituted (i.e. R1, any R3 and R4, and also R2 = H) or else, depending on the number and nature of the.hetero atoms, may carry other R, to R4 substituents on the'-carbon atoms. Suitable substituents are especially branched and unbranched alkyl radicals of from 1 to 4 carbon atoms and also unsubstituted phenyl radicals. of these, particular preference is given to methyl and ethyl.
The present invention also provides a simple and easy process for preparing the above compounds, which process comprises reacting a dicyanimide with the appropriate heterocycle ring in the presence of an acid.
Preferably, the process comprises reacting sodium dicyanimide with the appropriate heterocyclic compound, more especially with an imidazole, pyrrole or 1,2,4 triazole, ideally at an elevated temperature, in the presence of an acid.
The reaction may be carried out not only in the melt but also in a suitable solvent. Suitable solvents are in principle all organic solvents in which the heterocyclic component is sufficiently soluble. For economic reasons it is particularly advantageous to carry out the reaction in an aqueous medium, since the two starting components are soluble in water and the work-up of the reaction product is then particularly simple. In this case the concentration is preferably set to 5-50% by weight, based on the two starting components.
The reaction temperature may be varied within wide limits, and is preferably elevated, a preferred approx- imate-temperature range being from 25 to 100OC-, more especially from 40 to 80C.
The reaction requires the addition of an acid, of which equimolar amounts, based on the sodium dicyanimide, are in general sufficient. The acid used is for cost reasons preferably a customary mineral acid such as, for example, hydrochloric acid or sulphuric acid. Preferably, the reaction is carried out in an aqueous solution, in which case it is advisable to set the pH to from 1 to 6.
The starting components should in general be used in approximately equimolar amounts. It is of course also possible to use for example a small excess of either component.
The manner of the addition of the individual starting compounds is in general freely choosable. For instance, the sodium dicyanimide may be added to a mixture of the heterocyclic component and the acid. This is advisable in particular in the case of a melt reaction. In a preferred embodiment, the two starting components are dissolved in water and then the acid is added at the appropriate reaction temperature.
Following an average reaction time of about 3 to 5 hours, the mixture may subsequently be stirred at room 1 i i 1 i 1 j f i i i 1 temperature for a certain time or cooled down to lower temperatures (for example 0 to 100C) for several hours in order for the reaction product to crystallize out completely. The product may be separated from the aqueous phase, purified (for example by washing) and, if appropriate, dried in a conventional manner.' We have obtained products in high purity and good yield (about 50 to 90%).
The present invention also provides the use of a compound as specified above in the curing of an epoxy resin, in particular as an accelerant, more especially together with latent hardener(s), in the curing of an epoxy resin composition.
We have found that compounds of the invention can be used with great success as accelerants for the heatcurable epoxy resin compositions. Suitable epoxy resins here are all commercial products which customarily have more than one 1,2-epoxide group and are saturated or unsaturated aliphatic, cycloaliphatic, aromatic or heterocyclic compounds with or without substituents such as halogens, phosphorus and hydroxyl groups, etc.
Particular preference is given to epoxy resins based on glycidyl polyethers of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) and the bromine-substituted derivative tetrabromobisphenol A, glycidyl polyethers of 2,2- bis(4-hydroxyphenyl)methane (bisphenol F) and glycidyl ethers of novolac resins.
If the present compounds are used as accelerants combined with other latent hardeners, it is in general sufficient to employ from 0.1 to 2.0% by weight, based on the weight of the epoxy resin, to be able to obtain adequately high reactivities.
Latent hardeners for use with the accelerants are known and usually commercially available. of these, preference is given to hardeners which contain amino, imino, amido, imido, triazine or hydrazide groups.
Suitable hardeners are, for example, boron trichloride and trifluoride/amine complexes, dicyandiamide, aminotriazines such as melamine or diallylmelamine and guanamines such as acetoguanamine or benzoguanamine, aminotriazoles such as 3-amino-1,2,4-triazole, carboxylic hydrazides such as adipo-mono- or - dihydrazide, stearic hydrazide, isophthalo-mono- or - dihydrazide, semicarbazide, cyanoacetaraide and aromatic polyamines such as diaminodiphenyl sulphone. Particular preference is given to dicyandiamide, isophthalic dihydrazide and adipodihydrazide.
The present invention further provides a process for producing an epoxy-resin containing product, wherein one of the present compounds is used to accelerate the curing of the epoxy-resin, as well as an epoxy-resin containing product made by such a process.
Depending on the intended use, the present compounds may be mixed together with the hardeners into a liquid or i i i 1 i i f i f 1 i 1 f i v i i 1 1 1 1 i 1 1 i i i 1 1 1 1 1 1 i 1 j molten epoxy resin for suspension therein or may be introduced in the form of a solution into the epoxy resin or into a solution thereof. Suitable solvents are in principle all liquids in which the epoxy resin, the hardener and the accelerant are sufficiently soluble. Examples of such solvents are various glycolethers, such as ethylene glycol or propylene glycol monomethyl ether and also esters thereof, and also ketones such as, for example, acetone or DMF.
The present compounds should be used in a very finely divided form to ensure uniform dispersion and maximum effect. The particle size should therefore preferably be < 150 im.
The curing of epoxy with the aid of the accelerants of the invention may be carried out at temperatures of from 100 to 2000C, preferably at from 120 to 1600C, and generally starts very rapidly.
The gel times at for example 140C may range from 4 to 6 minutes,, depending on the amount of accelerant. At lower temperatures the gel time may be reduced still further by using higher amounts of accelerants.
The present invention also provides an epoxy resin composition including one of the present compounds. We have shown that a further advantage of compounds of the invention when used as accelerants is the long shelf life. As storage tests have shown, epoxy resin formulations which contain accelerants of the invention are normally stable to storage at 400C for from 10 to 12 days and at room temperature for from 4 to 6 weeks.
Owing to the favourable application properties of these compounds and their inexpensive preparation, they are particularly suitable for use in industry.- The invention will now be illustrated in more detail by the following Examples, and with reference to Figs. 1 and 2 of the accompanying drawings, which are graphs of gel time against amount of accelerant in different resin 10 formulations. Examnle 1 Preparation of 1-(NI- cyanoguanyl)inidazole 13.6g of imidazole and 18.16 g of sodium dicyanimide are dissolved in 30 ml of water, and the solution is is heated to 50'C. 22.8 g of 32% strength hydrochloric acid are added dropwise over 3 hours. The mixture is subsequently stirred for a further 3 hours. After cooling overnight down to 4'C, the product is filtered off with suction, washed chloride-free with about 100 mI of water and dried.
This gives 15.2 g (yield 57%) of a slightly old rose-colored powder which gives the correct elemental analysis. Thin layer chromatography and the IR spectrum indicate no by-products or starting materials. Melting point 189 to 1900C (the melt resolidifies at 210C).
1 i 1 i i i 1 1 1 1 1 Elemental analysis: C5H5N.5 (MW = 135.12) Calculated C 44.44% Found C 44.13% Calculated H 3.73% Found H 3.59% Calculated N 51.83% Found N 52.40% ExamDle 2 Preparation of 1-(Ntcyanoguanyl)-2-methylinidazole 16.4 g of 2-methylimidazole are neutralized with about 22.8 g of 32% strength hydrochloric acid to a pH of 5.0 in 30 ml of water. The solution is concentrated at 80C under reduced pressure. The molten residue is intimately mixed with 18.16 g of sodium dicyanimide and maintained at 80C for 4 hours with vigorous stirring.
Any caking together of the reaction mixture should be avoided. The solid reaction product obtained is sus pended in 100 ml of water. filtered off with suction, washed with 50 ml of water and dried.
This gives 26.3 g (yield 88.3%) of an almost white powder which gives the correct elemental analysis. TLC 20 and IR show no by-products or starting materials. Melting point 153C (the melt resolidifies to form a mass which has no melting point up to 280'C). Elemental analysis: C07NS(MW = 149.16) Calculated C 48.32% Found C 47.91% Calculated H 4.73% Found H 4.59% Calculated N 46.95% Found N 47.35% Example 3 Preparation of 1-(NI-eyanoguanyl)pyrrole 6.7 g of pyrrole and 9.1 g of sodium dicyanimide are dissolved in 25 ml of water, and the solution is heated to 80't. 11.4 g of 32% strength hydrochloric 'acid are added dropwise over 3 hours, and the mixture is subsequently stirred for 2 hours. After cooling down overnight the product is filtered off with suction, washed with 50 ml of water and dried at 65'C under reduced pressure.
This gives 11.5 g (yield 86%) of a dark brown powder contaminated by oxidation products (TLC, IR) which gives the correct elemental analysis. Melting point: > 280'C 15 Elemental analysis C6H6N4(MW - 134.14) Calculated C 53.72% Found C 52.3% Calculated H 4.51% Found H 4.3% Calculated N 41.77% Found N 40.2% ExanDle 4 Preparation of 1-(NO-cyanoguanyl)-1,2,4-triazole 6.9 g of 1,2,4-triazole and 9.1 g of sodium dicyanimide are dissolved in 25 ml of water. 11.4 g of 32% strength hydrochloric acid are added at 800C over 3 hours, and the mixture is subsequently stirred for a further 2 hours. After cooling down to 40C the precipitated product is filtered off with suction, washed with 1 1 1 I 1 1 1 i i i i i 1 1 1 1 i 1 ml of water and dried under reduced pressure.
This gives 7.6 g (yield 56%) of a white powder which gives the correct elemental analysis. TLC and IR show no by-products or starting materials. The product does not change on heating to 300C. Elemental analysis: C4H4N6 136.12) Calculated C 35.30% Found C 34.88% Calculated H 2.96% Found H 2.65% Calculated N 61.74% Found N 61.90% ExamDle 5 Investigation of gel times The effect of using the novel compounds 1-(N1cyanoguanyl)inidazole (preparation see Example 1) and (NI-cyanoguanyl)-2-methylimidazole (see Example 2) as accelerants in epoxy resin compositions will be inves tigated at various temperatures. To this end formula tions consisting of 100 g of a bisphenol A liquid resin (for example Epikote 828 from Shell), 6 g of dicyan diamide ( Dyhard 100S, SKW Trostberg) and also from 0.1 to 2 g of the novel compounds (accelerants) are prepared and subjected to gel time determinations at 120cC, 140C and 1600C. The results for the compounds of Example 1 and Example 2 are summarized as graphs in Figures 1 and 2, respectively, which graphs show the gel time in Trademark minutes against the amount of each accelerant added (per hundred resin (phr)). As can be seen, these compounds produce very good gel times at from 140 to 1600C. ExamDle 6 Investigation of storage stability The storage stability of thermally curable mixtures which contain the novel acceleratns 1-(NI-eyanoguanyl)imidazole and 1-(NI-cyanoguanyl)-2- methylinidazole is investigated. To this end formulations are prepared from 100 g of a bisphenol A liquid resin (for example Epikote 828), 7 g of dicyandiamide Dyhard 100S, by SKW Trostberg) and also 1 g of the accelerants. The viscosity of the formulation is measured at 250C in a Haake rotary viscometer following storage at 25C. The results indicate good storage stability:
viscosity 0 d in Pa s Accelerant 1 Accelerant 2 Trademark j No. of days (d) 1 d 2 d 4 d 8 d 12d 16.0 16.1 16.3 16.9 18.0 21.9 16.0 16.2 16.4 17.1 18.4 22.5 1 1 i i i i i 1 1 1 1 1 For comparision (not according to the invention) a formulation prepared from 100 g of Epikote 828, 7 g of dicyandiamide and 1 g of 2- methylimidazole was investigated. The result indicates very poor storage stability:
No. of days (d) viscosity 0 d 1 d in Pa s 2-methyl imidazole 14.2 solid, no longer measurable Trade mark claims:
1. A compound of the general formula:
X-= ==---Y where R1 NH I IX - C - NH - CN X = N, CR3 Y = N, CR4 R, - R4 = H, alkyl of from 1 to 4 carbon atoms or phenyl. 2. A compound as claimed in claim 1, wherein the fivemembered ring heterocycle is an imidazole, pyrrole or 1,2,4-triazole ring. 3. A compound as claimed in claim 1 or claim 2, wherein any R, - R4 alkyl radicals are methyl or ethyl. 4. A compound as claimed in claim I which is specified in any one of Examples 1 to 4 herein.
5. A process for preparing a compound as claimed in any one of claims 1 to 4, which comprises reacting a dicyanimide with the appropriate heterocycle ring in the presence of an acid. 6. A process as claimed in claim 5, which comprises reacting sodium dicyanimide with an appropriate imid- 1 1 1 i i j 1 1 i i 1 1 1 i i i 1 i azole, pyrrole or 1,2,4-triazole ring in the presence of an acid.
7. A process as claimed in claim 5 or claim 6, wherein the reaction temperature is adjusted to within an approximate range of 25-1000C.
8. A process as claimed in claim 7, wherein the reaction temperature is adjusted to within an approximate range of 40-80C.
9. A process as claimed in any one of claims 5 to 8, wherein the reaction is carried out in an aqueous medium. 10. A process as claimed in claim 9, wherein the reaction is carried out at a pH of from 1 to 6. 11. A process for preparing a compound as claimed in claim 1, carried out substantially as described in any one of Examples 1 to 4 herein. 12. A compound as claimed in claim 1 whenever prepared by a process as claimed in any one of claims 5 to 11. 13. The use of a compound as claimed in any one of claims 1 to 4 and 12 in the curing of an epoxy resin.
14. The use as claimed in claim 13 of the compound as an accelerant, together with latent hardener(s), in the curing of an epoxy resin composition. 15. The use as claimed in claim 14, wherein the amount of accelerant is from 0.1 to 2.0% by weight, based on the weight of the epoxy resin. 16. The use as claimed in claim 14 or claim 15, wherein the latent hardener used is dicyandiamide.
17. A process for producing an epoxy resin-containing product, wherein a compound as claimed in any one of claims 1 to 4 is used to accelerate the curing of the epoxy resin. 18. An epoxy resin- containing product made by_a process as claimed in claim 17.
19. An epoxy resin composition including a compound as claimed in any one of claims 1 to 4.
Published 1992 at The Patent Office. Concept House. Cardfir Road. Newport. Gwent NP9 1 RE. Further copies may be obtained froni Sales Branch. Unit 6. Nine Mile Point. Cwmfelinfach. Cross Keys. Newport. NP1 7HZ. Printed by Multiplex techniqueshd. St Mar. v Cray. Kent.
i i I 7 J 1 1 i
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19904026363 DE4026363A1 (en) | 1990-08-21 | 1990-08-21 | 1- (N'-CYANOGUANYL) DERIVATIVES OF N-CONTAINING FUENFRINGHETEROCYCLES |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB9117979D0 GB9117979D0 (en) | 1991-10-09 |
| GB2247237A true GB2247237A (en) | 1992-02-26 |
| GB2247237B GB2247237B (en) | 1994-05-18 |
Family
ID=6412591
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9117979A Expired - Fee Related GB2247237B (en) | 1990-08-21 | 1991-08-20 | 1-(N'-Cyanoguanyl) derivatives of N-containing five-membered ring heterocycles |
Country Status (3)
| Country | Link |
|---|---|
| DE (1) | DE4026363A1 (en) |
| FR (1) | FR2667067A1 (en) |
| GB (1) | GB2247237B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0519329A1 (en) * | 1991-06-18 | 1992-12-23 | E.I. Du Pont De Nemours And Company | 1,3-Bis-carbamoyl imidazolium compounds and a process for hardening coatings containing gelatin |
| US9296855B2 (en) | 2011-02-23 | 2016-03-29 | Alzchem Ag | High-latency hardeners for epoxy resins |
| US9382374B2 (en) | 2012-08-02 | 2016-07-05 | Alzchem Ag | Liquid hardeners for hardening epoxide resins (II) |
| US10266644B2 (en) * | 2015-04-06 | 2019-04-23 | Nisshinbo Chemical Inc. | Epoxy resin composition |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005057590A1 (en) * | 2005-12-02 | 2007-06-06 | Degussa Ag | Use of 1- (N'-cyanoguanyl) derivatives of N-containing five-membered heterocycles as curing agents for epoxy resin compositions |
| DE102012015315A1 (en) * | 2012-08-02 | 2014-05-15 | Alzchem Ag | Liquid curing agent useful for curing polymer resins, preferably curable polymer resins comprising epoxide resins, preferably impregnated fiber materials or impregnated fabrics, comprises cyanamide, urea derivative, and viscosity modifier |
| DE102012015316A1 (en) * | 2012-08-02 | 2014-05-15 | Alzchem Ag | Liquid curing agent useful for curing polymer resins, preferably curable polymer resins comprising epoxide resins, preferably impregnated fiber materials or impregnated fabrics, comprises cyanamide, urea derivative, and viscosity modifier |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3562215A (en) * | 1967-06-09 | 1971-02-09 | Minnesota Mining & Mfg | Low temperature,latent epoxy resin curing system |
| US3717612A (en) * | 1970-06-22 | 1973-02-20 | Hitco | Curable epoxy resin composition containing a substituted diurea compound |
| US3956237A (en) * | 1974-07-08 | 1976-05-11 | The Dow Chemical Company | Epoxy resin compositions comprising latent amine curing agents and novel accelerators |
| JPS53116391A (en) * | 1977-03-18 | 1978-10-11 | Shikoku Kasei Kougiyou Kk | Novel imidazoleisocyanuric adduct synthesizing method thereof polyepoxy hardening method containing same as main component polyepoxy hardening method using same as hardening improver and method of pur |
| US4335228A (en) * | 1978-02-27 | 1982-06-15 | Air Products And Chemicals, Inc. | Isocyanate blocked imidazoles and imidazolines for epoxy powder coating |
| CH642068A5 (en) * | 1979-03-14 | 1984-03-30 | Rech Syntheses Organ | THERAPEUTICALLY ACTIVE CYANO-UREA AND CYANO-THIOURAE. |
| CH646956A5 (en) * | 1981-12-15 | 1984-12-28 | Ciba Geigy Ag | Imidazolides. |
| DE3308373A1 (en) * | 1983-03-09 | 1984-09-13 | Siemens AG, 1000 Berlin und 8000 München | Catalytically curable reaction resin compositions which can be processed in screen printing |
| US4742148A (en) * | 1987-04-17 | 1988-05-03 | Hexcel Corporation | Modified imidazole latent epoxy resin catalysts and systems comprising them |
| EP0310545A3 (en) * | 1987-09-02 | 1989-07-26 | Ciba-Geigy Ag | Cyanoguanidines as hardeners for epoxy resins |
| DE3818214A1 (en) * | 1988-05-28 | 1989-12-07 | Schering Ag | IMIDAZOLYL UREA COMPOUNDS AND THE USE THEREOF AS A CURING ACCELERATOR IN EPOXY RESIN COMPOSITIONS FOR THE PRODUCTION OF MOLDED BODIES |
| DE3919431A1 (en) * | 1988-06-28 | 1990-01-04 | Sueddeutsche Kalkstickstoff | Additive for thermocurable epoxy resin compositions |
-
1990
- 1990-08-21 DE DE19904026363 patent/DE4026363A1/en not_active Withdrawn
-
1991
- 1991-08-20 FR FR9110446A patent/FR2667067A1/en not_active Withdrawn
- 1991-08-20 GB GB9117979A patent/GB2247237B/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0519329A1 (en) * | 1991-06-18 | 1992-12-23 | E.I. Du Pont De Nemours And Company | 1,3-Bis-carbamoyl imidazolium compounds and a process for hardening coatings containing gelatin |
| US9296855B2 (en) | 2011-02-23 | 2016-03-29 | Alzchem Ag | High-latency hardeners for epoxy resins |
| US9499653B2 (en) | 2011-02-23 | 2016-11-22 | Alzchem Ag | Curing agents for epoxy resins |
| US9382374B2 (en) | 2012-08-02 | 2016-07-05 | Alzchem Ag | Liquid hardeners for hardening epoxide resins (II) |
| US9499659B2 (en) | 2012-08-02 | 2016-11-22 | Alzchem Ag | Liquid hardeners for hardening epoxide resins (I) |
| US10266644B2 (en) * | 2015-04-06 | 2019-04-23 | Nisshinbo Chemical Inc. | Epoxy resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9117979D0 (en) | 1991-10-09 |
| GB2247237B (en) | 1994-05-18 |
| FR2667067A1 (en) | 1992-03-27 |
| DE4026363A1 (en) | 1992-03-12 |
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| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19950820 |