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WO1992019601A1 - Diaminocyclohexane-imidazolines et leur utilisation - Google Patents

Diaminocyclohexane-imidazolines et leur utilisation Download PDF

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Publication number
WO1992019601A1
WO1992019601A1 PCT/EP1991/002474 EP9102474W WO9219601A1 WO 1992019601 A1 WO1992019601 A1 WO 1992019601A1 EP 9102474 W EP9102474 W EP 9102474W WO 9219601 A1 WO9219601 A1 WO 9219601A1
Authority
WO
WIPO (PCT)
Prior art keywords
compounds
general formula
iii
optionally
glycidyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP1991/002474
Other languages
German (de)
English (en)
Inventor
Christian Burba
Alwin Krotzek
Werner Mrotzek
Bernd Neffgen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer Pharma AG
Lanxess Organometallics GmbH
Original Assignee
Witco GmbH
Schering AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Witco GmbH, Schering AG filed Critical Witco GmbH
Publication of WO1992019601A1 publication Critical patent/WO1992019601A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
    • C07D235/08—Radicals containing only hydrogen and carbon atoms
    • 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
    • C08G59/182—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 using pre-adducts of epoxy compounds with curing agents
    • C08G59/184—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 using pre-adducts of epoxy compounds with curing agents with amines
    • 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
    • C08G59/40—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 curing agents used
    • C08G59/50—Amines
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
    • C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring

Definitions

  • the invention relates to new imidazolyl derivatives, their use as curing agents in epoxy resin compositions, curable epoxy resin compositions comprising them, consisting of an epoxy resin and of the compounds of the general formula I and optionally conventional curing agents and solvents for the production of moldings.
  • the reinforcing materials are impregnated with the curable mixture and cured in one step in the heat to the duromeric final state (one-step process).
  • prepregs are first produced from the reinforcement materials and the curable mixture, which are then processed into finished parts in a second, separate process step.
  • process engineering a distinction is once again to be made between the use of solvent-containing and solvent-free procedures.
  • the prepregs are normally produced in a continuous process in which the reinforcing materials are either passed through an impregnating bath of the resin-hardener mixture to be used, or the impregnating agent is mixed only immediately before it is applied to the carrier material and knocked on using a special device.
  • the control of the amount of impregnating agent to be applied to a certain web of carrier material takes place in addition to the viscosity of the impregnating agent via downstream squeeze rollers.
  • the solvent contained in the impregnation solution is evaporated by the application of heat after the impregnation process, and the resin system is simultaneously converted from the A to the B state.
  • the reinforcing materials soaked with liquid to highly tacky impregnating agent become a slightly tacky to almost dry prepreg.
  • the latent hardener required for the prepreg curing in the second process step does not yet start, in order to allow the impregnated reinforcing materials to react unintentionally to prevent.
  • the prepregs obtained in this way can be temporarily stored and transported as rolls before being used for the respective application. case, be cut accordingly and layered on top of each other in component thickness.
  • the prepreg stack is cured into a high-strength molded part by the simultaneous action of pressure and temperature, the still low-molecular, flowable resins being converted into the high-molecular C state of the duromer.
  • the prepreg production they should be cured at the lowest possible temperatures within a short time, the temperature maximum of the exothermic reaction should remain at a low level even with larger layer thicknesses, and the level of physical properties of the end products should be adapted to practical requirements.
  • Dicyandiamide which has long been used as a latent hardener in curable mixtures based on epoxy resins, is generally combined with co-curing agents and / or accelerators to achieve the desired properties.
  • co-curing agents and / or accelerators to achieve the desired properties.
  • the dicyandiamide is either dispersed directly in the required amount in the epoxy resin or a highly filled dicyandiamide / epoxy resin paste is prepared beforehand, which is subsequently added to the main amount Epoxy resin and the accelerator to the desired resin / hardener concentrations is set.
  • the choice of the accelerator represents a compromise between the level of the required curing temperature and the prepeg storage stability.
  • a strong accelerator not only reduces the curing temperature of an epoxy-dicyandiamide mixture to a technically desirable temperature level, but also there is also the danger that this accelerator reacts with the epoxy resin already during the prepreg storage, whereby the stability of the prepreg storage is permanently reduced.
  • the object of the present invention was, while avoiding the disadvantages of the prior art, curable mixtures based on epoxy compounds and latent and in the To find epoxy resins soluble or homogeneously distributable curing agents which, at relatively low temperatures, harden within a short time without high exothermic temperature peaks to the dimensionally stable state or harden to the final final state, have a thermal resistance which corresponds to the requirements of practice , and which have sufficient storage stability in prepregs at room temperature.
  • This object is achieved by using a new hardening agent, if appropriate also using conventional latent hardening agents.
  • the invention therefore relates to imidazolyl compounds of the general formula (I)
  • R 1 is an optionally branched alkyl radical with 1-9, preferably 1-5, carbon atoms.
  • the invention further relates to imidazolyl compounds of the general formula II,
  • R 4 and R s can be independently H or CH3 -.
  • Another object of the invention are curing agents for glycidyl compounds which can be prepared by reacting
  • R 1 is an optionally branched alkyl radical having 1-9 carbon atoms, preferably 1-5 carbon atoms, to the imidazolyl compounds of the general formula I
  • R 4 and R 5 can independently be H or CH3 -.
  • the products of the formula III according to the invention can also be prepared via the isolated adducts of 1,2-diaminocyclohexane and glycidyl compounds by reaction with monocarboxylic acids.
  • Another object of the invention is the use of compounds of the general formula I - III, optionally with the use of conventional amine compounds, auxiliaries and additives, as curing agents for glycidyl compounds.
  • Another object of the invention are Epoxidharzform ⁇ body, which are characterized in that in the first stage, the reinforcing or insert materials with the binder consisting of
  • the imidazolyl compounds of the formula I according to the invention can be prepared by condensing 1,2-diaminocylohexane with monocarboxylic acids of the general formula V.
  • R 1 is an optionally branched alkyl radical with 1-9 carbon atoms, such as the methyl, ethyl, n-propyl, i-propyl, primary, sec, tert-butyl radical, 2-ethylpentyl radical, 3.3 .5 (3.5.5) -trimethylpenty
  • the reaction is preferably carried out in such a way that the excess amine and the water resulting from the imidazoline formation are removed in vacuo.
  • R 4 and R s can independently be H or CH3.
  • glycidyl compounds in particular the commercially available glycidyl ethers, as described in the Handbook of Epoxy Resins, Lee & Neville, 1967, Chapter 2, can be used here as glycidyl compounds.
  • glycidyl ethers based on polyhydric phenols preference is given to using the glycidyl ethers based on polyhydric phenols, in particular those based on 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) Epoxy values from 0.2 - 0.6.
  • bisphenol A 2,2-bis (4-hydroxyphenyl) propane
  • the glycidyl ethers based on bisphenol F and polypropylene glycols have also proven to be advantageous.
  • the compounds of the general formula I are reacted with the diglycidyl ethers mentioned by processes known per se. According to the invention, the procedure is preferably such that the imidazolyl compounds of the general formula I are reacted with stoichiometric amounts of the diglycidyl ethers at 60-80 ° C. with or without a solvent.
  • the acrylate compounds used according to the invention for the preparation of the addition compounds are transesterification or transesterification products of dihydric alcohols and acrylic acids or their esters. These reactions take place in accordance with the methods belonging to the known prior art.
  • the straight-chain or branched dihydric aliphatic alcohols such as ethylene glycol, propylene glycol, butanediol, hexanediol, octanediol, decanediol or their isomers can be used here as alcohols.
  • the diacrylates are reacted with the compounds of the formula I, preferably with stoichiometric amounts, based on acrylic double bonds, at about 60-80 ° C.
  • the reaction of the glycidyl compounds and / or the acrylates with the imidazoline compounds of the general formula I is carried out according to the methods known for the respective reactive groups, the ratio of mono-imidazolyl compound to the other reactive group preferably being 1: 1 is.
  • the compounds of the formulas I, II, III according to the invention can be used as curing agents alone or as a mixture, 5-50 g, preferably 5-40 g, but especially 5-30 g curing agent being used per 100 g epoxy resin.
  • the quantities depend on the structure of the respective hardening agent and can be optimized by simple orienting tests.
  • the epoxy resins used as a binder component according to the invention are glycidyl esters and ethers with two or more epoxy groups per molecule (as described in Lee & Neville, Handbook of Epoxy esins, 1967 Chapter 2), but preferably the glycidyl ethers based on mono- or polyvalent ones Phenols.
  • the glycidyl ethers based on bisphenol F and the novolaks have also proven to be advantageous.
  • the commercially available halogenated, in particular brominated, epoxy resins based on the phenols listed above can also be used, in particular for products which are to be used in the electronics sector (printed circuit boards).
  • the imidazoline compounds according to the invention can also be used in a mixture with the aminic curing agents customary in this field.
  • dicyandiamide In combination with dicyandiamide, they can act both as co-hardening agents and as accelerators and accordingly can be used in the desired mixing ratio.
  • the hardening or acceleration / hardening behavior achieved is influenced by the respective structures and quantitative ratios.
  • modification or auxiliary substances such as phenolic resins, melamine resins, silicone resins, inorganic and organic fillers such as quartz powder, titanium dioxide, carbon black, silicone rubber or butadiene rubber can also be used to modify the properties of the end product.
  • viscous resins or diluents can be used, but also the customary solvents such as diethylformamide, acetone, methyl ethyl ketone, methyl glycol, propylene glycol monomethyl ether, short-chain alcohols or mixtures thereof.
  • customary solvents such as diethylformamide, acetone, methyl ethyl ketone, methyl glycol, propylene glycol monomethyl ether, short-chain alcohols or mixtures thereof.
  • Organic and inorganic fibers, nonwovens and fabrics based on aramid, carbon or cellulose, metals such as boron, steel etc., ceramics, but especially glass, are also used to produce the prepregs.
  • the preparation of the solvent-containing prepregs takes place according to the method known per se, in which the carrier materials are impregnated with the reactive resin mixture in an impregnation bath and, after the excess amount of resin has been squeezed off, continuously with the supply of energy (usually heat), with simultaneous removal of the solvent means to be converted from the A to the B state.
  • the desired prepreg consistency sticking to firm
  • these are then provided with a release film on both sides and rolled up for storage and transport.
  • the further processing takes place by cutting and folding the individual prepreg layers into a stack, from which a highly cross-linked workpiece is produced by shaping measures with simultaneous supply of heat.
  • the curing agents according to the invention can also be used successfully in solvent-free prepregs based on epoxy resins and, if appropriate, customary curing agents.
  • the carrier materials are impregnated with the binder systems, if appropriate at elevated temperature, by methods known per se and stored appropriately for the system before they are further processed like the solvent-containing systems.
  • solvent-free systems are wet laminates, in-situ fiber-reinforced molded parts (RTM), heat-curing one-component adhesives, for. B. for the bonding of body parts in the automotive industry and epoxy resin castings and epoxy resin coatings, which are applied either wet or as a powder.
  • reaction product present in the bottom is purified by distillation at 200-230 ° C / 100 mbar.
  • a colorless, semi-solid product at RT is obtained with the following key figures:
  • Adduct of imidazoline according to Example 1 and liquid epoxy resin (average molecular weight 380)
  • a brominated epoxy resin dissolved in 25 g methyl ethyl ketone (MEK) (epoxy value approx. 0.18, bromine content approx. 18) are mixed with 10 g of a 50% hardener solution from the reaction product according to the invention and MEK and used for prepreg production .
  • MEK methyl ethyl ketone
  • the hardener solution is prepared at RT, and its concentration can in principle be chosen arbitrarily.
  • the prepreg was further processed into approximately 1 mm thick laminates in one hour at 150 ° C with a pressing pressure of approximately 1 bar.
  • the end product cured in this way showed no defects with regard to the liability of the individual prepreg layers.
  • 100 ⁇ 10 mm 2 specimens were then removed from the laminates and examined in a torsional vibration test in accordance with DIN 53455. The results of this test are shown in Table 1 for various mixing ratios.
  • Example 2 The other TG values of Examples 2-4, likewise listed in Table 1, were determined analogously to Example 1.
  • the mixtures consisting solely of epoxy resin and hardening agent, are hardened and tested in order to avoid falsifying influences from reinforcing and additional materials.
  • test specimens 100 g of the epoxy resin are mixed with the amount of curing agent mentioned in Table 2 at room temperature and cured in a steel tool to give 4 mm thick flat moldings. These molded parts are then bwz by sawing. Milling Test specimens taken on which the property values listed in Table 2 were determined in compliance with the test standards listed below.
  • the commercially available phenylimidazoline was also included in the table.

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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)

Abstract

L'invention a pour objet des composés de formule générale (I): dans laquelle R1 est un reste alkyle, éventuellement ramifié, de 1 à 9, de préférence de 1 à 5 atomes de carbone, et leur utilisation comme agents de durcissement pour résines époxy.
PCT/EP1991/002474 1991-04-27 1991-12-20 Diaminocyclohexane-imidazolines et leur utilisation Ceased WO1992019601A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19914113870 DE4113870A1 (de) 1991-04-27 1991-04-27 Diaminocyclohexan-imidazoline und ihre verwendung
DEP4113870.8 1991-04-27

Publications (1)

Publication Number Publication Date
WO1992019601A1 true WO1992019601A1 (fr) 1992-11-12

Family

ID=6430535

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1991/002474 Ceased WO1992019601A1 (fr) 1991-04-27 1991-12-20 Diaminocyclohexane-imidazolines et leur utilisation

Country Status (2)

Country Link
DE (1) DE4113870A1 (fr)
WO (1) WO1992019601A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107771175A (zh) * 2015-06-22 2018-03-06 Sika技术股份公司 用于可固化组合物的脒催化剂
US10988415B2 (en) 2015-09-24 2021-04-27 Sika Technology Ag Dispersant for calcium sulphate-based compositions

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2663712A (en) * 1949-11-22 1953-12-22 Gen Aniline & Film Corp Hydroxy-benzimidazoles and method for their preparation
EP0450322A1 (fr) * 1990-04-02 1991-10-09 Witco GmbH Dérivés d'imidazole, leur utilisation comme durcisseur pour compositions de résine époxyde, compositions de résines époxydes les contenant et objets qui en sont formés
EP0457046A1 (fr) * 1990-05-18 1991-11-21 Witco GmbH Dérivés imidazolyliques, leur application comme durcisseurs dans des compositions de résines époxydes, compositions durcissables de résines époxydes les contenant et objets formés de résines époxydes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2663712A (en) * 1949-11-22 1953-12-22 Gen Aniline & Film Corp Hydroxy-benzimidazoles and method for their preparation
EP0450322A1 (fr) * 1990-04-02 1991-10-09 Witco GmbH Dérivés d'imidazole, leur utilisation comme durcisseur pour compositions de résine époxyde, compositions de résines époxydes les contenant et objets qui en sont formés
EP0457046A1 (fr) * 1990-05-18 1991-11-21 Witco GmbH Dérivés imidazolyliques, leur application comme durcisseurs dans des compositions de résines époxydes, compositions durcissables de résines époxydes les contenant et objets formés de résines époxydes

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107771175A (zh) * 2015-06-22 2018-03-06 Sika技术股份公司 用于可固化组合物的脒催化剂
US11292771B2 (en) 2015-06-22 2022-04-05 Sika Technology Ag Amidine catalyst for curable compositions
US10988415B2 (en) 2015-09-24 2021-04-27 Sika Technology Ag Dispersant for calcium sulphate-based compositions

Also Published As

Publication number Publication date
DE4113870A1 (de) 1992-10-29

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