EP0883638A1 - Produits d'addition d'epoxyde et d'amine utiles comme emulsifiants de resines epoxydes; dispersions de resine epoxyde a base aqueuse et leur procede de preparation - Google Patents

Produits d'addition d'epoxyde et d'amine utiles comme emulsifiants de resines epoxydes; dispersions de resine epoxyde a base aqueuse et leur procede de preparation

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Publication number
EP0883638A1
EP0883638A1 EP97951203A EP97951203A EP0883638A1 EP 0883638 A1 EP0883638 A1 EP 0883638A1 EP 97951203 A EP97951203 A EP 97951203A EP 97951203 A EP97951203 A EP 97951203A EP 0883638 A1 EP0883638 A1 EP 0883638A1
Authority
EP
European Patent Office
Prior art keywords
epoxy
amine
mixture
polyalkylene glycol
terminated
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.)
Withdrawn
Application number
EP97951203A
Other languages
German (de)
English (en)
Inventor
Michael Hess
Horst Schneider
Michael Hiller
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.)
Sika Holding GmbH
Original Assignee
Sika Chemie GmbH
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Filing date
Publication date
Application filed by Sika Chemie GmbH filed Critical Sika Chemie GmbH
Publication of EP0883638A1 publication Critical patent/EP0883638A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/281—Polyepoxides
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0645—Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds
    • C09K2200/0647—Polyepoxides

Definitions

  • Epoxy-amine adducts for use as emulsifiers for epoxy resins Water-based epoxy resin dispersions and process for their preparation.
  • the present invention relates to epoxy-amine adducts for use as emulsifiers for epoxy resins; Water-based epoxy resin dispersions using said emulsifiers and a process for their preparation.
  • Epoxy resin dispersions are generally quite unstable and tend to settle after a short time Binder, especially at temperatures above 25 ° C.
  • the resulting epoxy resin dispersions generally have particle sizes of more than 1 ⁇ m and, after storage for several weeks or several months, tend to coalesce, increase in particle size and thus deteriorate the film properties.
  • epoxy resin dispersions can also be added with reactive thinners to lower the viscosity and stabilize the dispersion during their production.
  • reactive thinners due to their irritating properties and mostly high vapor pressures, these are undesirable from a work hygiene point of view.
  • the chemical resistance of the cured epoxy resin films is often negatively affected by these reactive thinners.
  • Epoxy resin dispersions also solvents, benzyl alcohol and glycols or glycol ethers and the like. which are also undesirable.
  • DE-OS 43 10 198 describes, for example, that special nonionic emulsifiers, which polyol-epoxy addition products from (A) an aliphatic diol with a weight-average molar mass of 200 to 20,000 g / mol and from (B) an epoxy compound with at least are two epoxy groups per molecule and an epoxide equivalent weight of 100 to 2000 g / mol and an equivalent ratio of the OH groups to the epoxide groups of 1: 3.6 to 1:10, and the epoxide equivalent weight of the addition product between 150 g / mol and at least 8000 g / Mole, for use in water-dilutable epoxy liquid resin systems are particularly suitable.
  • special nonionic emulsifiers which polyol-epoxy addition products from (A) an aliphatic diol with a weight-average molar mass of 200 to 20,000 g / mol and from (B) an epoxy compound with at least are two epoxy groups per molecule and
  • Said aliphatic polyols (A) are polyether polyols (polyalkylene glycols), the epoxy compounds (B) are polyglycidyl ethers based on dihydric alcohols or novolaks, particularly preferably bisphenol A.
  • the emulsifiers described above are obtained by condensation of the polyether polyols (A) with the epoxy compounds (B) prepared in the presence of suitable catalysts.
  • liquid epoxy resins based on bisphenol A and bisphenol F diglycidyl ethers By mixing the emulsifiers thus obtained with liquid epoxy resins based on bisphenol A and bisphenol F diglycidyl ethers, self-emulsifying liquid resin systems are obtained which can be treated with water-dilutable amine hardeners, e.g. B. crosslink polyamines and polyoxyalkylene di- and polyamines with molecular weights of 100 to 2000 (Jeffamine R Texaco Corp.) to films with good properties, which are used primarily as protective coatings for mineral substrates.
  • water-dilutable amine hardeners e.g. B. crosslink polyamines and polyoxyalkylene di- and polyamines with molecular weights of 100 to 2000 (Jeffamine R Texaco Corp.) to films with good properties, which are used primarily as protective coatings for mineral substrates.
  • DE-OS 43 09 639 describes aqueous epoxy resin dispersions which contain:
  • (A-l-c) 0 to 25% by weight of modifying compounds with at least two epoxy-reactive groups, (A-2) a dispersant in the form of a
  • Epoxide equivalent weight of this condensation product is between 5000 and 400,000 g / mol
  • (C) optionally conventional additives, components (A-1), (A-2) and (B) being used in such amounts by weight that the equivalent ratio of the epoxy groups capable of reaction to the carboxyl groups is at least 1: 0.5.
  • the compounds according to (A-l-c) are compounds for the targeted modification of the base resin (A-l), e.g. B. polyamines, poly (alkylene oxides) with terminal amino groups (z. B. Jeffamine (ß) from Texaco Corp.), polycarboxylic acids and their anhydrides and the like. They can be used to adjust desired properties of the base resin (Al) by targeted modification .
  • the first part, component (A) or the base resin consists of a diglycidyl ether of bispenol A or a derivative thereof.
  • the diglycidyl ether is partially reacted with a polyoxyalkylene amine.
  • the second part, component (B) or the curing agent consists of a reactive polyamide polyamine.
  • the polyoxyalkylene amine is a block copolymer of ethylene oxide and propylene oxide with primary amino groups in the end position, for example a monoamine (Jeffamine (R M series from Texaco Corp.) or a diamine (Jeffamine (R) ED series from Texaco Corp.).
  • Part (B) of the two-component composition comprises a reactive, water-compatible polyamide polyamine which has been prepared by reacting multifunctional carboxylic acids, esters, anhydrides or mixtures thereof with a polyfunctional amine, which may be aliphatic, cycloaliphatic or aromatic, or with mixtures thereof.
  • U.S. Patent No. 5,459,208 describes elastic cured epoxy resin compositions which include: (A) reaction products of (AI) compounds with at least two 1,2-epoxy groups per molecule with (A2) polyoxyalkylene monoamines with average molecular weights (by number)> 900 g / mol, the
  • Polyoxyalkylene monoamines contain a mole fraction of up to 20% of polyoxyethylene units, based on the total amount of polyoxypropylene and polyoxyethylene units, and, if desired, with (A3) polycarboxylic acids, and
  • Preferred epoxy components (AI) are glycidyl ethers which are derived from bisphenols and novolaks and whose epoxide equivalent weights are between 150 and 500 g / mol. Polyglycidyl ethers based on aliphatic alcohols can also be used. preferred
  • Polyoxyalkylene monoamines (A2) are monoamine block copolymers which contain oxypropylene and oxyethylene groups and are available from Texaco Chemical Co. under the trademarks Jeffamine (g) M series, for example Jeffamine ( ⁇ ) M-2005 with a molecular weight of approximately 2000 g / Mol and an oxypropylene-oxyethylene ratio of 32/3.
  • the object of the invention is achieved by providing epoxy-amine adducts which contain:
  • (A-2) one or more epoxy-amine adducts, obtained by reacting at least one or more epoxy compound (s) based on polyhydric aliphatic alcohols with an epoxy functionality> 1 and ⁇ 4 and an average epoxide equivalent weight between 70 g / eq and 6000 g / eq with at least one or more polyalkylene glycol (s) terminated with an amino group or with mixtures thereof of polyalkylene glycols terminated with two amino groups, with an average amine functionality of 0.5 to 1.5; an average molecular weight of 700 to 5000; Ethylene oxide contents of> 60% by weight, based on the total content of polyalkylene glycol and a ratio of the reactive equivalents of the amine-terminated polyalkylene glycol or of the amine-terminated Polyalkylene glycol mixture to that of the polyepoxide or the polyepoxide mixture from 0.01: 1 to 0.9: 1;
  • the mixing ratio of the one or more epoxy-amine adducts according to (A-1) with one or more of the epoxy-amine adducts according to (A-2) is between 5:95 and 95: 5.
  • the epoxy-amine adducts according to the invention are used as emulsifiers for epoxy resins.
  • the invention also relates to curable, aqueous solvent-free or low-solvent epoxy resin dispersions which contain:
  • (B-l) epoxy resins in the form of polyglycidyl ethers based on polyhydric aromatic or cycloaliphatic alcohols and of novolaks with an epoxy functionality> 1 and ⁇ 3.5 and an average epoxide equivalent weight between 70 g / eq and 1000 g / eq;
  • (B-2) optionally epoxy resins in the form of polyglycidyl esters based on aromatic or cycloaliphatic polycarboxylic acids with an epoxy functionality> 1 and ⁇ 3.5 and an average epoxy equivalent weight between 70 g / eq and 1000 g / eq;
  • the epoxy compounds which are converted to the emulsifiers according to the invention in accordance with (A1) have epoxy functionalities of> 1 and ⁇ 4, preferably of> 1.5 and ⁇ 2.7, and average epoxy equivalent weights between 70 g / eq and 1000 g / eq, preferably between 150 g / eq and 550 g / eq and particularly preferably between 160 g / eq and 300 g / eq.
  • epoxy compounds are preferably polyglycidyl ethers based on polyhydric, preferably dihydric aromatic or cycloaliphatic alcohols, such as phenols, hydrogenation products of these phenols and / or novolaks (reaction products of mono- or polyhydric phenols with aldehydes, especially formaldehyde in the presence of acidic catalysts) .
  • polyhydric phenols examples include: resorcinol, hydroquinone, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), mixtures of isomers of dihydroxydiphenylmethane (bisphenol F), tetrabromobisphenol A, 4, 4 'dihydroxydiphenylcyclohexane, 4, 4'-dihydroxy-3, 3'-dimethyldiphenylpropane, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxybenzophenol, bis- (4-hydroxyphenyl) -1, 1-ethane, 2,2-bis- [4- ( 2-hydroxy-propoxy) phenyl] propane, bis- (4-hydroxyphenyl) -1, 1-isobutane, bis- (4-hydroxy-tert-butylphenyl) -2, 2-propane, bis (4-hydroxy- phenyl) -2, 2-propane, bis- (2-hydroxynaphthyl) methane, 1, 5-di
  • polyglycidyl esters of polycarboxylic acids which are obtained by reacting epichlorohydrin or similar epoxy compounds with an aromatic or cycloaliphatic polycarboxylic acid, for example with phthalic acid, terephthalic acid, hexahydrophthalic acid or else 2,6-naphthalenedicarboxylic acid.
  • examples are diglycidyl phthalate, diglycidyl terephthalate, diglycidyl hexahydrophthalic acid, diglycidyl 2,6-naphthalenedicarboxylate.
  • Halogenation or hydrogenation products or mixtures of the abovementioned compounds, and mixtures with the above-mentioned epoxy compounds can also be used.
  • the above-mentioned epoxy compounds are reacted with at least one, but preferably with two amine-terminated polyalkylene glycols (polyoxyalkylene amines).
  • Polyoxyalkylene monoamines or mixtures thereof, or mixtures thereof with polyoxyalkylene diamines having molecular weights of about 700 to about 5000, are suitable as such.
  • the preferred amine-terminated polyalkylene glycols or mixtures thereof have ethylene oxide contents of> 60% by weight, preferably> 65% by weight, based on the total content of polyalkylene glycol, and average amine functionalities of 0.5 to 1.5, preferably 0.7 to 1 , 2 and molecular weights of preferably 1000 to 2000. They have at least one, but preferably two, active amine hydrogen atoms which are bonded to a nitrogen atom.
  • the amine terminated polyalkylene glycols with the aforementioned preferred properties are typical Polyoxyalkylene monoamines, ie compounds which are sold, for example, under the trademark Jeffamine R by Texaco Corp. (now Huntsman Corp.).
  • Jeffamine ( ⁇ ) M-1000 is, for example, an (ethylene oxide / propylene oxide) copolymer with a molar ratio x of approximately 18.6 (ethylene oxide fraction) to y of approximately 1.6
  • polyoxyalkylene diamines ethylene oxide / propylene oxide copolymers with molecular weights from about 900 to 5000, preferably from 1000 to 2000, which are terminated with two primary amino groups, can be used.
  • Diamines of this type are available from Texaco Corp. distributed under the trademark Jeffamine (ly ED series.
  • reaction products to form epoxy-functional dispersants / emulsifier resins have, for example, the following idealized structure resulting from the structure of the starting components:
  • the ratio of the reactive equivalents of the polyoxyalkylene amine or the polyoxyalkylene amine mixture to those of the polyepoxide or the polyepoxide mixture is in the range from about 0.01: 1 to 0.9: 1, preferably in the range from 0.1: 1 to 0, 7: 1.
  • the reaction of polyoxyalkylene amine and polyepoxide takes place in a temperature range from about 70 ° C to 180 ° C, preferably from 90 ° C to 150 ° C, in a nitrogen atmosphere and possibly in the presence of epoxy-amine accelerators, for. B. in the presence of salicylic acid, tri (dimethylaminomethyl) phenol or other suitable tert. Amines and the like.
  • the reaction is carried out until the reactive amine hydrogen equivalents contained in the amine-terminated polyalkylene glycols have been converted to at least 50%.
  • the preferred degree of conversion of amine and epoxide is> 70%, preferably> 85%, based on the reactive amine hydrogen equivalents in the amine-terminated polyalkylene glycol.
  • the epoxy compounds which are converted into the dispersants / emulsifiers according to the invention according to (A-2) have an epoxy functionality> 1 and ⁇ 4, preferably of> 1.5 and ⁇ 2.7, and average epoxy equivalent weights between 70 g / eq and 6000 g / eq, preferably between 150 g / eq and 3500 g / eq and particularly preferably between 250 g / eq and 800 g / eq.
  • These epoxy compounds are preferably polyglycidyl ethers based on polyhydric aliphatic, preferably dihydric aliphatic alcohols and particularly preferably dihydric polyalkylene glycols. Polypropylene glycol diglycidyl ether and diglycidyl ether based on (ethylene oxide / propylene oxide) copolymers or mixtures of these diglycidyl ethers are particularly preferred.
  • polyglycidyl esters of polycarboxylic acids which are obtained by reacting epichlorohydrin or similar epoxy compounds with an aliphatic polycarboxylic acid, for example with adipic acid, suberic acid, sebacic acid and the like, or also with polyglycol diacids, for example with an average molecular weight of about 600 (as in Chemical Abstracts under CAS No. 39 927-08-07), which are available from Hoechst AG.
  • Halogenation products of the abovementioned compounds are also suitable, as well as mixtures with the aforementioned epoxy compounds.
  • the above-mentioned epoxy compounds are reacted with at least one, but preferably with a mixture of two amine-terminated polyalkylene glycols (polyoxyalkylene amines).
  • Polyoxyalkylene monoamines or mixtures thereof, or mixtures thereof with polyoxyalkylenediamines having molecular weights of about 700 to 5000 are suitable as such.
  • the preferred amine-terminated polyalkylene glycols have ethylene oxide contents of> 60% by weight, preferably> 65% by weight, based on the total content of polyalkylene glycol, with their mixtures average amine functionalities from 0.5 to 1.5, preferably from 0.7 to 1.2 and have molecular weights of preferably 1000 to 2000.
  • polyoxyalkylene amines are the polyoxyalkylene monoamines described in more detail above under (A-1) and are available, for example, under the trademarks Jeffamine R M-1000 and Jeffamine (R) M-2070 from Texaco Corp. to be expelled. Mixtures of Jeffamine (R) M-1000 and (g) M-2070 are preferably used.
  • Jeffamine (R) M-715 with a molecular weight of about 700 or Experimental Amine No. 6940-29 with a molecular weight of about 3000 terminated with an amino group can also be used.
  • polyoxyalkylene diamines ethylene oxide / propylene oxide copolymers with
  • the ratio of the reactive equivalents of the polyoxyalkylene amine or the polyoxyalkylene amine mixture to those of the polyepoxide or the polyepoxide mixture is in the range from about 0.01: 1 to 0.9: 1, preferably in the range from 0.1: 1 to 0, 7: 1.
  • the reaction of polyoxyalkylene amine and polyepoxide takes place in a temperature range from about 70 ° C to 180 ° C, preferably from 90 ° C to 150 ° C, in a nitrogen atmosphere and possibly in the presence of epoxy-amine accelerators, for. B. in the presence of salicylic acid, tri (dimethylaminomethyl) phenol or other suitable tert. Amines and the like.
  • the reaction is carried out until the reactive amine hydrogen equivalents contained in the amine-terminated polyalkylene glycols are converted to at least 50% are.
  • the preferred degree of conversion of amine and epoxide is> 70%, preferably> 85%, based on the reactive amine hydrogen equivalents in the amine-terminated polyalkylene glycol.
  • the emulsifier mixtures according to the invention contain at least one epoxy resin-amine adduct from each of the groups of substances described under (A-1) and (A-2).
  • the mixing ratio of an epoxy-amine adduct or an epoxy-amine adduct mixture according to (Al) to an epoxy-amine adduct or an epoxy-amine adduct mixture according to (A-2) is between 5:95 and 95: 5 , preferably between 10:90 and 90:10, but particularly preferably between 20:80 and 80:20.
  • Mixing ratios of 33:67, 67:33 and 50:50 are given in the exemplary embodiments, the latter being particularly preferred.
  • the dispersants / emulsifiers based on amine-terminated polyalkylene glycols with the amine functionalities mentioned lead to extremely low-viscosity systems.
  • Another advantage is that after the reaction and incorporation of the dispersant / emulsifier into the polymer structure and through hardening with suitable amine hardeners, the systems provide coatings and coatings with good water and chemical resistance and, as coatings on metallic substrates, provide excellent corrosion protection and have good mechanical properties such as high impact strength and low embrittlement tendency.
  • the dispersant / emulsifier components described above under (A1) and (A-2) are mixed and homogenized with the epoxy resins described below under (B1) and (B-2) or mixtures thereof.
  • the epoxy resins according to (B1) and (B-2) or mixtures thereof have an epoxy functionality> 1 and ⁇ 3.5, preferably of> 1.5 and ⁇ 2.7 and mean epoxy equivalent weights between 70 g / eq and 1000 g / eq , preferably between 100 g / eq and 550 g / eq and particularly preferably between 150 g / eq and 300 g / eq.
  • the epoxy compounds according to (B1) are preferably polyglycidyl ethers based on polyhydric, preferably dihydric aromatic or cycloaliphatic alcohols, such as phenols, hydrogenation products of these phenols and / or novolaks (reaction products of mono- or polyhydric phenols with aldehydes, especially formaldehyde in Presence of acidic catalysts).
  • polyhydric phenols examples include resorcinol, hydroquinone, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), mixtures of isomers of dihydroxydiphenylmethane (bisphenol F), tetrabromobisphenol A, 4, 4 'dihydroxydiphenylcyclohexane, 4, 4'-dihydroxy-3, 3'-dimethyldiphenylpropane, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxybenzophenol, bis- (4-hydroxyphenyl) -1, 1-ethane, 2,2-bis- [4- ( 2-hydroxy-propoxy) phenyl] propane, bis- (4-hydroxyphenyl) -1, 1-isobutane, bis- (4-hydroxy-tert-butylphenyl) -2, 2-propane, bis (4-hydroxy- phenyl) -2, 2-propane, bis (2-hydroxynaphthyl) methane, 1,5-dihydroxy
  • polyglycidyl esters of polycarboxylic acids which are obtained by the reaction of epichlorohydrin or the like can also be used
  • Epoxy compounds with an aromatic or cycloaliphatic polycarboxylic acid for example with phthalic acid, terephthalic acid, hexahydrophthalic acid or also 2,6-naphthalenedicarboxylic acid.
  • Examples are diglycidyl phthalate, diglycidyl terephthalate, diglycidyl hexahydrophthalate, diglycidyl 2,6-naphthalenedicarboxylate.
  • Halogenation or hydrogenation products of the abovementioned compounds and mixtures with the above-mentioned epoxy compounds can also be used.
  • the average molecular weights of the polyoxyalkylene amines contained in the water-dilutable or water-based mixtures of dispersant / emulsifier components (Al) and (A-2) and epoxy resins (Bl) and (B-2) described above are at least 800, based on the polyoxyalkylene amine content in the total mixture and are preferably between 900 to 2500 and most preferably between 1200 to 1800, in each case based on the polyoxyalkyleneamine content in the total mixture.
  • the mixtures of dispersants / emulsifier components (Al) and (A-2) and epoxy resin components (B1) and optionally (B-2) and optionally reactive diluents also contain at least 2.9% by weight, preferably 3.5 to 9, 3% by weight and most preferably 3.7 to 6% by weight of chemically bound ethylene oxide, based on the total mixture of the epoxy-functional components, which is introduced exclusively by the dispersant / emulsifier components.
  • the mixing and homogenization of the individual components can be achieved using liquid emulsifier components (Al) and (A-2) and liquid epoxy compounds (Bl) and (B-2) in agitators or by hand stirring within a few minutes at room temperature (about 20 up to 25 ° C) respectively. If partially crystallized, waxy or solid dispersant components and / or epoxy compounds are used, a careful preheating of the dispersant components and / or the epoxy compounds, preferably under a nitrogen atmosphere, is necessary until they melt.
  • the abovementioned mixtures of substances are dispersed in water by means of suitable dispersing processes in suitable dispersing apparatus.
  • the epoxy resin dispersions can be prepared with batchwise, preferably continuous, addition of water to the substance mixtures with vigorous stirring and with high shear at temperatures of ⁇ 100 ° C., preferably ⁇ 60 ° C. and even more preferably ⁇ 45 ° C.
  • suitable defoaming and deaerating additives for example polysiloxanes, mineral oil defoamers and the like, can be added.
  • Byk (R) -024 (mixture of foam-destroying polymers and polysiloxanes) from BYK-Chemie GmbH is mentioned as an example.
  • Suitable dispersing devices are colloid mills, homogenizers, dissolvers with toothed disks or other high-speed mixers with high shear forces.
  • auxiliaries can be added to lower the viscosity and improve the rheological properties of the dispersant and epoxy resin mixtures and of the aqueous dispersions.
  • the auxiliaries are, for example, the mono- to polyfunctional reactive diluents customary for epoxy resin systems, such as, for. As alkyl C12 / C14 glycidyl ether, cresyl glycidyl ether, hexanediol diglycidyl ether, polyglycidyl ester and the like. But also extenders, plasticizers and plasticizers, and solvents and mixtures thereof.
  • the epoxy resin dispersions according to the invention are usually mixed with suitable curing agents or curing agent mixtures before application in the mixing ratio suitable for the particular application.
  • suitable curing agents for curing at room temperature and / or lower temperatures are water-dilutable, water-dispersible or water-based amine curing agents for epoxy compounds with an amine hydrogen functionality> 2 which belong to the prior art, for example based on modified Mannich bases, aminoamides, aminoimidazolines or modified amine Epoxy adducts or mixtures thereof and others, as described in the patent applications and patent specifications WO 93/12187, DE 4303562, WO 93/21250, EP 0567831, EP-A-0000605, EP 0387418, DE 2332177 and DE 2361671.
  • Araliphatic amines, polyalkylene amines and polyoxyalkylene diamines are also suitable.
  • Corresponding curing agents are commercially available, for example, under the trademarks Beckopox (Hoechst AG), Epilink (Akzo Chemicals GmbH), Euredur (Witco GmbH), Casamid, Versamid (Henkel KGaA), RTC 14421/17 (product name Dow Chem. Co.), Jeffamine D and T (Texaco Corp. / Huntsman Corp.) etc. available.
  • water-dilutable, water-dispersible or water-based, modified mercaptans or mercaptan-epoxy adducts with a mercaptan-hydrogen functionality> 2 are also suitable as hardening agents.
  • the curing agents or curing agent mixtures are generally used in the epoxy to amine or mercaptan hydrogen equivalent ratio of 1: 0.5 to 1: 2.0. Forced curing of the coatings or coatings can take place, for example, by heating to about 50 ° C. to 120 ° C. over a period of about 10 to 130 minutes.
  • customary additives which may be present in the dispersions according to the invention are, for example, the customary paint additives such as pigments, pigment pastes, antioxidants, leveling or thickening agents, defoamers / deaerators and / or wetting agents, reactive thinners, fillers, catalysts, preservatives, protective colloids and the like.
  • the pigmentation and filling can be carried out either in the epoxy resin dispersions according to the invention or in the curing agent, or in each case separately in both components and / or separately in a third and / or fourth component.
  • Three-component or higher-component mixing systems are usually produced for epoxy-resin-modified cement systems, but two-component formulations are also possible.
  • the paint, coating and coating components are produced using customary paint and coating technology using suitable mixing equipment, e.g. dissolvers, agitators, bead mills and homogenizers.
  • the epoxy resin dispersions according to the invention and the water-dilutable, water-dispersible or water-based substance mixtures with the epoxy components described above are particularly suitable as dispersion binders for a) corrosion protection paints, lacquers and coating compositions on metal (e.g. on blasted, phosphated, galvanized or otherwise pretreated Steel); Aluminum, blasted, chromated, anodized or otherwise pretreated aluminum; Copper, pretreated copper; Brass, pretreated brass; Alloys and the like) and on corroded metal (e.g. on corroded steel; corroded zinc and aluminum), b) coatings and coverings for floors and industrial floors, c) epoxy resin-coated mineral systems (e.g.
  • ECC Systems epoxy-resin coated cement systems
  • g) combinations, mixtures and polymerizations with other dispersion binders or dispersions for the adjustment of certain properties, in particular for the defined adjustment of the water-dilutability, the dispersibility with fillers and pigments, the film-forming properties and the drying behavior
  • Reaction mixture is kept at a temperature between 122 and 130 ° C. Then the temperature for kept at 125 ° C for a further two hours. After the reaction mixture has cooled to room temperature (23 ° C.), a liquid reaction product is obtained which becomes cloudy when stored at room temperature (tendency to crystallize). Until further use, it is stored in a nitrogen atmosphere.
  • the titration to determine the EEW is carried out as described in PCT application WO 95/01387 on page 21.
  • the titrated EEW of the reaction product is 1483 g / eq.
  • the emulsifier component is prepared as described in Example III, but using a PPGDGE with an epoxide equivalent weight (EEW) of 300 to 330, which is available under the trademark Grilonit (g) F 704 from Ems-Chemie.
  • EW epoxide equivalent weight
  • g Grilonit
  • the emulsifier component is prepared as described in Example II, but using a PPGDGE with an epoxide equivalent weight (EEW) of 455 to 550, which is available from Witco GmbH under the trademark Eurepox (R) RV-F.
  • EW epoxide equivalent weight
  • R Eurepox
  • 315.43 g of PPGDGE are placed in the reaction vessel. After the reaction, a titrated EEW of 1811 is obtained. A liquid reaction product is obtained which becomes cloudy when stored at room temperature. Until further use, it is stored in a nitrogen atmosphere.
  • the emulsifier component is prepared as described in Example II, but using a PPGTGE with an epoxide equivalent weight (EEW) of 625 to 769, which is available under the trademark Eurepox ® RV-L from Witco GmbH and with the process changes described below .
  • EW epoxide equivalent weight
  • 435.35 g of PPGTGE are placed in the reaction vessel and preheated to 125.degree.
  • the preheated JAM1 / JAM2 mixture is then continuously added dropwise over a period of about 3.5 hours with thorough stirring, the temperature of the reaction mixture being kept at a temperature between 122 and 135 ° C.
  • the temperature is then kept at 125 ° C. for a further hour.
  • the preheated JAM1 / JAM2 mixture is then continuously added dropwise over a period of about three hours with thorough stirring, the temperature of the reaction mixture being kept at a temperature between 122 and 130 ° C. The temperature is then kept at 125 ° C. for a further hour. After the reaction mixture has cooled to room temperature (23 ° C.), a liquid reaction product is obtained which becomes cloudy when stored at room temperature (slight tendency to crystallize). Until further use, it is stored in a nitrogen atmosphere.
  • the EEW determined by titration is 1183 g / eq.
  • the emulsifier component is produced as in Example 1.5, but using a BPADGE with an epoxide equivalent weight (EEW) of 182 to 192, which is available under the trademark Eurepox 710 from Witco GmbH is.
  • EW epoxide equivalent weight
  • a mixture of emulsifier components is prepared by mixing and homogenizing the emulsifier components from Example II and Example 1.5 in a mixing ratio of 1: 2.
  • the cloudy emulsifier components are preheated to 60 ° C. and kept at this temperature until an optically clear one Component is present. This is followed by mixing and homogenization and further processing as described below in the examples under point II.
  • a mixture of emulsifier components is prepared by mixing and homogenizing the emulsifier components from Example 1.3 and Example 1.5 in a mixing ratio of 2: 1.
  • the cloudy emulsifier components are heated to 60 ° C. in advance and kept at this temperature until an optically clear one Component is present. This is followed by mixing and homogenization and further processing as described below in the examples under point II. 1.7.3 Emulsifier mixture 3
  • a mixture of emulsifier components is prepared by mixing and homogenizing the emulsifier components from Example 1.4 and Example 1.5 in a mixing ratio of 1: 1.
  • the cloudy emulsifier components are heated to 60 ° C. in advance and kept at this temperature until an optically clear one Component is present. This is followed by mixing and homogenization and further processing as described below in the examples under point II.
  • a mixture of emulsifier components is prepared by mixing and homogenizing the emulsifier components from Example 1.2 and Example 1.6 in a mixing ratio of 1: 1.
  • the cloudy emulsifier components are heated to 60 ° C. in advance and kept at this temperature until an optically clear one Component is present. This is followed by mixing and homogenization and further processing as described below in the examples under point II.
  • Epoxide equivalent weight (EEW) from 172 to 182, which is available under the trademark Araldit (fT) PY 304 from Ciba-Geigy. Then 10.5 g of Crystallization-free emulsifier mixture 1 added. The mixture is homogenized at low speeds using an anchor stirrer. It has an EEW of around 190 to 200 g / eq and can be used as a water-dispersible mixture of substances.
  • Emulsifier mixture 2 and polyglycidyl ether based on phenol novolak (PNPGE)
  • Epoxy equivalent weight (EEW) from 175 to 185, which is available under the trademark Eurepox () 720 LV from Witco GmbH. 48 g of the crystallization-free emulsifier mixture 4 are then added. The mixture is homogenized at low speeds using an anchor stirrer. It has an EEW of around 192 to 202 g / eq and can be used as a water-dispersible mixture of substances.
  • a Molteni disperser model TM.5 RSV from Officine Meccaniche Molteni Srl, 1-20030 Senago, Italy, with a stainless steel double-walled vessel with an inside diameter of about 20 cm, edge scraper, a toothed disc with a disc diameter from 10 cm as a stirrer and connected water cooling to 5 ° C.
  • the temperature should not exceed 45 to 50 ° C.
  • the maximum temperature in the preparation of the dispersion described above is about 41 ° C.
  • the average particle size, which was determined using a Microtrac UPA particle size measuring device with a connected computing unit from Leeds & Northrup GmbH, Krefeld, is 0.8 ⁇ m.
  • a mixture of emulsifier components is produced by mixing and emulsifying the emulsifier component 1.2 with the emulsifier component 1.5 in a mixing ratio of 1: 1.
  • Partially crystallized emulsifier components which are cloudy are preheated to 60 ° C. in advance and kept at this temperature until an optically clear component is present in each case.
  • the emulsifier components are then mixed with the epoxy resin and homogenized.
  • This mixture of emulsifier components and PNPGE is pre-cooled to 5 ° C. with stirring at low speeds in the dispersing apparatus. Demineralized water is then continuously cooled to 8 to 10 ° C at about 4800 rpm via a dropping funnel. metered into the closed vessel and dispersed. The amount added is always 150 to 160 ml / 10 min. In a range of about 82% solids, the viscosity increases sharply, and in the case of the following one
  • the temperature should not exceed 45 to 50 ° C.
  • the maximum temperature in the preparation of the dispersion described above is about 42 ° C.
  • a mixture of the emulsifier components is produced by mixing and emulsifying the emulsifier component 1.2 with the emulsifier component 1.5 in a mixing ratio of 1: 2.
  • Partially crystallized emulsifier components which are cloudy are preheated to 60 ° C. in advance and kept at this temperature until an optically clear component is present in each case.
  • the emulsifier components are then mixed with the epoxy resin and homogenized.
  • This mixture is pre-cooled to 5 ° C. in the dispersing apparatus with stirring at low speeds.
  • Demineralized water is then continuously cooled to 8 to 10 ° C at about 4800 rpm via a dropping funnel. metered into the closed vessel and dispersed. The amount added is always 150 to 160 ml / 10 min.
  • the viscosity increases strongly, and when the solid is subsequently reduced, the phase is reversed and an epoxy resin emulsion of the 0 / W (oil in water) type is formed.
  • the viscosity gradually drops, and when spraying heavily, the speed gradually increases to around 2000 rpm. reduced.
  • the epoxy resin dispersion III (EPD III) prepared is defoamed overnight.
  • the temperature should not exceed 45 to 50 ° C.
  • the maximum temperature in the preparation of the dispersion described above is about 42 ° C.
  • the average particle size, which was determined using a Microtrac UPA particle size measuring device with a connected computing unit from Leeds & Northrup GmbH, Krefeld, is 0.8 ⁇ m.
  • the temperature should not exceed 45 to 50 ° C.
  • the maximum temperature in the preparation of the dispersion described above is about 40 ° C.
  • the average particle size, which was determined using a Microtrac UPA particle size measuring device with a connected computing unit from Leeds & Northrup GmbH, Krefeld, is 0.7 ⁇ m.
  • the pigmentation of the epoxy resin dispersion EPD II for a floor coating as described in Table 1 is carried out in a closed 1 liter plastic container with presentation of about 2/3 of the amount of EPD II and the dispersing additive Disperbyk (R) 181 (solution of an alkylolammonium salt of a polyfunctional polymer with anionic / non-ionic character) and the defoamer Byk ( ⁇ ) 024 (mixture of foam-destroying polymers and polysiloxanes) from Byk-Chemie GmbH and subsequent dispersion of the pigment titanium dioxide (Kronos 2160 (R) from Kronos Titan GmbH) and of the filler barite flour N (barium sulfate from Dr. R.
  • Disperbyk (R) 181 solution of an alkylolammonium salt of a polyfunctional polymer with anionic / non-ionic character
  • ⁇ defoamer Byk
  • ⁇ mixture of foam-destroying polymers and polysiloxanes
  • the hardener component is added before application.
  • a water-based amine adduct hardener (Beckopox (R VEH 2177 w from Hoechst AG) is used for hardening. This has an amine hydrogen equivalent weight (AEW) of 170 to 180 g / eq in the delivery form.
  • AEW amine hydrogen equivalent weight
  • component 2 in VP 1 is set to 35% solids in formulation VP 1, component 1, described in table 1.
  • a stochiometric crosslinking one equivalent per epoxy group
  • Table 2 shows the formulation of a cement mortar.
  • the formulation VP 2, component 1 is produced by mixing sand and the mixture of substances according to II.2 on a compulsory mixer for about one hour. The Portland cement and the plasticizer are then added, and mixing is continued on the compulsory mixer until the mixture is evenly distributed. The mixture is free-flowing and dust-resistant and remains stable in storage for many weeks.
  • An amine adduct to which the water is added is used as the hardener, component 2.
  • the mixture of the hardener component is thin and stable for a few months between 5 and 30 ° C.
  • an amine adduct hardener on a water basis Beckopox (R EH 623, from Hoechst AG) with an amine hydrogen equivalent weight (AEW) of 185 to 215 g / eq used in the delivery form.
  • the formulation is distinguished by the fact that the epoxy resin-containing mixture of substances according to II.2 does not contain a reactive diluent and the formulation VP 2 therefore behaves far less problematically from the point of view of industrial hygiene.
  • two amine adduct hardeners on a water basis from Hoechst AG and Akzo Chemicals GmbH which come under the trademark Beckopox (R) EH 623 with an amine hydrogen equivalent weight (AEW) of 185 to 215 g / eq in the delivery form and Epilink ® DP 700 with an amine hydrogen equivalent weight (AEW) of 250 to 350 g / eq.
  • the curing agents are adjusted to 35% solids.
  • a stochiometric crosslinking one equivalent per epoxy group
  • the epoxy resin dispersions according to the invention show very low viscosities without the addition of reactive thinners or other solvents and thinners. Drying and curing can be varied in combination with appropriate curing agents depending on the application requirements. Because there is no need for reactive diluents and solvents, the epoxy resin dispersions according to the invention and water-dispersible or water-dilutable substance mixtures behave far less problematically from the point of view of industrial hygiene.
  • Solid body EPD II, EPD III and EPD IV 50% Pigmented and filled formulations and combination with hardening agents
  • VP 1 is tested after blending and application by means of a spatula on blasted panel base bodies in accordance with the technical test specification TP BE-PCC, point 6 (1990 edition). It is then vented using a spiked roller.
  • VP 2 is tested after blending and application to blasted panel base bodies in accordance with TP BE-PCC, point 6 (1990 edition) or incorporation into the primer.
  • the cement mortar is removed using height gauges and compacted and smoothed with a plastic trowel or with a wing or plate trowel with a plastic plate.
  • the covering thickness is about 5 to 7 mm. Further treatment is carried out in accordance with the rules for the post-treatment of mortars by storing the test specimens in damp conditions for about 5 days.
  • the test results with and without primer, with EPD II from Table 3, are summarized in Table 4.
  • Dispersants / emulsifiers on an aliphatic basis also depending on the mixing ratio (A-1) and (A-2) and the curing agents used, the flexibility and the film-forming properties are greatly improved.
  • the film formation property of the EPD II dispersion is one
  • Dispersant / emulsifier mixtures can be used to obtain particularly fine-particle dispersions with particle sizes ⁇ 1 ⁇ m.
  • the invention relates to: epoxy-amine adducts obtained by reacting (Al) at least one or more

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Abstract

Ces produits d'addition d'époxyde et d'amine sont obtenus en faisant réagir (A-1) au moins un ou plusieurs composés époxydes à base d'alcools aromatiques ou cycloaliphatiques polyvalents et/ou de novolaques avec une fonction époxyde ⊃1 et ≤4 et un poids moyen équivalent d'époxyde entre 70 g/eq et 1000 g/eq avec au moins un ou plusieurs polyalcylèneglycols terminés par un groupe amine avec une fonction amine moyenne de 0,5 à 1,5 et un poids moléculaire moyen de 700 à 5000; des teneurs en oxyde d'éthylène ≥60 % en poids, par rapport à la teneur totale en polyalcylèneglycol et un rapport entre les équivalents réactifs du polyalcylèneglycol à terminaison amine ou du mélange de polyalcylèneglycol à terminaison amine et les équivalents réactifs de polyépoxyde compris entre 0,01:1 et 0,9:1; (A-2) au moins un ou plusieurs composés époxydes à base d'alcools aliphatiques polyvalents avec une fonction époxyde ⊃1 et ≤4 et un poids moyen équivalent d'époxyde entre 70 g/eq et 6000 g/eq avec au moins un ou plusieurs polyalcylèneglycols terminés par un groupe amine avec une fonction amine moyenne de 0,5 à 1,5 et un poids moléculaire moyen de 700 à 5000; des teneurs en oxyde d'éthylène ≥60 % en poids, par rapport à la teneur totale en polyalcylèneglycol et un rapport entre les équivalents réactifs du polyalcylèneglycol à terminaison amine ou du mélange de polyalcylèneglycols à terminaison amine et les équivalents réactifs de polyépoxyde compris entre 0,01:1 et 0,9:1. Le rapport de mélange entre le ou les produits d'addition amine décrits sous (A-1) et le ou les produits d'addition d'amines et d'époxydes décrits sous (A-2) se situe entre 5:95 et 95:5.
EP97951203A 1996-11-20 1997-11-14 Produits d'addition d'epoxyde et d'amine utiles comme emulsifiants de resines epoxydes; dispersions de resine epoxyde a base aqueuse et leur procede de preparation Withdrawn EP0883638A1 (fr)

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US6077884A (en) 2000-06-20
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AU5482298A (en) 1998-07-03
JP2000504372A (ja) 2000-04-11

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