Classifications

• • 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
• • 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

Definitions

• the invention relates to curable mixtures of glycidyl compounds and aminic curing agents which contain heteroeyclic tertiary amines as curing accelerators and which have a fast curing rate even with a long pot life.
• Curable mixtures based on glycidyl compounds and amine hardening agents are widely used in industry for coating and coating metallic and mineral surfaces.
• the amines used are, in particular, aliphatic, cycloaliphatic, aromatic or araliphatic compounds and, if appropriate, polyaminoamides containing imidazoline groups based on mono- or polybasic acids and their adducts with epoxy resins.
• the curable mixtures based on epoxy resins and these amine compounds generally have a sufficiently long pot life, but their rate of hardening after application to the various substrates is too slow for many areas of application.
• the viscosity of many compounds is relatively high, especially in the range of low temperatures.
• the hardening rate can be increased by adding suitable hardening accelerators.
• Mannich bases of tertiary amines are used in some systems, such as. B. Tris (dimethylaminomethyl) phenol (DMP30).
• DMP30 Tris (dimethylaminomethyl) phenol
• phenol-free accelerators containing at least one tertiary amine group are used in some applications.
• a typical representative of this class is dimethylaminopropylamine.
• the object of the present invention was therefore to prepare curable mixtures
• Amines each containing a primary and a tertiary amine group.
• the invention therefore relates to curable mixtures based on epoxy resins and aminic curing agents, optionally with the use of solvents, plasticizers, UV stabilizers, dyes, pigments, fillers, which are characterized in that as curing accelerators
• the invention further relates to curable mixtures consisting of: a) 30-70% by weight, based on epoxy resin + curing agent, epoxy resin with an EP value of 0.4-0.56 b) 25-70% by weight , based on epoxy resin + hardener, aminic
• heterocyclic amines used in accordance with the invention can be prepared by reacting formaldehyde with amines of the general formula (II)
• Formaldehyde to amine from 0.9: 1 to preferably 1: 1.
• the amine is generally introduced and formaldehyde, preferably paraformaldehyde, is added in portions.
• the reaction is exothermic.
• the addition of the aldehyde is therefore controlled so that the reaction temperature of about 100 ° C is not exceeded. According to the invention, it is preferably carried out between approximately 30 ° C.-80 ° C.
• the water of reaction formed is removed from the reaction mixture by raising the temperature to about 130 ° C. and, if appropriate, under reduced pressure. The remaining residue can be used as a curing accelerator without further purification.
• the epoxy compounds used in accordance with the invention are commercially available products with more than one epoxy group per molecule, which are derived from mono- or / and polyvalent, mono- or / and polynuclear phenols, in particular bisphenols, and novolaks.
• a comprehensive list of these di- or polyphenols can be found in the manual "Epoxiditatien und Epoxidharze” by A. M. Paquin, Springer Verlag, Berlin, 1958, Chapter IV, and Lee & Neville "Handbook of Epoxy Resins", 1967, Chapter 2.
• Glycidyl compounds based on bisphenol A (4,4'-dihydroxydiphenylpropane-2,2) with epoxy values of 0.4 to 0.56 are preferably used.
• the epoxy resins mentioned for example can be used both for the curable combinations and for the preparation of the curing agent-epoxy adducts which can likewise be used in the process according to the invention.
• the curing agents used in accordance with the invention are aliphatic, cycloaliphatic, araliphatic or aromatic amines, aminoamides optionally containing imidazoline groups and their adducts with glycidyl compounds which contain more than two reactive amines in hydrogen atoms per molecule. These compounds belong to the general state of the art and are described in, for example, Lee & Neville, "Handbook of Epoxy Resins", Mc Graw Hill Book Company, 1967, Chapter 6-10.
• Cycloaliphatic amines or polyaminoamides based on mono- or polyvalent carboxylic acids and polyalkylene polyamines and their adducts with glycidyl compounds are preferably used for the coating of metallic or mineral substrates.
• hardeners are commercially available products and are offered, for example, by Witco GmbH under the trademark EUREDUR®, in particular EUREDUR (ED) 43, ED 46, ED 350.
• Hardening agents and epoxy compounds are preferably used in the process according to the invention in approximately equivalent amounts, that is to say based on active amine atoms and reactive epoxy groups. However, it is also possible to use curing agents or glycidyl components in excess or deficit. The respective amounts are in the range of approx. 10-200% by weight, based on glycidyl compounds, and depend on the desired end properties of the reaction product. Usual catalytic hardeners for epoxy resins can be used in addition to the hardening accelerators according to the invention.
• the procedure is such that the curing accelerators according to the invention and the customary catalytic or reactive curing agents are added separately in the desired ratio or as a mixture of the epoxy compound.
• the mixing ratio of glycidyl compound to the curing accelerators of formula I which are also used according to the invention is dependent on the particular Weil used compound and the desired end properties of the hardened end products controlled.
• an accelerator amount of 1-20% by weight, based on glycidyl ether is used; According to the invention, an amount of about 3-10% by weight is preferred.
• the particular advantage of the curable mixtures according to the invention lies in their excellent curing behavior at temperatures of 10-40 ° C. and high relative air humidity values of up to approx. 95%.
• inorganic and / or organic additives such as finely divided sands, talc, silicic acid, alumina, metals or metal compounds in chip and powder form, thixotropic agents, fibrous substances such as, for example, can be added to the epoxy resin / curing agent mixtures according to the invention.
• inorganic and / or organic additives such as finely divided sands, talc, silicic acid, alumina, metals or metal compounds in chip and powder form, thixotropic agents, fibrous substances such as, for example, can be added to the epoxy resin / curing agent mixtures according to the invention.
• asbestos and glass staple fibers pigments, flame retardants, solvents, dyes, plasticizers, bitumen, mineral oils, are added.
• the curable mixtures according to the invention can be used to coat absorbent or non-absorbent substrates such as natural stones, marble, concrete, metals, glass.
• the mixture was then left to react for about 30 minutes until a clear reaction product free of solids was present. Then the reaction product was heated. The distillation of the released water began at a bottom temperature of around 102 ° C. The temperature was raised to 130 ° C. in the course of about 30 minutes. The mixture was left to stir at 130 ° C. for 30 min and then reduced to 1 mbar in order to free the product from residual water and residual free dimethylaminopropylamine.
• the total distillate was approximately 19 g.
• the vacuum was then broken with nitrogen and the reaction product was allowed to cool.
• Example 1 130 g of diethylaminopropylamine and 30 g of paraformaldehyde
• Example 1 According to Example 1, the following were implemented: 130 g of diethylaminopropylamine, 204 g of dimethylaminopropylamine and 90 g of paraformaldehyde
• Example 1 According to Example 1, the following were implemented: 195 g diethylaminopropylamine 153 g dimethylaminopropylamine 90 g paraformaldehyde
• Example 1 According to Example 1, the following were implemented: 174 g of diethylaminoethylamine, 153 g of dimethylaminopropylamine and 80 g of paraformaldehyde
• DMAPA N, N-dimethylaminopropylamine
• ED 46 modified adduct based on cycloaliphatic and araliphatic amines and glycidyl ether based on bisphenol A with an amine number (AZ) of approx. 325
• ED 43 modified adduct based on cycloaliphatic and araliphatic amines and glycidyl ether based on bisphenol A with an AZ of approx. 270
• EP 783 modified epoxy resin based on bisphenol A
• ED 350 polyaminoimidazoline with an AZ of 390
• EP 710 diglycidyl ether based on bisphenol A with an EP value of

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Epoxy Resins (AREA)
• Paints Or Removers (AREA)

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Citations (5)

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• 1997
  • 1997-04-16 ES ES97106231T patent/ES2159067T3/es not_active Expired - Lifetime
  • 1997-04-16 DE DE59704012T patent/DE59704012D1/de not_active Expired - Lifetime
  • 1997-04-16 EP EP97106231A patent/EP0872505B1/de not_active Expired - Lifetime
• 1998
  • 1998-01-22 KR KR1019997009553A patent/KR20010006463A/ko not_active Ceased
  • 1998-01-22 WO PCT/EP1998/000327 patent/WO1998046660A1/de not_active Ceased
  • 1998-01-22 AU AU62932/98A patent/AU732395B2/en not_active Ceased
  • 1998-01-22 US US09/402,980 patent/US6355763B1/en not_active Expired - Lifetime
  • 1998-01-22 CA CA002287395A patent/CA2287395A1/en not_active Abandoned
  • 1998-01-22 JP JP54339298A patent/JP3932404B2/ja not_active Expired - Fee Related

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Non-Patent Citations (2)

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