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  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/06—Phosphorus compounds without P—C bonds
  • C07F9/08—Esters of oxyacids of phosphorus
  • C07F9/141—Esters of phosphorous acids
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  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/06—Phosphorus compounds without P—C bonds
  • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
  • C07F9/165—Esters of thiophosphoric acids
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  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/06—Phosphorus compounds without P—C bonds
  • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
  • C07F9/165—Esters of thiophosphoric acids
  • C07F9/1653—Esters of thiophosphoric acids with arylalkanols
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  • C07F9/02—Phosphorus compounds
  • C07F9/28—Phosphorus compounds with one or more P—C bonds
  • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
  • C07F9/32—Esters thereof
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  • C07F9/02—Phosphorus compounds
  • C07F9/28—Phosphorus compounds with one or more P—C bonds
  • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
  • C07F9/32—Esters thereof
  • C07F9/3258—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
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  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/28—Phosphorus compounds with one or more P—C bonds
  • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
  • C07F9/40—Esters thereof
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  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/28—Phosphorus compounds with one or more P—C bonds
  • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
  • C07F9/40—Esters thereof
  • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
  • C07F9/4021—Esters of aromatic acids (P-C aromatic linkage)
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  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/28—Phosphorus compounds with one or more P—C bonds
  • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
  • C07F9/40—Esters thereof
  • C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
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  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/28—Phosphorus compounds with one or more P—C bonds
  • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
  • C07F9/40—Esters thereof
  • C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
  • C07F9/4075—Esters with hydroxyalkyl compounds
• • C—CHEMISTRY; METALLURGY
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  • 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
  • C08G59/20—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 epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/24—Di-epoxy compounds carbocyclic
  • C08G59/245—Di-epoxy compounds carbocyclic aromatic
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  • 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
  • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
  • C08G59/4064—Curing agents not provided for by the groups C08G59/42 - C08G59/66 sulfur containing compounds
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  • 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
  • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
  • C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
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  • 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
  • C08G59/44—Amides
• • C—CHEMISTRY; METALLURGY
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  • 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
  • C08G59/688—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 phosphorus
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
  • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
  • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/5398—Phosphorus bound to sulfur
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/18—Fireproof paints including high temperature resistant paints
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
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  • 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
  • C09K21/00—Fireproofing materials
  • C09K21/06—Organic materials
  • C09K21/12—Organic materials containing phosphorus
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G59/00—Treatment of naphtha by two or more reforming processes only or by at least one reforming process and at least one process which does not substantially change the boiling range of the naphtha
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  • C08G2150/00—Compositions for coatings
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  • C08G2190/00—Compositions for sealing or packing joints
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  • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

Definitions

• the present invention relates to novel curing agents and curing accelerators for curing and accelerated curing of epoxy resins and epoxy resin compositions comprising these curing agents or curing accelerators.
• thermosetting epoxy resins are due to their good
• epoxy resins show good adhesion to many substrates and are therefore ideally suited for use in fiber composites and as adhesives.
• the curing of epoxy resins proceeds according to different mechanisms. In addition to curing with phenols or anhydrides, hardening with amines is often carried out. These substances are usually liquid and mix very well with epoxy resins.
• Epoxy resin compositions made two-component. This means that the resin (A component) and hardener (B component) are stored separately and are mixed in the correct ratio just before use.
• “latent” means that a mixture of the individual components, namely the A component and the B component, is stable under defined storage conditions.
• These two-component resin formulations are also referred to as so-called cold-curing resin formulations, wherein the hardeners used for this are usually selected from the group of amines or amidoamines.
• thermosetting epoxy resin formulations are ready to use ready-made, that is, that epoxy resin and hardener are factory mixed. Mixing errors of the individual components in use on site are therefore excluded. A prerequisite for this is formed by latent hardener systems which do not react with the epoxy resin at room temperature (can be stored), but readily react when heated, depending on the energy input.
• latent hardener systems which do not react with the epoxy resin at room temperature (can be stored), but readily react when heated, depending on the energy input.
• dicyandiamide is a particularly suitable and also cost-effective hardener. Under ambient conditions, appropriate resin-hardener mixtures can be stored for up to twelve (12) months.
• Flame retardants are, for example, salt-like flame retardants, in particular melamine phosphate, and phosphorus-containing flame retardants, in particular based on 9,10-dihydro-9-oxa-10-phosphaphenanthren-10-oxide (DOPO) and derivatives thereof, to name (cf. Rakotomalala, S. Wagner and M. Döring, Materials 2010, 3, 4300-4327).
• DOPO 9,10-dihydro-9-oxa-10-phosphaphenanthren-10-oxide
• reactive organic phosphorus compounds such as
• EP 384 940 A1 discloses epoxy resin mixtures for use in printed circuit board materials which comprise a phosphorus-free polyepoxide resin in combination with an epoxide group-containing
• German Offenlegungsschriften DE 43 08 184 A1 and DE 43 08 187 A1 also disclose epoxy resin mixtures containing a phosphorus-modified epoxy resin having an epoxide value of 0.02 to 1 mol / 100 g in combination with the abovementioned polyamine.
• the phosphorus-modified epoxy resins are composed of structural units which are on the one hand of polyepoxide compounds having at least two
• anhydride curable epoxy casting resins which contain phosphonic anhydride as a curing agent or are obtained by modifying epoxy resin or hardener components with phosphorus compounds (cf DE 42 37 132 C1, DE 195 06 010 A1). These casting resins are predominantly highly viscous and can be processed without solvents only at temperatures> 60 ° C; for curing temperatures of> 80 ° C are needed.
• Phosphoric acid amides known that can be used in epoxy resins.
• the present invention is therefore based on the object of providing novel compounds which can be used for curing epoxy resins and epoxy resin compositions, in particular as curing agents and / or curing accelerators, and which, after being incorporated into epoxy resin compositions, additionally provide a flameproofing effect. such that the products made from or with the epoxy resin composition are flame retardant or fire retardant can be classified. There remains the need to provide such hardeners and curing accelerators with flame retardancy, which can be classified as latent and thus a high storage stability in epoxy resins below the
• Curing temperature and have a high reactivity at the curing temperature to allow complete crosslinking of the epoxy resin.
• Curing accelerator according to claim 2 Curing accelerator according to claim 2.
• Advantageous embodiments of the invention are specified in the subclaims, which can optionally be combined with one another.
• a curing agent for curing epoxy resins comprising at least one compound from the group of esters of phosphorus-containing acids according to formula (I) is the subject of the present invention, wherein for formula (I):
• R 1 , R 2 simultaneously or independently of one another hydrogen or alkyl
• R 3 alkyl, aryl, -O-alkyl, -O-aryl, -O-alkylaryl or -O-arylalkyl,
• R 6 hydrogen, alkyl or -NHC (0) NR 1 R 2 ,
• n 0, 1 or 2
• n 3
• R 1 , R 2 simultaneously or independently of one another hydrogen or alkyl
• R 3 alkyl, aryl, -O-alkyl, -O-aryl, -O-alkylaryl or -O-arylalkyl,
• R 6 hydrogen, alkyl or -NHC (0) NR 1 R 2 ,
• n 0, 1 or 2
• n 3
• Hardeners and curing accelerators comprising in each case at least one compound from the group of the esters of phosphorus-containing acids according to formula (I) are preferred for the index p of which:
• Hardening accelerator comprising in each case at least one compound selected from the group of esters of phosphorus-containing acids according to formula (Ia), where formula (Ia) applies
• R 1 , R 2 simultaneously or independently of one another hydrogen or alkyl
• R 3 alkyl, aryl, -O-alkyl, -O-aryl, -O-alkylaryl or -O-arylalkyl,
• R 6 hydrogen, alkyl or -NHC (O) NR R 2 ,
• hardeners and curing accelerators comprising in each case at least one compound from the group of the esters of phosphorus-containing acids according to formula (I) or formula (Ia) are preferred for whose radicals R 3 :
• R 3 aryl, -O-aryl or -O-alkylaryl.
• hardeners and curing accelerators comprising in each case at least one compound from the group of the esters of phosphorus-containing acids according to formula (I) or formula (Ia), to the radicals R 6 of which :
• R 6 hydrogen or alkyl.
• hardeners and curing accelerators comprising in each case at least one compound from the group of the esters of phosphorus-containing acids according to formula (I) or formula (Ia), for the radical X:
• Hardeners and curing accelerators comprising in each case at least one compound from the group of the esters of phosphorus-containing acids according to formula (I) or formula (la), whose radicals R 1 , R 2 simultaneously or independently of one another are also preferred, are preferred.
• R 1 , R 2 simultaneously or independently of one another are alkyl, in particular simultaneously or independently of one another, methyl or ethyl, in particular simultaneously methyl or ethyl.
• curing agents and curing accelerators comprising in each case at least one compound from the group of the esters of phosphorus-containing acids according to formula (I), for whose radicals R 1 , R 2 , R 6 , X and indices m, n, p in formula (I) simultaneously or independently of each other:
• R 1 , R 2 simultaneously or independently of one another methyl or ethyl
• R 3 aryl, -O-aryl or -O-alkylaryl
• R 6 hydrogen or alkyl
• n 0, 1 or 2
• m + n 3
• curing agents and curing accelerators comprising in each case at least one compound from the group of esters of phosphorus-containing acids according to formula (Ia), for the radicals R 1 , R 2 , R 6 , X and indices m, n in formula (Ia) simultaneously or independently of each other applies:
• R 1 , R 2 simultaneously or independently of one another methyl or ethyl
• R 3 aryl, -O-aryl or -O-alkylaryl
• R 6 hydrogen or alkyl
• alkyl is a linear or branched, monovalent radical which has the general formula C n H 2n + i, where n represents the number of carbon atoms of the radical and n is in particular a number from 1 to 10, preferably 1 to 5, particularly preferably 1 or 2.
• alkyl according to the present invention may in particular be methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, 1-methylethyl,
• alkyl particularly preferably means methyl, ethyl, 1-methylethyl, n-propyl, n-butyl, 2-methylbutyl or 1, 1-dimethylethyl. Most preferably, alkyl according to the present invention means methyl or ethyl.
• aryl is a monovalent aromatic radical having in particular 3 to 20 carbon atoms, preferably 6 to 20 carbon atoms, more preferably 6 carbon atoms, which may be monocyclic, bicyclic or polycyclic.
• aryl may in particular be phenyl, naphthyl, anthryl, phenantryl, pyrenyl or perylenyl.
• aryl particularly preferably denotes phenyl.
• alkylaryl means an aryl radical of the above
• Alkylaryl radical is located to the backbone on the aromatic nucleus.
• alkylaryl according to the present invention may in particular be tolyl, xylyl, pseudocumyl or mesityl.
• alkylaryl particularly preferably means tolyl.
• arylalkyl means an alkyl radical of the above
• arylalkyl may in particular be benzyl, 1-phenylethyl or 1-methyl-1-phenylethyl.
• arylalkyl particularly preferably means benzyl.
• -NHC (O) NR 1 R 2 represents a carbamoylamino radical substituted on the carbamoyl nitrogen with the radicals R 1 and R 2 , wherein R 1 and R 2 have the meanings given above, and the above the amino nitrogen is attached to the backbone.
• -NHC (O) means NR 1 R 2 particularly preferred
• -O-alkyl means an alkoxy radical, this alkoxy radical being bonded via the oxygen to the skeleton, and wherein alkyl otherwise has the meaning given above.
• -O-alkyl may in particular be methoxy, ethoxy, n-propoxy or 1-methylethoxy.
• -O-alkyl more preferably means methoxy or ethoxy.
• -O-aryl means an aryloxy radical, this aryloxy radical being linked via the oxygen to the skeleton, and wherein aryl otherwise has the meaning given above.
• -O-aryl may in particular denote phenoxy or naphthoxy.
• -O-aryl particularly preferably represents phenoxy.
• O-alkylaryl means an alkylaryloxy radical, this alkylaryloxy radical being linked to the skeleton via the oxygen, and the bond of the alkylaryl radical to the oxygen being located at the aromatic nucleus of the alkylaryl radical, and wherein alkylaryl otherwise has the meaning given above.
• -O-alkylaryl may in particular mean tolyloxy or xylyloxy.
• -O-alkylaryl particularly preferably means tolyloxy.
• -O-arylalkyl means an arylalkoxy radical, said arylalkoxy radical being attached to the skeleton via the oxygen, and wherein the bonding of the arylalkyl radical to the oxygen is located at the alkyl radical of the arylalkyl radical and wherein arylalkyl otherwise has the meaning given above.
• -O-arylalkyl may in particular mean benzyloxy.
• -O-arylalkyl particularly preferably represents benzyloxy.
• Curing accelerator for accelerated curing of epoxy resins which are cured, for example, with a conventional dicyandiamide hardener, can be used.
• the compounds according to the invention independently of one another, both as hardeners and as curing accelerators in
• the compounds thus provided react as a hardener or curing accelerator with the epoxy resin to be cured and thus become part of the polymer network of the cured epoxy resin.
• the indices m and n and the nature of the radical R 3, in particular hardener and curing accelerator are the subject of present invention, each comprising at least one compound selected from the group of phosphoric acid esters and thiophosphoric acid ester according to formula (I), or in each case at least one compound selected from the group of phosphonates and
• Thiophosphonates esters of organophosphorus compounds of phosphonic acid or their thio derivatives
• at least one compound selected from the group of phosphinates and thiophosphinates esters of organophosphorus compounds of phosphinic acid or their thio derivatives according to formula (I).
• Preferred according to the present invention are phosphoric acid esters and
• a hardener and / or a curing accelerator comprising in each case at least one compound selected from the group of phosphoric acid esters and thiophosphoric acid esters according to formula (I) are particularly preferred, for the radicals R 1 , R 2 , R 3 , R 6 , X and indices m, n, p are the same or independent of each other:
• R 1 , R 2 simultaneously or independently of one another hydrogen or alkyl
• R 3 -O-alkyl, -O-aryl, -O-alkylaryl or -O-arylalkyl,
• R 6 hydrogen, alkyl or -NHC (0) NR 1 R 2 ,
• Phosphoric acid esters and thiophosphoric acid esters according to formula (I) are particularly preferred for their index p:
• Hardening accelerator comprising in each case at least one compound selected from the group of phosphoric esters and thiophosphoric acid esters according to formula (Ia) is preferred, wherein for formula (Ia):
• R 1 , R 2 simultaneously or independently of one another hydrogen or alkyl
• R 3 -O-aryl, -O-alkylaryl or -O-arylalkyl
• R 6 hydrogen, alkyl or -NHC (O) NR R 2 ,
• a curing agent and / or a curing accelerator comprising in each case at least one compound selected from the group of phosphoric esters or thiophosphoric esters according to formula (I), for the radicals R 1 , R 2 , R 3 , R 6 , X and indices m, n , p is the same or independent of each other:
• R 1 , R 2 simultaneously or independently of one another alkyl, in particular methyl or
• n 0, 1 or 2
• n 3
• a curing agent and / or a curing accelerator comprising in each case at least one compound selected from the group of phosphoric acid esters or thiophosphoric acid esters according to formula (I), for the radicals R 1 , R 2 , R 6 , X and indices m, n, p simultaneously or independently of each other:
• R 1 , R 2 simultaneously or independently of one another methyl or ethyl
• R 6 hydrogen or alkyl, in particular hydrogen or methyl
• a curing agent and / or a curing accelerator comprising in each case at least one compound selected from the group consisting of phosphoric esters or thiophosphoric esters according to formula (Ia), for the radicals R 1 , R 2 , R 6 , X and indices m, n simultaneously or independently of each other applies:
• a hardener and / or a curing accelerator comprising in each case at least one compound selected from the group of phosphonates and thiophosphonates according to formula (I) are particularly preferred, for the radicals R 1 , R 2 , R 3 , R 6 , X and indices m, n, p are the same or independent of each other:
• R, R 2 simultaneously or independently of one another hydrogen or alkyl
• R 3 alkyl or aryl
• R 6 hydrogen, alkyl or -NHC (0) NR 1 R 2 ,
• Phosphonates and thiophosphonates according to formula (I) are particularly preferred for their index p:
• Hardening accelerator comprising in each case at least one compound selected from the group of the phosphonates and thiophosphonates according to formula (Ia), preference being given to formula (Ia):
• R 3 alkyl or aryl, in particular phenyl,
• R 6 hydrogen, alkyl or -NHC (O) NR 1 R 2 , in particular hydrogen or methyl,
• n 1.
• a hardener and / or a curing accelerator comprising in each case at least one compound selected from the group of the phosphonates and thiophosphonates according to formula (I), for the radicals R 1 , R 2 , R 3 , R 6 , X and Indices m, n, p are the same or independent of each other:
• R 1 , R 2 simultaneously or independently of one another alkyl, in particular methyl or
• R 3 aryl, in particular phenyl
• R 6 hydrogen or alkyl, in particular hydrogen or methyl
• phosphinates and thiophosphinates are particularly preferred, for the radicals R 1 , R 2 , R 3 , R 6 , X and indices m, n, p are the same or independent of each other:
• R 1 , R 2 simultaneously or independently of one another hydrogen or alkyl
• R 3 alkyl or aryl
• R 6 hydrogen, alkyl or -NHC (0) NR 1 R 2 ,
• a curing agent and / or a curing accelerator comprising in each case at least one compound selected from the group of phosphinates and thiophosphinates according to formula (Ia)
• R 6 hydrogen, alkyl or -NHC (0) NR 1 R 2 ,
• Hardening accelerator comprising in each case at least one compound selected from the group of the phosphinates and thiophosphinates according to formula (I), whose radicals R, R 2 , R 3 , R 6 , X and indices m, n, p are the same or independent of one another:
• R 1 , R 2 simultaneously or independently of one another alkyl, in particular methyl or
• R 3 aryl, in particular phenyl
• R 6 hydrogen or alkyl, in particular hydrogen or methyl
• the radicals R 1 and R 2 in formula (I) are preferably hydrogen or alkyl, where at least one radical R 1 or R 2 does not denote hydrogen or the radicals R 1 and R 2 do not simultaneously denote hydrogen.
• the radicals R 1 and R 2 particularly preferably mean, simultaneously or independently of one another, alkyl, where R 1 and R 2 may be different or the same. Most preferably, the radicals R 1 and R 2 are simultaneously methyl or ethyl.
• Hardening accelerator in flame retardancy tests compared to known hardeners or hardening accelerators as flame retardant hardeners and hardening accelerators. These hardeners and hardening accelerators are halogen-free. Without being bound by theory, it can be said that these hardeners and
• Curing accelerator have an additional effect as a flame retardant compared to known hardeners or curing accelerators due to the phosphorus contained in the compounds.
• the hardener according to the invention and
• Hardening accelerator a good to very good effect as a flame retardant in the cured epoxy resins.
• Flame retardants in epoxy resins, or in powder coatings, potting compounds, adhesives or cured molding compositions comprising at least one epoxy resin, object of the present invention are flame retardants in epoxy resins, or in powder coatings, potting compounds, adhesives or cured molding compositions comprising at least one epoxy resin, object of the present invention.
• these compounds can be used as hardeners and / or as curing accelerators. So could in experimental Investigations are shown that these compounds can be used as a curing agent for the curing of epoxy resins, in particular as the sole hardener for curing epoxy resins.
• the compounds of the formula (I) can also be used as curing accelerators for the accelerated curing of epoxy resins.
• the inventive compounds of the formula (I) can also be used as curing accelerators for the accelerated curing of epoxy resins.
• Hardened dicyandiamide can also be used as curing accelerators together with hardeners from the group of guanidine derivatives, aromatic amines, modified polyamines, semicarbazone derivatives or cyanamide. Hardening can also be accelerated with these hardeners.
• Curing accelerator according to the present invention is used together with another hardening and / or hardening accelerator according to formula (I), which is different from the former hardener or hardening accelerator of the present invention.
• a hardener composition comprising or in particular consisting of at least two different hardeners and / or curing accelerators in each case according to formula (I) is the subject of the present invention.
• Hardener composition comprising or in particular consisting of i) at least two different curing agents each comprising at least one compound from the group of esters of phosphorus-containing acids according to formula (I) or according to formula (Ia), or ii) at least two different curing accelerators each comprising at least one compound from the Group of the esters of phosphorus-containing acids of the formula (I) or of the formula (Ia), or iii) at least one curing agent comprising at least one compound from the group of esters of phosphorus-containing acids of the formula (I) or of the formula (Ia), and at least one curing accelerator comprising at least one compound from the group of esters of phosphorus-containing acids according to formula (I) or according to formula (Ia), wherein the curing agent and the curing accelerator are different from each other and
• a curing agent or a curing accelerator of the present invention may also be used in conjunction with known hardeners or accelerators.
• a hardener composition comprising or in particular consisting of a) a curing agent for curing epoxy resins which is different from a curing agent or curing accelerator according to formula (I), or a curing accelerator for accelerated curing of epoxy resins, which is different from a curing agent or curing accelerator according to formula (I) and
• a hardener composition comprising or in particular consisting of
• At least one hardener for curing epoxy resins which is different from a curing agent and / or a curing accelerator comprising a compound from the group of esters of phosphorus-containing acids according to formula (I) or formula (Ia), and b) at least one accelerating accelerator for accelerated Hardening of
• Epoxy resins comprising a compound from the group of esters of phosphorus-containing acids according to formula (I) or formula (Ia).
• the hardeners and curing accelerators according to the invention can not only be used particularly well for curing or accelerated curing of epoxy resins, but also have excellent storage stability in epoxy resins.
• the hardeners and curing accelerators according to the invention can not only be used particularly well for curing or accelerated curing of epoxy resins, but also have excellent storage stability in epoxy resins.
• Hardening accelerators are called high latent.
• the hardeners according to the invention can thus also be used as one-component pastes, i. pre-formulated, ready mixed with epoxy resin. All in all, these results were completely unexpected.
• epoxy resin compositions comprising a) at least one epoxy resin and b) at least one curing agent according to the type described above and / or at least one curing accelerator according to the above-described type of the present invention.
• the epoxy resin composition in addition to the hardener or
• Hardening accelerators in each case according to formula (I) or mixtures thereof a) no further hardeners, co-hardeners, curing accelerators or other catalysts for curing epoxy resins and / or b) no further flame retardant additives or flame retardant additives.
• an epoxy resin composition is the subject of the present invention, which contains a) at least one epoxy resin and b) at least one curing agent according to formula (I) and / or at least one curing accelerator according to formula (I).
• epoxy resin compositions are the subject of the present invention, which include
• At least one curing agent for curing epoxy resins comprising at least one
• Epoxy resins comprising at least one compound from the group of the esters of phosphorus-containing acids according to formula (I) or formula (Ia),
• inventive epoxy resin composition a) at least one epoxy resin, b) a curing accelerator according to formula (I) and c) a curing agent for curing epoxy resins, which is different from a curing agent or curing accelerator according to formula (I ), in particular consists thereof.
• the inventive epoxy resin composition a) at least one epoxy resin, b) a curing accelerator for accelerated curing of epoxy resins, which is different from a curing agent or curing accelerator according to formula (I), and c) a curing hardener of epoxy resins according to formula (I), in particular consists thereof.
• epoxy resin compositions are the subject of the present invention, which include
• a curing agent and a curing accelerator comprising a compound from the group of the esters of phosphorus-containing acids according to formula (I) or formula (Ia), and c) at least one curing accelerator for the accelerated curing of
• Epoxy resins comprising a compound from the group of esters
• formula (I) and formula (Ia) have the structure described herein.
• component b) it is possible in particular to use hardeners from the group of guanidine derivatives, in particular dicyandiamide, aromatic amines, modified polyamines, semicarbazone derivatives or cyanamide.
• the present invention is not limited. There are all commercial products in question, which usually have more than one 1, 2-epoxide group (oxirane) and thereby can be saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic.
• the epoxy resins may have substituents such as phosphorus and hydroxyl groups.
• Glycidyl polyethers of 2,2-bis (4-hydroxyphenyl) methane (bisphenol F) and glycidyl polyethers of novolaks can be obtained by using the curing agents of the invention and
• Hardening accelerators are hardened particularly well.
• the amount of the hardener or curing accelerator according to the invention is not subject to any restrictions. However, 0.01 to 15 parts of hardener or curing accelerator are preferably used per 100 parts of resin, preferably 0.1 to 15 parts, preferably 0.1 to 10 parts and most preferably 0.1 to 8 parts. A combination of several hardeners according to the invention or a combination of hardeners according to the invention with further co-hardeners is also covered by this invention.
• a hardener according to the invention is used as the sole hardener, it is preferable to use 0.1 to 15 parts per 100 parts of resin, preferably 1 to 15 parts, preferably 4 to 15 parts and most preferably 4 to 8 parts.
• a curing accelerator according to the invention is used for accelerated curing together with a known hardener, such as dicyandiamide, 0.1 to 15 parts, preferably 0.1 to 10 parts, preferably 0.1 to 5 parts, are preferably used per 100 parts of resin and most preferably 0.1 to 4 parts.
• a known hardener such as dicyandiamide
• the curing of the epoxy resins with the aid of the hardener and / or curing accelerator used according to the invention is generally carried out at temperatures of 20 to 140 ° C.
• the choice of curing temperature depends on the specific processing and
• Product requirement and can be varied on the formulation especially by regulating the amount of hardener and by adding additives. It is irrelevant, in a soft way the resin formulations energy is supplied. By way of example, this can be done in Form of heat through an oven or heating elements, but also done by means of infrared radiators or excitation by microwaves or other rays.
• the curing profile of the formulations according to the invention can be varied.
• Additives for improving the processability of the uncured epoxy resin compositions or for adapting the thermo-mechanical properties of the thermoset products to the requirement profile include, for example
• Reactive diluents such as thixotropic agents or
• Dispersing additives Dispersing additives, defoamer, dyes, pigments, toughening modifiers or
• a prepreg or composite material is the subject of the present invention.
• a carrier material in particular a fiber material
• a prepreg or composite material is the subject matter of the present invention
• a carrier material in particular a fiber material
• At least one hardener for curing epoxy resins which is different from a curing agent and a curing accelerator comprising a compound from the group of esters of phosphorus-containing acids according to formula (I) or formula (Ia), and
• Epoxy resins comprising a compound from the group of esters
• formula (I) and formula (Ia) have the structure described herein.
• all conventional carrier materials can be used as carrier material.
• fibers made of glass, carbon, aramid and wood or natural fibers are not conclusive: fibers made of glass, carbon, aramid and wood or natural fibers.
• R 1 , R 2 simultaneously or independently of one another hydrogen or alkyl
• R 3 alkyl, aryl, -O-alkyl, -O-aryl, -O-alkylaryl or -O-arylalkyl, in particular phenyl, phenoxy or tolyloxy,
• R 6 hydrogen, alkyl or -NHC (O) NR 1 R 2 , in particular hydrogen or alkyl, particularly preferably hydrogen or methyl,
• n 0, 1 or 2
• n 3
• p 0, 1 or 2, in particular 0, comprising the method steps:
• R 1 , R 2 simultaneously or independently of one another alkyl, in particular simultaneously
• Alkyl in particular simultaneously or independently of one another methyl or
• R 6 hydrogen, alkyl or -NHC (O) NR 1 R 2 , in particular hydrogen or alkyl, particularly preferably hydrogen or methyl,
• Process step A) provided a compound according to formula (IIa) and this compound according to formula (IIa) in process stage B), as described above, where formula (IIa) applies
• R 1 , R 2 simultaneously or independently of one another alkyl, in particular simultaneously
• Alkyl in particular simultaneously or independently of one another, methyl or ethyl, in particular simultaneously methyl or ethyl,
• R 6 hydrogen, alkyl or -NHC (O) NR 1 R 2 , in particular hydrogen or alkyl, particularly preferably hydrogen or methyl.
• reaction in process stage B) particularly successfully in a polar aprotic solvent in particular acetonitrile, / V, A / dimethylformamide and / or acetone, preferably acetonitrile, can be performed.
• a polar aprotic solvent in particular acetonitrile, / V, A / dimethylformamide and / or acetone, preferably acetonitrile
• the reaction takes place in the presence of a tertiary amine, in particular triethylamine, tri-n-butylamine, triisopropylamine and / or pyridine, preferably triethylamine.
• the reaction can be carried out more preferably at a temperature in the range from -10 to 100 ° C., in particular at a temperature in the range from -10 to 80 ° C., very particularly preferably at a temperature in the range from -10 to 60 ° C. wherein gleich Attachen or independently thereof, in particular a pressure in the range of 850 to 1200 mPa, in particular a pressure in the range of 950 to 1200 mPa, and most preferably a pressure in the range of 1000 to 1200 mPa is set.
• reaction in process stage B) can be carried out if the molar ratio of the compound of the formula (II) or formula (IIa) to the compound according to Formula (III) a ratio in the range of 4: 1 to 1: 1, preferably 3: 1 to 1: 1, more preferably 3: 1 to 2: 1 corresponds.
• Process sub-steps can be done. Particularly advantageous and in good purities, the compounds of the invention can be isolated by
• the desired compounds of formula (I) may also be prepared by the reaction of isocyanates with amines.
• a process for the preparation of a compound of formula (I), in particular a compound selected from the group of phosphoric esters, thiophosphoric acid esters, phosphonates, thiophosphonates, phosphinates and thiophosphinates according to formula (I) is the subject of the present
• R, R 2 simultaneously or independently of one another hydrogen or alkyl
• R 3 alkyl, aryl, -O-aryl, -O-alkylaryl or -O-arylalkyl, in particular phenyl, phenoxy or tolyloxy,
• n 0, 1 or 2
• n 3
• p 0, 1 or 2, in particular 0, comprising the method steps:
• R 3 alkyl, aryl, -O-aryl, -O-alkylaryl or -O-arylalkyl, in particular phenyl,
• R 6 hydrogen, alkyl or -NCO, in particular hydrogen or alkyl, particularly preferably hydrogen or methyl,
• n 0, 1 or 2
• n 3
• R 2 being the same or independent of each other for the radicals R 1 , R 2 :
• R, R 2 simultaneously or independently of one another hydrogen or alkyl
• a compound according to formula (IV) is preferably provided in process step A), where the radicals R 3 , R 6 , X and the indices m, n, p simultaneously or independently of one another are:
• R 3 alkyl, aryl, -O-aryl, -O-alkylaryl or -O-arylalkyl,
• R 6 hydrogen, alkyl or -NICO, in particular hydrogen or alkyl
• n 0, 1 or 2
• n 3
• Process step A) provided a compound according to formula (IVa) and this compound according to formula (IVa) in process step B), as described above, is reacted, wherein for formula (IVa) applies
• R 3 alkyl, aryl, -O-aryl, -O-alkylaryl or -O-arylalkyl,
• R 6 hydrogen, alkyl or -NCO, in particular hydrogen or alkyl, particularly preferably hydrogen or methyl,
• a solvent As a solvent, a solvent or a particularly preferred
• Solvent mixture selected from the group of a) polar aprotic solvents, in particular ethyl acetate, acetonitrile, / V, / V-dimethylformamide or acetone, preferably Ethyl acetate or b) non-polar aprotic solvent, in particular toluene, cyclohexane or n-hexane, preferably toluene, or c) a solvent mixture consisting of a solvent of a) and a solvent of b), in particular a mixture of ethyl acetate and toluene ,
• the reaction can be carried out further preferably at a temperature in the range from -10 to 100 ° C., in particular at a temperature in the range from -10 to 80 ° C., very particularly preferably at a temperature in the range from 0 to 60 ° C., wherein gleich Attachen or independently thereof, in particular a pressure in the range of 850 to 1200 mPa, in particular a pressure in the range of 950 to 1200 mPa, and most preferably a pressure in the range of 1000 to 1200 mPa is set.
• reaction in process stage B) can be carried out with particularly good results if the molar ratio of the compound according to formula (IV) to the compound according to formula (V) is in the range from 1: 6 to 1: 1, preferably 5: 1 to 1: 1, preferably 4: 1 to 1: 1, preferably 3: 1 to 1: 1 corresponds.
• curing accelerator for accelerated curing of prepregs, laminates, coatings, polymer resin mixtures, powder coatings, potting compounds or adhesives, each comprising at least one epoxy resin, or
• Adhesives or cured molding compositions comprising in each case at least one epoxy resin,
• v (cm -1 ) 3356 (w); 1647 (s); 1605 (m); 1533 (m); 1501 (vs); 1407 (s);
• HA-II The preparation of HA-II is carried out analogously to Example 1, wherein dimethylamine is replaced by 19.75 g (0.27 mol) of diethylamine (99% strength, Fluka).
• v (cm -1 ) 3291 (w); 2973 (w); 2931 (w); 1632 (s); 1603 (m); 1502 (vs);
• v (cm -1 ) 3352 (w); 2924 (w); 1650 (m); 1605 (w); 1532 (m);
• Phosphoric acid phenyl ester dichloride (97% strength, ABCR) in 80 ml of acetonitrile is added dropwise so that the temperature does not rise above 5 ° C. Thereafter, the ice bath is removed and the
• v (cm -1 ) 3310 (w); 1656 (s); 1601 (w); 1531 (s); 1505 (s); 1488 (s);
• Phosphoric acid diphenylester chloride (97% strength, ABCR) in 80 ml of acetonitrile is added dropwise so that the temperature does not rise above 5 ° C. After removal of the ice bath, the mixture is stirred for 90 min at room temperature and then again for 90 min at a temperature of 50 ° C. After cooling to room temperature, 400 ml of water are added, resulting in a two-phase mixture. The upper, aqueous phase is separated and the organic phase is mixed with 240 ml of water. The resulting solid is separated, washed with water and dried at 60 ° C in a vacuum.
• reaction mixture stirred overnight at room temperature.
• the reaction mixture is with Diluted 150 ml of water.
• the resulting solid is separated, washed with a little water and dried at 60 ° C in a vacuum.
• v (cm -1 ) 3266 (w); 2923 (w); 1652 (s); 1603 (w); 1532 (s); 1504 (s);
• v (cm -1 ) 3312 (w); 3061 (w); 2921 (w); 1658 (s); 1601 (w); 1532 (m);
• v (cm -1 ) 3369 (w); 3088 (w); 1633 (m); 1602 (m); 1537 (s); 1484 (s);
• v (cm -1 ) 3318 (w); 2924 (w); 1677 (m); 1637 (s); 1596 (m); 1525 (s);
• the invention is shown by the example of the formulations of epoxy resin compositions listed in Table 1.
• Example Components of the formulation (parts by weight)
• the mixture of the individual components of a formulation is carried out in a dissolver. These are the components in one
• T G - determination A sample of the formulation is heated at a heating rate of 10 K / min of 30-250 ° C.
• the evaluation of the exothermic reaction peak is carried out by determining the onset temperature (T 0 nset) > the temperature in the peak maximum (T Max ) and the peak area as a measure of the released heat of reaction ( ⁇ ⁇ ⁇ ).
• final T G a sample of the cured formulation is subjected to the following DSC temperature program: heating from 30 to 200 ° C at 20 K / min, holding at 200 ° C for 10 min, cooling from 200 to 50 ° C at 20 K / min, 5 min hold at 50 ° C, heating from 50-200 ° C at 20 K / min, hold for 10 min at 200 ° C, cooling from 200-50 ° C at 20 K / min, 5 min hold at 50 ° C, heating from 50 - 220 ° C at 20 K / min.
• a sample of the formulation is held constant at the indicated temperature for the indicated time (isothermal cure of the formulation).
• the evaluation is carried out by determining the time of the peak maximum (as a measure of the onset of the curing process) and the 90% conversion (as a measure of the end of the
• the hardeners / curing accelerators according to the invention slightly higher than when using HA (Examples A and C), ie the curing is slightly slower when using the curing agent / curing accelerator according to the invention.
• the energy A R H liberated upon curing is of the same order of magnitude for all formulations, indicating that curing actually takes place in all the formulations tested.
• the achievable glass transition temperature is at least comparable to the particular formulation with the technically conventional curing / curing accelerator and in some examples significantly higher (Examples B, D, F, J and L).
• the flame retardancy of the compounds of the invention is shown by the example of HA-I in comparison to HA, a common hardening / curing accelerator. Test specimens of cured formulations are used for the tests mentioned below. The following fire tests are carried out: a) oxygen index:
• the determination of the oxygen index (also Limiting Oxygen Index, LOI) is carried out in accordance with DIN EN ISO 4589-2 (Plastics - Determination of the burning behavior by the
• Oxygen Index - Part 2 Testing at ambient temperature). The tests are carried out with specimens measuring 100 mm ⁇ 10 mm ⁇ 4 mm (specimen type III)
• the small burner test is carried out according to UL 94 V (Tests for Flammability of Plastic Materials for Parts in Devices and Applications). The tests are carried out with 5 test specimens measuring 127 mm x 13 mm x 4 mm.
• the oxygen index indicates which oxygen content (in% by volume) in an oxygen-nitrogen gas mixture is at least necessary so that an ignited test specimen continues to burn after removal of the ignition source. If the oxygen index is greater than the oxygen content of about 21% by volume present in the normal atmosphere, a self-extinction of the tested materials is observed and thus a flame-retarding effect is shown.
• oxygen index values 21.1% by volume and 20.7% by volume were determined.
• the normal atmosphere oxygen content about 21% by volume
• a continuous burning after the ignition by means of a burner flame is detected here.
• a higher value is found for the examples D, E, F and G (according to the invention, containing HA-I, HA-III, HA-IV and HA-V, respectively, as curing accelerator).
• the best result is determined for example B (according to the invention containing HA-I as hardener) at 26.7% by volume. In the latter materials, a fast self-extinction is expected in the normal atmosphere (air).
• the flame tests of the small burner test in accordance with UL 94 V show an improvement in the flameproofing effect when using the hardener / curing accelerator HA-I according to the invention instead of the technically customary hardener / curing accelerator HA.
• a and example C both not according to the invention
• the in the individual tests more than 180 s, and there is a burning dripping (with inflammation of the underlying cotton wool) as well as a complete burn-off of the test specimens.
• B and D both according to the invention, containing HA-I as curing agent or curing accelerator
• the afterburning time in the individual experiments is predominantly less than 180 s, sometimes even significantly less (formulation B).
• test specimens of Formulation B in contrast to Formulation A, show self-extinction without dripping or falling off of test specimen parts.
• test specimens of Formulation D partial burning (with ignition of the underlying cotton wool) and complete burnup was observed, but part of the specimens also showed self-extinction without dripping or falling off of test specimen parts.
• analogous formulation C containing HA as a curing accelerator
• an improved flameproofing effect can also be seen for the formulation D (containing HA-I as curing accelerator).
• the investigations show that the compound HA-I according to the invention, when used as the sole curing agent or as a curing accelerator, leads to an improvement in the flameproofing effect within an otherwise comparable epoxy resin composition in comparison with the technically conventional hardener / curing accelerator HA.
• the use of the hardener / curing accelerator HA-I according to the invention in Examples B and D instead of a technically conventional hardener such as HA (Examples A and C) within an epoxy resin composition leads both to the improvement of the oxygen index and to an improved Fire behavior in the small burner test.
• the formulations according to the invention have at least 60 days a markedly higher storage stability than the comparable, not according to the invention formulations having a storage stability of 32 days (formulation A) or 30 days (formulation C).

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• 2016
  • 2016-04-14 US US15/566,837 patent/US10526355B2/en not_active Expired - Fee Related
  • 2016-04-14 CA CA2978986A patent/CA2978986A1/en not_active Abandoned
  • 2016-04-14 WO PCT/EP2016/058249 patent/WO2016166229A1/de not_active Ceased
  • 2016-04-14 EP EP16718292.2A patent/EP3283494B1/de active Active
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