EP3033319A1 - Glycidyl ethers of lime derivatives and oligomers of said glycidyl ethers as curable epoxy resins - Google Patents

Glycidyl ethers of lime derivatives and oligomers of said glycidyl ethers as curable epoxy resins

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Publication number
EP3033319A1
EP3033319A1 EP14749745.7A EP14749745A EP3033319A1 EP 3033319 A1 EP3033319 A1 EP 3033319A1 EP 14749745 A EP14749745 A EP 14749745A EP 3033319 A1 EP3033319 A1 EP 3033319A1
Authority
EP
European Patent Office
Prior art keywords
glycidyl
glycidyl ether
oligomeric
group
epoxy resin
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Withdrawn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
EP14749745.7A
Other languages
German (de)
French (fr)
Inventor
Ulrich Karl
Monika CHARRAK
Hans-Josef Thomas
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.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP14749745.7A priority Critical patent/EP3033319A1/en
Publication of EP3033319A1 publication Critical patent/EP3033319A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/13—Monohydroxylic alcohols containing saturated rings
    • C07C31/133—Monohydroxylic alcohols containing saturated rings monocyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/27—Polyhydroxylic alcohols containing saturated rings
    • C07C31/272—Monocyclic
    • C07C31/276—Monocyclic with a six-membered ring
    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • 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
    • C08G59/20—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines

Definitions

  • the present invention relates to glycidyl ethers of the formula I, which are glycidyl ethers of limonene derivatives of the formula II having two or more glycidyl groups.
  • the invention further relates to oligomers of the glycidyl ethers of the formula I.
  • the invention also relates to processes for the preparation of these monomeric and oligomeric glycidyl ethers, and their use for the production of adhesives, composites, moldings or coatings.
  • the present invention further relates to a curable epoxy resin composition
  • a curable epoxy resin composition comprising a hardener component and a resin component containing as polyepoxide compound at least one glycidyl ether of the formula I, an oligomer of a glycidyl ether of the formula I or an oligomer based on a glycidyl ether of the formula I.
  • the invention further relates to a process for curing these curable epoxy resin compositions and to cured epoxy resins obtainable by curing this curable epoxy resin composition.
  • the invention also relates to the limonene derivatives of the formula II having 3 or 4 hydroxyl groups used as an intermediate for the preparation of the glycidyl ethers according to the invention.
  • epoxy resins are usually called oligomeric compounds having on average more than one epoxide group per molecule, which are converted by reaction with suitable curing agents or by polymerization of the epoxy groups in thermosets or cured epoxy resins.
  • Cured epoxy resins are highly resistant to abrasion, high abrasion resistance, good heat and chemical resistance, in particular high resistance to alkalis, acids, oils and organic solvents, high weather resistance, excellent adhesion to many materials and high due to their excellent mechanical and chemical properties electrical insulation, widely used. They serve as a matrix for composites and are often the main component in electro laminates, structural adhesives, casting resins, coatings and powder coatings.
  • Epoxy resins derived from epichlorohydrin are referred to as glycidyl based resins.
  • glycidyl based resins As a rule, bisphenol A or bisphenol F diglycidyl ethers or the corresponding oligomers are used as epoxy resins.
  • the coating should withstand strongly acidic or salt-containing foods (eg tomatoes) or beverages, so that no corrosion of the metal occurs, which in turn could lead to contamination of the contents.
  • the coating must not affect the taste or appearance of the food. Since often already coated containers are formed during the production of the containers. the coating needs to be flexible. Many fillings, eg food, are first pasteurized in a can; therefore, the coating must survive heating to 121 ° C for at least 2 hours undamaged and without migration of ingredients.
  • the use of bisphenol A or bisphenol F diglycidyl ether based epoxy resins is being reconsidered in an increasing number of fields, since the corresponding diols are considered to be problematic because of their endocrine activity.
  • US 2012/01 16048 discloses a bisphenol-A (BPA) and bisphenol-F (BPF) -free polymer which, in addition to ester linkages, also comprises hydroxy ether bridges, using diepoxides based on open-chain aliphatic diols such as neopentyl glycol (NPG), simple cycloaddition
  • BPA bisphenol-A
  • BPF bisphenol-F
  • NPG neopentyl glycol
  • WO 2012/089657 discloses a BPA-free preparation of a film-forming resin and an adhesion promoter.
  • an epoxidized resin is prepared, for example, from the diglycidyl ethers of NPG, ethylene glycol, propylene or dipropylene glycol, 1,4-butanediol or 1,6-hexanediol.
  • NPG diglycidyl ethers
  • ethylene glycol propylene or dipropylene glycol
  • 1,4-butanediol 1,6-hexanediol
  • WO 2010/100122 proposes a coating system obtainable by reacting an epoxidized vegetable oil with hydroxy-functional compounds, e.g. Propylene glycol, propane-1,3-diol, ethylene glycol, NPG, trimethylolpropane, diethylene glycol, and the like.
  • hydroxy-functional compounds e.g. Propylene glycol, propane-1,3-diol, ethylene glycol, NPG, trimethylolpropane, diethylene glycol, and the like.
  • WO 2012/091701 proposes various diols or their diglycidyl ethers as substitutes for BPA or BADGE for epoxy resins, inter alia derivatives of BPA and ring-hydrogenated BPA, alicyclic diols based on cyclobutane and diols with a furan ring as the basic structure.
  • the present invention has for its object to provide monomeric or oligomeric glycidyl ether compounds for use in epoxy resin systems, in particular as at least partial replacement of BADGE in corresponding epoxy resin systems, especially for use for coating containers. Accordingly, the present invention relates to glycidyl ethers of the formula I.
  • A is a glycidyl group ) or an H atom
  • R 7 and R 8 are each independently an H atom or a C 1 -C 4 -alkyl group, preferably an H atom,
  • At least 2, but preferably all A radicals are each a glycidyl group.
  • glycidyl ethers of the formula I in this specification of the radicals are also referred to for the purposes of this invention as "glycidyl ether I.”
  • the present invention relates to glycidyl ethers of the formula I in variant A,
  • A is a glycidyl group.
  • glycidyl ethers of the formula I in this specification of the radicals (variant A) are also referred to for the purposes of this invention as "glycidyl ether IA".
  • the present invention relates to glycidyl ethers of the formula I in variant B,
  • A is a glycidyl group or an H atom
  • R7 and R8 are each independently an H atom or a C1-C4 alkyl group, preferably an H atom, and
  • R3 and R6 are not both simultaneously an H atom
  • At least 2, but preferably all A radicals are each a glycidyl group.
  • glycidyl ethers of the formula I in this specification of the radicals (variant B) are also referred to in the context of this invention as "glycidyl ether IB" for short.
  • Glycidyl ethers IA and IB are subsets of glycidyl ether I.
  • the glycidyl ethers I, IA and IB expressly include all possible stereoisomers.
  • Ci-C4-alkyl group is a methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl or tert-butyl group.
  • glycidyl ether I, IA or IB also expressly relates to individual specific compounds from the respective group as well as mixtures of several specific compounds of the respective group.
  • Another object of the invention are also oligomers of glycidyl ethers I, IA and IB, by the intermolecular reaction of glycidylated residues with non-glycidylated, hydroxyl-containing residues of the glycidyl ethers I, IA and IB and their partial (1 glycidyl group having ) or non-glycidylated (no glycidyl group containing) derivatives under opening of the oxirane ring, wherein the resulting by the ring opening of the oxirane ring hydroxyl group of the oligomer may in turn be present in glycidylated form.
  • the oligomers have 2 to 100, preferably 2 to 30 monomeric units (degree of oligomerization). They can be linear or branched, preferably they are linear. On average, they have at least 1, 3, preferably at least 1, 5, more preferably at least 2 glycidyl groups.
  • the term oligomer of glycidyl ethers I, IA and IB also includes mixtures various oligomers (for example, oligomers with different degree of oligomerization, with different branching structures or from different monomers of the respective variant (glycidyl ether I, IA or IB)). These oligomers are also referred to in the context of this invention as oligomeric glycidyl ethers I, IA and IB.
  • the invention thus provides a glycidyl ether selected from the group consisting of glycidyl ether I and oligomeric glycidyl ethers thereof (oligomeric glycidyl ether I), where the oligomeric glycidyl ether is prepared by the intermolecular reaction of glycidylated residues with non-glycidylated, hydroxyl-containing residues of the monomeric glycidyl ether of the invention.
  • mel I and their partially or non-glycidylated derivatives with formation of the oxirane ring are formed, wherein the hydroxyl group of the oligomeric glycidyl ether formed by the ring opening of the oxirane ring can again also be present in glycidylated form, and wherein the oligomeric glycidyl ether has a degree of oligomerization of 2 to 100 and has on average at least 1, 3 glycidyl groups.
  • the invention thus also provides a glycidyl ether selected from the group consisting of glycidyl ether IA and oligomeric glycidyl ethers thereof (oligomeric glycidyl ethers IA), the oligomeric glycidyl ether being obtained by the intermolecular reaction of glycidylated residues with non-glycidylated, hydroxyl-containing residues of the monomeric glycidyl ether of the formula I and their partially or non-glycidylated derivatives to form the opening of the oxirane ring, the resulting by the ring opening of the oxirane ring hydroxyl group of the oligomeric glycidyl ether may in turn be present in glycidylierter form, and wherein the oligomeric glycidyl ether a degree of oligomerization of 2 to 100 and on average at least 1 , 3 glycidyl groups.
  • the invention thus likewise provides a glycidyl ether selected from the group consisting of glycidyl ether IB and oligomeric glycidyl ethers IB (oligomeric glycidyl ether IB), the oligomeric glycidyl ether being obtained by the intermolecular reaction of glycidylated radicals with non-glycidylated, hydroxyl-containing radicals of the monomeric glycidyl ether of the formula I and their partially or non-glycidylated derivatives to form the opening of the oxirane ring, the resulting by the ring opening of the oxirane ring hydroxyl group of the oligomeric glycidyl ether may in turn be present in glycidylierter form, and wherein the oligomeric glycidyl ether a degree of oligomerization of 2 to 100 and on average at least 1 , 3 glycidyl groups.
  • One embodiment of the invention relates to mixtures of monomeric glycidyl ether I, IA or IB and the corresponding oligomeric glycidyl ether I, IA or IB.
  • the present invention furthermore relates to a process for the preparation of monomeric and oligomeric glycidyl ethers I, IA or IB comprising the reaction of the corresponding derivatives II, IIA or IIB with epichlorohydrin.
  • Derivatives II are limonene derivatives of the formula II
  • R7 and R8 are each independently an H atom or a C1-C4 alkyl group, preferably an H atom.
  • the limonene derivatives IIA are limonene derivatives of the formula II in variant A with the following specification of the radicals:
  • the limonene derivatives IIA are diols.
  • the limonene derivatives IIB are limonene derivatives of the formula II in the variant B with the following specification of the radicals:
  • R7 and R8 are each independently an H atom or a C1-C4 alkyl group, preferably an H atom, and
  • R1 1 and R14 are not both simultaneously an H atom.
  • the limonene derivatives I IB are trihydric and tetrahydric alcohols (polyols).
  • the glycidylation reaction generally produces a mixture of monomeric and oligomeric glycidyl ether.
  • the monomeric glycidyl ethers can be separated from the oligomeric glycidyl ethers by means of separation methods known to those skilled in the art, such as, for example, chromatographic, extractive or distillative processes.
  • the reaction according to the invention of the limonene derivatives II, IIA or IIB is carried out to the corresponding glycidyl ethers with 1 to 20, preferably with 1 to 10 equivalents of epichlorohydrin at a temperature in a range from 20 to 180 ° C, preferably from 70 to 150 ° C in the presence of a Lewis acid as a catalyst, preferably in the presence of stannic chloride.
  • the reaction mixture is mixed with a base (for example dilute sodium hydroxide solution) and heated for a further period of time (for example 1 to 5 h) (for example under reflux). Thereafter, the product can be isolated by means of phase separation and washing steps with water.
  • 1 to 20 equivalents, preferably 2 to 10 equivalents of epichlorohydrin are used for the preparation of the glycidyl ethers according to the invention.
  • the reaction is usually carried out in a temperature range from -10 ° C to 120 ° C, preferably 20 ° C to 60 ° C.
  • bases such as aqueous or alcoholic solutions or dispersions of inorganic salts, such as, for example, sodium salts, can be used.
  • LiOH, NaOH, KOH, Ca (OH) 2 or Ba (OH) 2 are added.
  • suitable catalysts such as tertiary amines can be used.
  • the limonene derivatives I IA and IIB can be prepared from limonene according to the following reaction scheme.
  • limonene is converted into the corresponding dicarbonyl compounds by hydroformylation (HF) with carbon monoxide (CO) and hydrogen (H2).
  • HF hydroformylation
  • CO carbon monoxide
  • H2 hydrogen
  • This can then either hydrogenated directly to the diols (limonene derivatives I IA), or after an aldol reaction (AD) with, for example, formaldehyde (H2CO) to the polyols (limonene derivatives I IB), for example with hydrogen (H2).
  • the aldol reaction is only possible if a hydrogen atom is bonded to the carbon atom alpha-permanent carbon atom.
  • the limonene derivatives II correspond to the entirety of the group of limonene derivatives I IA and II B. Limonene derivatives I IA and their preparation are also described in DE 32287
  • the reaction of limonene to the corresponding dialdehydes is usually carried out by means of hydroformylation.
  • the limonene is reacted with a mixture of carbon monoxide and hydrogen (synthesis gas) in the presence of a hydroformylation catalyst (for example organometallic cobalt or rhodium compounds) at elevated pressure (for example 10 to 100 bar overpressure) and at temperatures in the range of, for example 40 to 200 ° C converted to the corresponding dialdehydes.
  • a hydroformylation catalyst for example organometallic cobalt or rhodium compounds
  • the dialdehyde derivatives of limonene can be hydrogenated directly to the corresponding diols (limonene derivatives IIA). Such hydrogenation can be carried out, for example, by means of hydrogen under elevated pressure in the presence of a hydrogenation catalyst.
  • the dialdehyde derivatives of limonene can also be converted to the corresponding polyols (limonene derivatives IIB).
  • the invention thus provides a process for the preparation of glycidyl ether IA comprising (i) the hydroformylation of limonene with a mixture of carbon monoxide and hydrogen in the presence of a hydroformylation catalyst at elevated pressure to the corresponding dialdehydes, and (ii) the catalytic hydrogenation of Dialdehydes from the hydroformylation to the corresponding diols, and (iii) the reaction of the diols from the catalytic hydrogenation with epichlorohydrin to give the corresponding glycidyl ethers IA.
  • the invention also relates to the limonene derivatives IIB, which serve as an intermediate in the preparation of the glycidyl ether IB according to the invention.
  • the present invention further relates to processes for the preparation of oligomers based on glycidyl ether I, IA or IB, by reacting monomeric glycidyl ether I, IA, and IB with diols (chain extension). For this, monomeric glycidyl ether I, IA, or IB or a mixture of monomeric glycidyl ether I, IA, or IB and corresponding oligomeric glycidyl ether I, IA, or IB is reacted with one or more diols.
  • the oligomeric glycidyl ether I, IA or IB preferably has a low degree of oligomerization, in particular a degree of oligomerization of from 5 to 10. Preference is given to 0.01 to 0.95, more preferably 0.05 to 0.8, in particular 0.1 to 0.4 equivalents of the diol based on the glycidyl ether or used used. It is preferably achieved by substoichiometric use of the diol or diols that the resulting oligomer based on glycidyl ethers I, IA or IB has an average of more than 1, preferably more than 1.5, more preferably more than 1, 9 epoxide groups per molecule.
  • the reaction is usually carried out in a temperature range from 50 ° C to 200 ° C, preferably from 60 ° C to 160 ° C.
  • Suitable diols are typically aromatic, cycloaliphatic or aliphatic dihydroxy compounds, for example furandimethanol, ring-hydrogenated bisphenol A, ring-hydrogenated bisphenol F, neopentyl glycol, bisphenol A, bisphenol F or bisphenol S, preferably furandimethanol, ring-hydrogenated bisphenol A or ring-hydrogenated bisphenol F.
  • the subject of the present invention are also oligomers based on glycidyl ether I, IA, or IB, which are obtainable or obtainable, by reacting a monomeric glycidyl ether I, IA, or IB or the corresponding oligomeric glycidyl ether or a mixture of monomeric glycidyl ether I, IA, or IB and the speaking oligomeric glycidyl ether with one or more diols.
  • the oligomeric glycidyl ether I, IA or IB preferably has a low degree of oligomerization, in particular a degree of oligomerization of from 5 to 10.
  • the one or more diols used are not identical to the limonene derivatives IIA, whereby mixed oligomers based on glycidyl ethers I, IA or IB are obtainable or obtainable. In a particular embodiment, the one or more diols used are identical to the limonene derivatives IIA, whereby oligomers based on glycidyl ethers I, IA or IB are obtainable or obtainable.
  • oligomeric glycidyl ethers I, IA or IB can also be prepared starting from oligomeric glycidyl ethers I, IA or IB with a lower degree of oligomerization.
  • the present invention also relates to curable epoxy resin compositions comprising a hardener component containing at least one curing agent and a resin component containing at least one polyepoxide compound selected from the group consisting of monomeric glycidyl ether I, IA or IB, oligomeric glycidyl ether I, IA or IB and oligomer based on glycidyl ethers I, IA and IB, respectively.
  • the present invention also relates to curable epoxy resin compositions
  • curable epoxy resin compositions comprising a hardener component containing at least one curing agent and a resin component containing at least one polyepoxide compound selected from the group consisting of monomeric glycidyl ether I, IA or IB, oligomeric glycidyl ether I, IA or IB and Mischoligo- mer, which is based on glycidyl ethers I, IA and IB.
  • the present invention relates to curable epoxy resin compositions
  • curable epoxy resin compositions comprising a hardener component containing at least one curing agent and a resin component containing at least one polyepoxide compound selected from the group consisting of monomeric glycidyl ether I and oligomeric glycidyl ether I.
  • the present invention relates to curable resins Epoxy resin compositions comprising a hardener component containing at least one curing agent and a resin component containing at least one polyepoxide compound selected from the group consisting of monomeric glycidyl ether IA, monomeric glycidyl ether IB, oligomeric glycidyl ether IA and oligomeric glycidyl ether IB.
  • the present invention relates to curable epoxy resin compositions
  • EW epoxide equivalent
  • the curable epoxy resin composition according to the invention preferably has less than 40% by weight, preferably less than 10% by weight, particularly preferably less than 5% by weight, in particular less than 1% by weight of bisphenol A or F based compounds based on the total resin component.
  • the curable epoxy resin composition of the invention is free of bisphenol A or F based compounds.
  • Bisphenol A or F based compounds in the context of the present invention are bisphenol A and F themselves, their diglycidyl ethers, and oligomers or polymers based thereon.
  • the polyepoxide compounds according to the invention overall make up a proportion of at least 40% by weight, preferably at least 60% by weight, in particular at least 80% by weight, based on the total resin component.
  • the total resin component makes up at least 10% by weight, in particular at least 25% by weight, based on the total curable epoxy resin composition.
  • Epoxide compounds in the context of the present invention are compounds having at least one epoxide group, that is, for example, also corresponding reactive diluents.
  • the epoxy compounds of the resin component preferably have on statistical average at least 1.1, preferably at least 1.5, in particular at least 1.9 epoxide groups per molecule.
  • Hardeners in the context of the invention are compounds which are suitable for effecting crosslinking of the polyepoxide compounds according to the invention.
  • polyepoxide compounds By reaction with hardeners, polyepoxide compounds can be converted into non-fusible, three-dimensionally "crosslinked", duroplastic materials.
  • the curing agent has at least two functional groups which can react with the oxirane and / or hydroxyl groups of the polyepoxide compounds to form covalent bonds (polyaddition reaction). Curing then results in the formation of a polymeric network of covalently linked units derived from the polyepoxide compounds and units derived from the hardener molecules, the degree of crosslinking being controllable via the relative amounts of the functional groups in the hardener and in the polyepoxide compound.
  • a compound is used which effects the homopolymerization of polyepoxide compounds with one another. Such compounds are often referred to as initiator or catalyst.
  • Homopolymerization inducing catalysts are Lewis bases (anionic homopolymerization, anionic curing catalysts) or Lewis acids (cationic homopolymerization; cationic curing catalysts). They cause the formation of ether bridges between the epoxide compounds. It is believed that the catalyst reacts with a first epoxide group to ring opening to form a reactive hydroxy group, which in turn reacts with another epoxide group to form an ether bridge, resulting in a new reactive hydroxy group. Due to this reaction mechanism, the sub-stoichiometric use of such catalysts for curing is sufficient. Imidazole is an example of a catalyst that induces anionic homopolymerization of epoxide compounds.
  • Boron trifluoride is an example of a catalyst that initiates cationic homopolymerization. It is also possible to use mixtures of various polyaddition reaction hardeners and mixtures of homopolymerization-inducing hardeners, as well as mixtures of polyaddition reaction-inducing and homopolymerization-inducing hardeners for curing polyepoxide compounds.
  • Suitable functional groups which can undergo a polyaddition reaction with the oxirane groups of polyepoxide compounds are, for example, amino groups, hydroxy groups, thioalcohols or derivatives thereof, isocyanates and carboxyl groups or derivatives thereof, such as anhydrides.
  • epoxy resins aliphatic, cycloaliphatic and aromatic polyamines, carboxylic anhydrides, polyamidoamines, aminoplasts, e.g. Formaldehyde condensation products of melamine, urea, benzoguanamine or phenoplasts, such as e.g. Novolak, used.
  • acrylate-based oligomeric or polymeric curing agents having hydroxy or glycidyl functions in the side chain as well as epoxy vinylester resins are used.
  • the skilled worker knows for which applications a fast or slow-acting hardener is used.
  • a hardener which acts very slowly (or only at a relatively high temperature).
  • a hardener which is released as an active form only under conditions of use, for example ketimines or aldimines.
  • Known hardeners have a linear or at most weakly crosslinked structure. They are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition on CD-ROM, 1997, Wiley-VCH, Chapter "Epoxy Resins", which is hereby incorporated by reference in its entirety.
  • Suitable hardeners for the curable epoxy resin composition according to the invention are, for example, polyphenols, polycarboxylic acids, polymercaptans, polyamines, primary monoamines, sulfonamides, aminophenols, aminocarboxylic acids, carboxylic anhydrides, phenolic hydroxy-containing carboxylic acids, sulfanilamides, and mixtures thereof.
  • the respective poly compounds for example polyamine
  • di compounds for example diamine
  • Preferred hardeners for the curable epoxy resin composition of the present invention are amino hardeners and phenolic resins.
  • the curable epoxy resin composition of the invention includes an amino hardener as a curing agent.
  • Amino hardeners suitable for the polyaddition reaction are compounds which have at least two secondary or at least one primary amino group. Linkage of the amino groups of the amino hardener with the epoxide groups of the polyepoxide compound forms polymers whose units derive from the amino hardeners and the polyepoxide compounds. Amino hardeners are therefore usually used in a stoichiometric ratio to the epoxy compounds. If, for example, the amino hardener has two primary amino groups, ie can couple with up to four epoxide groups, crosslinked structures can be formed.
  • the amino hardeners of the curable epoxy resin composition of the present invention have at least one primary amino group or two secondary amino groups.
  • Starting from polyepoxide compounds having at least two epoxide groups hardening by a polyaddition reaction (chain extension) can be carried out with an amino compound having at least two amino functions.
  • the functionality of an amino compound corresponds to their number of NH bonds.
  • a primary amino group thus has a functionality of 2 while a secondary amino group has a functionality of 1.
  • amino hardeners having a functionality of at least 3 (for example at least 3 secondary amino groups or at least one primary and one secondary amino group), especially those having two primary amino groups (functionality of 4).
  • Preferred amino hardeners are dimethyldicykan (DMDC), dicyandiamide (DICY), isophoronediamine (IPDA), diethylenetriamine (DETA), triethylenetetramine (TETA), bis (p-aminocyclohexyl) methane (PACM), methylenedianiline (for example 4,4'-methylenedianiline)
  • Polyetheramines for example polyetheramine D230, diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), 2,4-toluenediamine, 2,6-toluenediamine, 2,4-diamino-1-methylcyclohexane, 2,6-diamino-1-methylcyclohexane, 2,4-diamino-3,
  • DICY isophorone diamine
  • IPDA isophorone diamine
  • methylenedianiline for example 4,4'-methylenedianiline
  • aminoplasts such as condensation products of aldehydes such as formaldehyde, acetaldehyde, crotonaldehyde or benzaldehyde with melamine, urea or benzoguanamine.
  • polyepoxide compound and amino hardener in a relative to the epoxide or amino-functional compound. used in about stoichiometric ratio. Particularly suitable ratios of epoxide groups to amino functionality are, for example, 1: 0.8 to 0.8: 1.
  • the curable epoxy resin composition of the present invention includes a phenolic resin as a curing agent.
  • Phenol resins suitable for the polyaddition reaction have at least two hydroxyl groups.
  • Phenolic resins can typically be used in both stoichiometric and substoichiometric proportions to the epoxy compounds.
  • the use of suitable catalysts promotes the reaction of the secondary hydroxyl groups of the already formed epoxy resin with epoxide groups.
  • Suitable phenolic resins are, for example, novolacs, phenolic resoles, generally condensation products of aldehydes (preferably formaldehyde and acetaldehyde) with phenols.
  • Preferred phenols are phenol, cresol, xylenols, p-phenylphenol, p-tert.-butyl-phenol, p-tert.amyl-phenol, cyclopentylphenol, p-nonyl and p-octylphenol.
  • the curable epoxy resin composition of the invention may also comprise an accelerator for curing.
  • suitable curing accelerators are imidazole or imidazole derivatives or urea derivatives (urones), for example 1,1-dimethyl-3-phenylurea (fenuron).
  • urones 1,1-dimethyl-3-phenylurea
  • tertiary amines such as triethanolamine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol and tetramethyl guanidine as curing accelerator is described (US 4,948,700).
  • the curing of epoxy resins with DICY can be accelerated by the addition of fenuron.
  • the curable epoxy resin composition of the present invention may also include a diluent.
  • Diluents for the purposes of this invention are conventional diluents or reactive diluents.
  • the addition of diluent to a curable epoxy resin composition usually lowers its viscosity.
  • Conventional diluents are typically organic solvents or mixtures thereof, for example ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), diethyl ketone or cyclohexanone, esters of aliphatic carboxylic acids such as ethyl acetate, propyl acetate, methoxypropyl acetate or butyl acetate, glycols such as ethylene glycol, diethylene glycol, triethylene glycol or propylene glycol, etc.
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), diethyl ketone or cyclohexanone
  • Glycol derivatives such as ethoxyethanol, ethoxyethanol acetate, ethylene or propylene glycol mono- or dimethyl ethers, aromatic hydrocarbons such as toluene or xylenes, aliphatic hydrocarbons such as heptane, and alkanols such as methanol, ethanol, n- or isopropanol or butanols.
  • Reactive diluents are low molecular weight substances which, in contrast to conventional solvents, have functional groups, generally oxirane groups, which can react with the hydroxy groups of the resin and / or the functional groups of the hardener to form covalent bonds.
  • Reactive diluents for the purposes of the present invention are aliphatic or cycloaliphatic compounds. They do not evaporate during curing, but are covalently bonded into the forming resin matrix during curing.
  • Suitable reactive diluents are, for example, mono- or polyfunctional oxiranes. Examples of monofunctional reactive diluents are glycidyl ethers of aliphatic and cycloaliphatic monohydroxy compounds having generally 2 to 20 carbon atoms, such as.
  • polyfunctional reactive diluents are, in particular, glycidyl ethers of polyfunctional alcohols having generally 2 to 20 C atoms which typically have on average 1.5 to 4 glycidyl groups, such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether or the glycidyl ethers of Trimethylolpropane or pentaerythritol.
  • the reactive diluents described so far improve the viscosity properties of the epoxy resin compositions, they often worsen the hardness of the cured resin and lead to lower solvent resistance. Furthermore, it is known that the reactive diluents reduce the reactivity of the epoxy resin compositions formulated therewith, resulting in longer cure times.
  • the curable epoxy resin composition of the present invention may also include fillers, for example, pigments.
  • suitable fillers are metal oxides such as titanium dioxide, zinc oxide and iron oxide or hydroxides, sulfates, carbonates, silicates of these or other metals, for example calcium carbonate, aluminum oxide, aluminum silicates.
  • Further suitable fillers are, for example, silicon dioxide, pyrogenic or precipitated silica and also carbon black, talc, barite or other nontoxic pigments. It is also possible to use mixtures of the fillers.
  • the proportion by weight of the fillers in the coating, their particle size, hardness and their aspect ratio will be selected by a person skilled in the art according to the application requirements.
  • the curable epoxy resin composition according to the invention may contain further additives as required, for example defoamers, dispersants, wetting agents, emulsifiers, thickeners, biocides, co-solvents, bases, corrosion inhibitors, flame retardants, release agents and / or waxes.
  • the curable epoxy resin composition of the present invention may also contain reinforcing fibers such as glass fibers or carbon fibers. These can be present for example as short fiber pieces of a few mm to cm in length, and as continuous fibers, wound or tissue.
  • the present invention further relates to a process for producing a cured epoxy resin comprising curing the curable epoxy resin composition.
  • the curing can be carried out at normal pressure and at temperatures below 250 ° C., in particular at temperatures below 235 ° C., preferably at temperatures below 220 ° C., in particular in a temperature range from 40 ° C. to 220 ° C.
  • the curing of the curable epoxy resin composition to moldings is usually carried out in a tool until dimensional stability is achieved and the workpiece can be removed from the tool.
  • the subsequent process for reducing residual stresses of the workpiece and / or completing the crosslinking of the cured epoxy resin is called tempering.
  • the tempering process usually takes place at temperatures at the limit of the stiffness of the mold (Menges et al., "Werkstoff ambience Kunststoffe” (2002), Hanser-Verlag, 5th edition, page 136.) Usually at temperatures of 120 ° C. to 220 ° C.
  • the curable epoxy resin composition is first applied to the substrate to be coated, followed by curing of the curable epoxy resin composition on the substrate
  • Molds of the desired article by dipping, spraying, rolling, brushing, doctoring or the like in liquid formulations or by applying a powder coating done.
  • the application can be carried out on individual pieces (for example can parts) or on basically endless substrates, for example steel rolls in coil coating. Suitable substrates are usually steel, tinplate (tinned steel) or aluminum (for example for beverage cans).
  • the curing of the curable epoxy resin composition after application to the substrate usually takes place in the temperature range from 20 ° C to 250 ° C, preferably from 50 ° C to 220 ° C, more preferably from 100 ° C to 220 ° C instead.
  • the time is usually 0.1 to 60 minutes, preferably 0.5 to 20 minutes, more preferably 1 to 10 minutes.
  • the present invention further relates to the cured epoxy resins obtainable or obtained by curing the curable epoxy resin composition according to the invention, in particular in the form of coatings on metallic substrates.
  • the present invention further relates to the use of monomeric or oligomeric glycidyl ethers I, IA or IB according to the invention or of oligomers based on glycidyl ether I, IA or IB or of the curable epoxy resin composition according to the invention for the production of adhesives, composites, moldings and coatings , in particular of coatings, preferably of containers, in particular of containers for the storage of foodstuffs.
  • Preparation of Limone Derivatives IIA limonene can, for example, after addition of an alcoholic solvent and a Rh-containing hydroformylation catalyst in an autoclave at elevated temperature of, for example, 70 to 150 ° C and pressing on synthesis gas (CO / H2 (1: 1)) to a reaction pressure of, for example, 150 to 300 bar, with stirring, to the corresponding dialdehydes.
  • the reaction mixture thus obtained which contains the corresponding dialdehydes, after depressurization to atmospheric pressure and admixing with distilled water and a hydrogenation catalyst such as Raney nickel and after pressing hydrogen to a reaction pressure of, for example, 50 to 200 bar at elevated temperature of eg 70 to 150 ° C in an autoclave are hydrogenated with stirring.
  • reaction mixture thus obtained which contains the corresponding diols, can then be freed by distillation from the hydrogenation catalyst and by distillative removal from the solvent and then fractionally distilled for purification to give the limonene derivative IIA, which is a mixture of different diols is to get.
  • the preparation of limonene derivative IIB from limonene can be carried out according to Example 1, wherein the reaction mixture from the reaction with synthesis gas (hydroformylation product) containing the corresponding dialdehydes, before performing the hydrogenation step, first an aldol reaction with eg. Formaldehyde subjected becomes.
  • the dialdehyde-containing reaction mixture from the hydroformylation reaction optionally after previously performed distillative purification, eg. With a molar excess of aqueous Formaldehyde (36.5% strength), whereupon this reaction mixture is then added slowly to a catalytic amount of triethanolamine, and it is then neutralized with formic acid (98% tig) after the aldol reaction.
  • the reaction mixture thus prepared can, if appropriate after distillative purification, be subjected to a hydrogenation as described in Example 1, so that divinylbenzene derivative IIB, which is a mixture of the different polyols, can be obtained.
  • Limonene derivative IIA (0.7 mol, 136 g, according to Ex. 1), which is, for example, a mixture of the various diols which results from the hydroformylation and subsequent hydrogenation of unions, heated to 90 ° C. and treated with tin ( IV) chloride (7.6 mmol, 2 g) are added. Subsequently, epichlorohydrin (1.4 mol, 129.5 g) may be added dropwise in portions, the temperature, for example, should not rise above 140 ° C and should not fall below 85 ° C. After completion of the addition, it is possible to stir at 90 ° C., for example, until an epoxide content can no longer be measured. After cooling to room temperature, for example, with 25% sodium hydroxide solution (1, 4 mol, 224 g) and heated once to boiling. For working up, the product can be washed with water.
  • the monomeric glycidyl ether IA can be purified by distillation from the oligomers.
  • the glycidyl ether IB can be prepared analogously to Example 3 by reaction with epichlorohydrin.
  • the molar amount of epichlorohydrin used is preferably adjusted based on the number of hydroxyl groups of the limonene derivative IIB in comparison with the limonene derivative IIA.
  • the monomeric glycidyl ether IB can be purified by distillation from the oligomers.
  • Glycidyl ether IA from Example 3 can be mixed immediately after the preparation and without further purification with a stoichiometric amount of an amine hardener.
  • an amine hardener can be used, for example. IPDA, TETA or polyetheramine D230.
  • BADGE bisphenol A-based epoxy resin
  • Epilox A19-03 from LEUNA resins, EEW 182 g / eq) and amine hardening become.
  • the mixtures can be incubated for theological characterization at, for example, 23 ° C., 40 ° C. or 75 ° C.
  • the rheological measurements for investigating the reactivity profile can be carried out on a shear stress controlled plate-plate rheometer (MCR 301 from Anton Paar) with a plate diameter of, for example, 15 mm and a gap spacing of, for example, 0.25 mm at the different temperatures.
  • MCR 301 shear stress controlled plate-plate rheometer
  • the measurement of the gelling time can be carried out in a rotationally oscillating manner on the abovementioned rheometer at, for example, 23 ° C. and 75 ° C.
  • the intersection of loss modulus (G ") and storage modulus (G ') provides the gelation time
  • the average viscosity for 2 to 5 minutes after preparation of the mixture may be considered as initial viscosity.
  • the measurement of the glass transition temperature (Tg) can be determined by DSC (Differential Scanning Calorimetry) of the curing reaction according to ASTM D 3418 at the second pass.
  • Glycidyl ether IB from Example 4 can be used and characterized according to Example 5.

Abstract

Cured epoxy resins are widespread because of the excellent mechanical and chemical properties of cured epoxy resins. Epoxy resins based on bisphenol A diglycidyl ether or bisphenol F diglycidyl ether are usually used, but said epoxy resins are problematic for many fields because of the endocrine effect of said epoxy resins. The invention relates to glycidyl ethers of lime-based diols and/or polyols and curable epoxy resin compositions based on said glycidyl ethers as an alternative to bisphenol A diglycidyl ether or bisphenol F diglycidyl ether and the epoxy resin compositions based on bisphenol A diglycidyl ether or bisphenol F diglycidyl ether.

Description

Glycidylether von Limonen-Derivaten und deren Oligomere als härtbare Epoxidharze  Glycidyl ethers of limonene derivatives and their oligomers as curable epoxy resins
Beschreibung Die vorliegende Erfindung betrifft Glycidylether der Formel I, bei denen es sich um Glycidylether von Limonen-Derivaten der Formel II mit zwei oder mehr Glycidylgruppen handelt. Die Erfindung betrifft weiter Oligomere der Glycidylether der Formel I. Die Erfindung betrifft auch Verfahren zur Herstellung dieser monomeren und oligomeren Glycidylether, sowie deren Verwendung zur Herstellung von Klebstoffen, Verbundwerkstoffen, Formkörpern oder Beschichtungen. Die vorliegende Erfindung betrifft weiter eine härtbare Epoxidharz-Zusammensetzung umfassend eine Härterkomponente und eine Harzkomponente, die als Polyepoxidverbindung mindestens einen Glycidylether der Formel I, ein Oligomer eines Glycidylethers der Formel I oder ein auf einen Glycidylether der Formel I basierendes Oligomer enthält. Die Erfindung betrifft weiter ein Verfahren zur Härtung dieser härtbaren Epoxidharz-Zusammensetzungen und durch Härtung dieser härtbaren Epoxidharz-Zusammensetzung erhältliche bzw. erhaltene gehärtete Epoxidharze. Gegenstand der Erfindung sind auch die als Zwischenprodukt für die Herstellung der erfindungsgemäßen Glycidylether eingesetzten Limonen-Derivate der Formel II mit 3 oder 4 Hydroxylgruppen. Als Epoxidharze bezeichnet man üblicherweise oligomere Verbindungen mit im Mittel mehr als einer Epoxidgruppe pro Molekül, die durch Umsetzung mit geeigneten Härtern oder durch Polymerisation der Epoxidgruppen in Duroplaste bzw. gehärtete Epoxidharze umgewandelt werden. Gehärtete Epoxidharze sind aufgrund ihrer hervorragenden mechanischen und chemischen Eigenschaften, wie hohe Schlagzähigkeit, hohe Abriebfestigkeit, gute Hitze- und Chemi- kalienbeständigkeit, insbesondere eine hohe Beständigkeit gegenüber Laugen, Säuren, Ölen und organischen Lösungsmitteln, hohe Witterungsbeständigkeit, ausgezeichnete Haftfähigkeit auf vielen Werkstoffen und hohes elektrisches Isolationsvermögen, weit verbreitet. Sie dienen als Matrix für Faserverbundwerkstoffe ("Composites") und sind oft Hauptbestandteil in Elekt- rolaminaten, Strukturklebstoffen, Gießharzen, Beschichtungen und Pulverlacken. The present invention relates to glycidyl ethers of the formula I, which are glycidyl ethers of limonene derivatives of the formula II having two or more glycidyl groups. The invention further relates to oligomers of the glycidyl ethers of the formula I. The invention also relates to processes for the preparation of these monomeric and oligomeric glycidyl ethers, and their use for the production of adhesives, composites, moldings or coatings. The present invention further relates to a curable epoxy resin composition comprising a hardener component and a resin component containing as polyepoxide compound at least one glycidyl ether of the formula I, an oligomer of a glycidyl ether of the formula I or an oligomer based on a glycidyl ether of the formula I. The invention further relates to a process for curing these curable epoxy resin compositions and to cured epoxy resins obtainable by curing this curable epoxy resin composition. The invention also relates to the limonene derivatives of the formula II having 3 or 4 hydroxyl groups used as an intermediate for the preparation of the glycidyl ethers according to the invention. As epoxy resins are usually called oligomeric compounds having on average more than one epoxide group per molecule, which are converted by reaction with suitable curing agents or by polymerization of the epoxy groups in thermosets or cured epoxy resins. Cured epoxy resins are highly resistant to abrasion, high abrasion resistance, good heat and chemical resistance, in particular high resistance to alkalis, acids, oils and organic solvents, high weather resistance, excellent adhesion to many materials and high due to their excellent mechanical and chemical properties electrical insulation, widely used. They serve as a matrix for composites and are often the main component in electro laminates, structural adhesives, casting resins, coatings and powder coatings.
Die meisten kommerziellen (ungehärteten) Epoxidharze werden durch Kupplung von Epich- lorhydrin an Verbindungen, die wenigstens zwei reaktive Wasserstoffatome besitzen, wie Poly- phenole, Mono- und Diamine, Aminophenole, heterocyclische Imide und Amide, aliphatische Diole oder Polyole oder dimere Fettsäuren, hergestellt. Epoxidharze, die sich von Epich- lorhydrin ableiten, werden als Glycidyl-basierte Harze bezeichnet. In der Regel werden Bi- sphenol-A- oder Bisphenol-F-Diglycidylether bzw. die entsprechenden Oligomere als Epoxidharze eingesetzt. Most commercial (uncured) epoxy resins are prepared by coupling epichlorohydrin to compounds having at least two reactive hydrogen atoms, such as polyphenols, mono- and diamines, aminophenols, heterocyclic imides and amides, aliphatic diols or polyols, or dimer fatty acids , Epoxy resins derived from epichlorohydrin are referred to as glycidyl based resins. As a rule, bisphenol A or bisphenol F diglycidyl ethers or the corresponding oligomers are used as epoxy resins.
Insbesondere an Beschichtungen von Behältern für die Lagerung von Lebensmitteln und Ge- tränken werden hohe Anforderungen gestellt. So soll die Beschichtung stark sauren oder salzhaltigen Lebensmitteln (z.B. Tomaten) oder Getränken widerstehen, damit keine Korrosion des Metalls eintritt, die wiederum zur Kontamination des Füllguts führen könnte. Andererseits darf die Beschichtung nicht den Geschmack oder das Aussehen der Lebensmittel beeinträchtigen. Da während der Herstellung der Behälter oft bereits beschichtete Behälter weiter geformt wer- den, muss die Beschichtung flexibel sein. Viele Füllgüter, z.B. Lebensmittel, werden erst in der Dose pasteurisiert; daher muss die Beschichtung eine Erhitzung auf 121 °C mindestens 2 Stunden unbeschädigt und ohne Migration von Inhaltsstoffen überstehen. Die Verwendung von Epoxidharzen auf Basis von Bisphenol-A- oder Bisphenol-F- diglycidylether wird in zunehmend mehr Bereichen überdacht, da die entsprechenden Diole wegen ihrer endokrinen Wirkung als problematisch angesehen werden. Especially on coatings of containers for the storage of food and beverages high demands are made. Thus, the coating should withstand strongly acidic or salt-containing foods (eg tomatoes) or beverages, so that no corrosion of the metal occurs, which in turn could lead to contamination of the contents. On the other hand, the coating must not affect the taste or appearance of the food. Since often already coated containers are formed during the production of the containers. the coating needs to be flexible. Many fillings, eg food, are first pasteurized in a can; therefore, the coating must survive heating to 121 ° C for at least 2 hours undamaged and without migration of ingredients. The use of bisphenol A or bisphenol F diglycidyl ether based epoxy resins is being reconsidered in an increasing number of fields, since the corresponding diols are considered to be problematic because of their endocrine activity.
Zur Lösung dieses Problems sind verschiedene Vorschläge gemacht worden: To solve this problem, various proposals have been made:
US 2012/01 16048 offenbart ein Bisphenol-A (BPA) und Bisphenol-F (BPF) freies Polymer, das neben Esterbindungen auch Hydroxyetherbrücken umfasst, wobei Diepoxide zum Einsatz kommen, die auf offenkettige aliphatische Diole wie Neopentylglykol (NPG), einfache cyc- loaliphatische Diole wie 1 ,4-Cyclohexandimethanol oder aromatische Diole wie Resorcin basie- ren. Erfahrungsgemäß ergeben die beschriebenen aliphatischen und cycloaliphatischen Diole jedoch sehr weiche und wenig temperatur- und chemikalienbeständige Beschichtungen. US 2012/01 16048 discloses a bisphenol-A (BPA) and bisphenol-F (BPF) -free polymer which, in addition to ester linkages, also comprises hydroxy ether bridges, using diepoxides based on open-chain aliphatic diols such as neopentyl glycol (NPG), simple cycloaddition However, experience has shown that the described aliphatic and cycloaliphatic diols give very soft coatings which are less resistant to temperature and chemicals.
WO 2012/089657 offenbart eine BPA-freie Zubereitung aus einem filmbildenden Harz sowie einem Adhäsionspromotor. Als Harz wird ein epoxidiertes Harz hergestellt beispielsweise aus den Diglycidylethern von NPG, Ethylenglycol, Propylen- oder Dipropylenglycol, 1 ,4-Butandiol oder 1 ,6-Hexandiol. Hier sind die gleichen Einschränkungen der Beschichtungseigenschaften wie im vorigen Beispiel zu erwarten. WO 2012/089657 discloses a BPA-free preparation of a film-forming resin and an adhesion promoter. As the resin, an epoxidized resin is prepared, for example, from the diglycidyl ethers of NPG, ethylene glycol, propylene or dipropylene glycol, 1,4-butanediol or 1,6-hexanediol. Here are the same limitations of the coating properties as expected in the previous example.
WO 2010/100122 schlägt ein Beschichtungssystem vor, das erhältlich ist durch Umsetzung eines epoxidierten Pflanzenöls mit hydroxyfunktionellen Verbindungen wie z.B. Propylenglycol, Propan-1 ,3-diol, Ethylenglycol, NPG, Trimethylolpropan, Diethylenglycol u.a. WO 2010/100122 proposes a coating system obtainable by reacting an epoxidized vegetable oil with hydroxy-functional compounds, e.g. Propylene glycol, propane-1,3-diol, ethylene glycol, NPG, trimethylolpropane, diethylene glycol, and the like.
US 2004/0147638 beschreibt ein 2-Schichten (Kern/Hülle)-System, bei dem der Kern aus einem BPA- oder BPF-basierten Epoxidharz und die Deckschicht z.B. aus einem Acrylatharz ge- bildet wird. Kritisch ist hier, ob die Deckschicht wirklich vollständig die Migration von BPA oder Bisphenol-A-Diglycidylether (BADGE) in das Füllgut verhindern kann. US 2004/0147638 describes a 2-layer (core / shell) system in which the core of a BPA- or BPF-based epoxy resin and the cover layer of e.g. is formed from an acrylate resin. Critical here is whether the top coat can really completely prevent the migration of BPA or bisphenol A diglycidyl ether (BADGE) into the product.
WO 2012/091701 schlägt verschiedene Diole bzw. deren Diglycidylether als Ersatz für BPA bzw. BADGE für Epoxidharze vor, unter anderem Derivate von BPA und kernhydriertem BPA, alicyclische Diole auf Basis von Cyclobutan sowie Diole mit einem Furanring als Grundstruktur. WO 2012/091701 proposes various diols or their diglycidyl ethers as substitutes for BPA or BADGE for epoxy resins, inter alia derivatives of BPA and ring-hydrogenated BPA, alicyclic diols based on cyclobutane and diols with a furan ring as the basic structure.
Der vorliegenden Erfindung lag die Aufgabe zugrunde, monomere bzw. oligomere Gly- cidylether-Verbindungen für die Verwendung in Epoxidharz-Systemen bereitzustellen, insbesondere als zumindest partieller Ersatz von BADGE in entsprechenden Epoxidharz-Systemen, vor allem für den Einsatz zur Beschichtung von Behältern. Entsprechend betrifft die vorliegende Erfindung Glycidylether der Formel I The present invention has for its object to provide monomeric or oligomeric glycidyl ether compounds for use in epoxy resin systems, in particular as at least partial replacement of BADGE in corresponding epoxy resin systems, especially for use for coating containers. Accordingly, the present invention relates to glycidyl ethers of the formula I.
wobei in which
R1 = H und R2 = CH2OA und R3 = H, oder R1 = H and R2 = CH 2 OA and R3 = H, or
R1 = H und R2 = CH2OA und R3 = CR7R80A, oder R1 = H and R2 = CH 2 OA and R3 = CR7R80A, or
R1 = CH2OA und R2 = H und R3 = H, R1 = CH 2 OA and R2 = H and R3 = H,
und wobei and where
R4 = H und R5 = CH2OA und R6 = H, oder R4 = H and R5 = CH 2 OA and R6 = H, or
R4 = H und R5 = CH2OA und R6 = CR7R80A, oder R4 = H and R5 = R6 = CH 2 OA and CR7R80A, or
R4 = CH2OA und R5 = H und R6 = H,  R4 = CH2OA and R5 = H and R6 = H,
und wobei and where
A eine Glycidylgruppe ) oder ein H-Atom ist, und A is a glycidyl group ) or an H atom, and
R7 und R8 jeweils unabhängig voneinander ein H-Atom oder eine Ci-C4-Alkylgruppe, vorzugsweise ein H-Atom, sind,  R 7 and R 8 are each independently an H atom or a C 1 -C 4 -alkyl group, preferably an H atom,
und wobei and where
mindestens 2, bevorzugt aber alle A-Reste jeweils eine Glycidylgruppe sind.  at least 2, but preferably all A radicals are each a glycidyl group.
Die Glycidylether der Formel I in dieser Spezifikation der Reste werden im Rahmen dieser Erfindung auch kurz als„Glycidylether I" bezeichnet. In einer besonderen Ausführungsform betrifft die vorliegende Erfindung Glycidylether der Formel I in der Variante A, The glycidyl ethers of the formula I in this specification of the radicals are also referred to for the purposes of this invention as "glycidyl ether I." In a particular embodiment, the present invention relates to glycidyl ethers of the formula I in variant A,
wobei in which
R1 = H und R2 = CH2OA und R3 = H, oder R1 = H and R2 = CH 2 OA and R3 = H, or
R1 = CH2OA und R2 = H und R3 = H,  R1 = CH2OA and R2 = H and R3 = H,
und wobei and where
R4 = H und R5 = CH2OA und R6 = H, oder R4 = H and R5 = CH 2 OA and R6 = H, or
R4 = CH2OA und R5 = H und R6 = H,  R4 = CH2OA and R5 = H and R6 = H,
und wobei and where
A eine Glycidylgruppe ist.  A is a glycidyl group.
Die Glycidylether der Formel I in dieser Spezifikation der Reste (Variante A) werden im Rahmen dieser Erfindung auch kurz als„Glycidylether IA" bezeichnet. In einer besonderen Ausführungsform betrifft die vorliegende Erfindung Glycidylether der Formel I in der Variante B, The glycidyl ethers of the formula I in this specification of the radicals (variant A) are also referred to for the purposes of this invention as "glycidyl ether IA". In a particular embodiment, the present invention relates to glycidyl ethers of the formula I in variant B,
wobei in which
R1 = H und R2 = CH2OA und R3 = H, oder R1 = H and R2 = CH 2 OA and R3 = H, or
R1 = H und R2 = CH2OA und R3 = CR7R80A, oder R1 = H and R2 = CH 2 OA and R3 = CR7R80A, or
R1 = CH2OA und R2 = H und R3 = H, R1 = CH 2 OA and R2 = H and R3 = H,
und wobei and where
R4 = H und R5 = CH2OA und R6 = H, oder R4 = H and R5 = CH 2 OA and R6 = H, or
R4 = H und R5 = CH2OA und R6 = CR7R80A, oder R4 = H and R5 = R6 = CH 2 OA and CR7R80A, or
R4 = CH2OA und R5 = H und R6 = H,  R4 = CH2OA and R5 = H and R6 = H,
und wobei and where
A eine Glycidylgruppe oder ein H-Atom ist, und  A is a glycidyl group or an H atom, and
R7 und R8 jeweils unabhängig voneinander ein H-Atom oder eine Ci-C4-Alkylgruppe, vorzugsweise ein H-Atom, sind, und  R7 and R8 are each independently an H atom or a C1-C4 alkyl group, preferably an H atom, and
R3 und R6 nicht beide gleichzeitig ein H-Atom sind,  R3 and R6 are not both simultaneously an H atom,
und wobei and where
mindestens 2, bevorzugt aber alle A-Reste jeweils eine Glycidylgruppe sind.  at least 2, but preferably all A radicals are each a glycidyl group.
Die Glycidylether der Formel I in dieser Spezifikation der Reste (Variante B) werden im Rahmen dieser Erfindung auch kurz als„Glycidylether IB" bezeichnet. The glycidyl ethers of the formula I in this specification of the radicals (variant B) are also referred to in the context of this invention as "glycidyl ether IB" for short.
Die Glycidylether IA und IB sind Teilmengen der Glycidylether I. Glycidyl ethers IA and IB are subsets of glycidyl ether I.
Die Glycidylether I, IA und IB umfassen ausdrücklich alle jeweils möglichen Stereoisomere. The glycidyl ethers I, IA and IB expressly include all possible stereoisomers.
Eine Ci-C4-Alkylgruppe ist eine Methyl-, Ethyl-, n-Propyl-, iso-Propyl-, n-Butyl-, iso-Butyl-, sec- Butyl- oder tert-Butyl-Gruppe. A Ci-C4-alkyl group is a methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl or tert-butyl group.
Der Begriff Glycidylether I, IA bzw. IB betrifft auch ausdrücklich einzelne spezifische Verbindun- gen aus der jeweiligen Gruppe wie auch Mischungen von mehreren spezifischen Verbindungen der jeweiligen Gruppe. The term glycidyl ether I, IA or IB also expressly relates to individual specific compounds from the respective group as well as mixtures of several specific compounds of the respective group.
Ein weiterer Gegenstand der Erfindung sind auch Oligomere der Glycidylether I, IA bzw. IB, die durch die intermolekulare Reaktion von glycidylierten Resten mit nicht-glycidylierten, Hydro- xylgruppen aufweisenden Resten der Glycidylether I, IA bzw. IB und deren partiell (1 Glycidylgruppe aufweisend) oder nicht glycidylierten (keine Glycidylgruppe aufweisend) Derivate unter Öffnung des Oxiranrings entstehen, wobei die durch die Ringöffnung des Oxiranrings entstandene Hydroxylgruppe des Oligomers wiederum auch in glycidylierter Form vorliegen kann. Die Oligomere haben 2 bis 100, vorzugsweise 2 bis 30 monomere Einheiten (Oligomerisie- rungsgrad). Sie können linear oder verzweigt sein, vorzugsweise sind sie linear. Sie weisen im Mittel mindestens 1 ,3, bevorzugt mindestens 1 ,5, besonders bevorzugt mindestens 2 Gly- cidylgruppen auf. Der Begriff Oligomer der Glycidylether I, IA bzw. IB umfasst auch Mischungen verschiedener Oligomere (bspw. Oligomere mit verschiedenen Oligmerisierungsgrad, mit verschiedenen Verzweigungsstrukturen oder aus verschiedenen Monomeren der jeweiligen Variante (Glycidylether I, IA bzw. IB)). Diese Oligomere werden im Rahmen dieser Erfindung auch als oligomere Glycidylether I, IA bzw. IB bezeichnet. Another object of the invention are also oligomers of glycidyl ethers I, IA and IB, by the intermolecular reaction of glycidylated residues with non-glycidylated, hydroxyl-containing residues of the glycidyl ethers I, IA and IB and their partial (1 glycidyl group having ) or non-glycidylated (no glycidyl group containing) derivatives under opening of the oxirane ring, wherein the resulting by the ring opening of the oxirane ring hydroxyl group of the oligomer may in turn be present in glycidylated form. The oligomers have 2 to 100, preferably 2 to 30 monomeric units (degree of oligomerization). They can be linear or branched, preferably they are linear. On average, they have at least 1, 3, preferably at least 1, 5, more preferably at least 2 glycidyl groups. The term oligomer of glycidyl ethers I, IA and IB also includes mixtures various oligomers (for example, oligomers with different degree of oligomerization, with different branching structures or from different monomers of the respective variant (glycidyl ether I, IA or IB)). These oligomers are also referred to in the context of this invention as oligomeric glycidyl ethers I, IA and IB.
Gegenstand der Erfindung ist somit ein Glycidylether ausgewählt aus der Gruppe bestehend aus Gylcidylether I und oligomere Glycidylether davon (oligomere Glycidylether I), wobei der oligomere Glycidylether durch die intermolekulare Reaktion von glycidylierten Resten mit nicht- glycidylierten, Hydroxylgruppen enthaltenden Resten des monomeren Glycidylethers der For- mel I und deren partiell oder nicht glycidylierten Derivate unter Öffnung des Oxiranrings entstehen, wobei die durch die Ringöffnung des Oxiranrings entstandene Hydroxylgruppe des oligo- merer Glycidylethers wiederum auch in glycidylierter Form vorliegen kann, und wobei der oli- gomerer Glycidylether einen Oligomerisierungsgrad von 2 bis 100 und im Mittel mindestens 1 ,3 Glycidylgruppen aufweist. The invention thus provides a glycidyl ether selected from the group consisting of glycidyl ether I and oligomeric glycidyl ethers thereof (oligomeric glycidyl ether I), where the oligomeric glycidyl ether is prepared by the intermolecular reaction of glycidylated residues with non-glycidylated, hydroxyl-containing residues of the monomeric glycidyl ether of the invention. mel I and their partially or non-glycidylated derivatives with formation of the oxirane ring are formed, wherein the hydroxyl group of the oligomeric glycidyl ether formed by the ring opening of the oxirane ring can again also be present in glycidylated form, and wherein the oligomeric glycidyl ether has a degree of oligomerization of 2 to 100 and has on average at least 1, 3 glycidyl groups.
Gegenstand der Erfindung ist somit auch ein Glycidylether ausgewählt aus der Gruppe bestehend aus Gylcidylether IA und oligomere Glycidylether davon (oligomere Glycidylether IA), wobei der oligomere Glycidylether durch die intermolekulare Reaktion von glycidylierten Resten mit nicht-glycidylierten, Hydroxylgruppen enthaltenden Resten des monomeren Glycidylethers der Formel I und deren partiell oder nicht glycidylierten Derivate unter Öffnung des Oxiranrings entstehen, wobei die durch die Ringöffnung des Oxiranrings entstandene Hydroxylgruppe des oligomerer Glycidylethers wiederum auch in glycidylierter Form vorliegen kann, und wobei der oligomerer Glycidylether einen Oligomerisierungsgrad von 2 bis 100 und im Mittel mindestens 1 ,3 Glycidylgruppen aufweist. The invention thus also provides a glycidyl ether selected from the group consisting of glycidyl ether IA and oligomeric glycidyl ethers thereof (oligomeric glycidyl ethers IA), the oligomeric glycidyl ether being obtained by the intermolecular reaction of glycidylated residues with non-glycidylated, hydroxyl-containing residues of the monomeric glycidyl ether of the formula I and their partially or non-glycidylated derivatives to form the opening of the oxirane ring, the resulting by the ring opening of the oxirane ring hydroxyl group of the oligomeric glycidyl ether may in turn be present in glycidylierter form, and wherein the oligomeric glycidyl ether a degree of oligomerization of 2 to 100 and on average at least 1 , 3 glycidyl groups.
Gegenstand der Erfindung ist somit ebenfalls ein Glycidylether ausgewählt aus der Gruppe bestehend aus Gylcidylether IB und oligomere Glycidylether davon (oligomere Glycidylether IB), wobei der oligomere Glycidylether durch die intermolekulare Reaktion von glycidylierten Resten mit nicht-glycidylierten, Hydroxylgruppen enthaltenden Resten des monomeren Glycidylethers der Formel I und deren partiell oder nicht glycidylierten Derivate unter Öffnung des Oxiranrings entstehen, wobei die durch die Ringöffnung des Oxiranrings entstandene Hydroxylgruppe des oligomerer Glycidylethers wiederum auch in glycidylierter Form vorliegen kann, und wobei der oligomerer Glycidylether einen Oligomerisierungsgrad von 2 bis 100 und im Mittel mindestens 1 ,3 Glycidylgruppen aufweist. The invention thus likewise provides a glycidyl ether selected from the group consisting of glycidyl ether IB and oligomeric glycidyl ethers IB (oligomeric glycidyl ether IB), the oligomeric glycidyl ether being obtained by the intermolecular reaction of glycidylated radicals with non-glycidylated, hydroxyl-containing radicals of the monomeric glycidyl ether of the formula I and their partially or non-glycidylated derivatives to form the opening of the oxirane ring, the resulting by the ring opening of the oxirane ring hydroxyl group of the oligomeric glycidyl ether may in turn be present in glycidylierter form, and wherein the oligomeric glycidyl ether a degree of oligomerization of 2 to 100 and on average at least 1 , 3 glycidyl groups.
Eine Ausführungsform der Erfindung betrifft Gemische aus monomerem Glycidylether I, IA, bzw. IB und dem entsprechenden oligomeren Glycidylether I, IA, bzw. IB. One embodiment of the invention relates to mixtures of monomeric glycidyl ether I, IA or IB and the corresponding oligomeric glycidyl ether I, IA or IB.
Die vorliegende Erfindung betrifft weiter ein Verfahren zur Herstellung von monomerem und oligomerem Glycidylether I, IA bzw. IB umfassend die Umsetzung von den entsprechenden Li- monen-Derivaten II, IIA bzw. IIB mit Epichlorhydrin. Dabei handel Derivaten II um Limonen-Derivate der Formel II The present invention furthermore relates to a process for the preparation of monomeric and oligomeric glycidyl ethers I, IA or IB comprising the reaction of the corresponding derivatives II, IIA or IIB with epichlorohydrin. Derivatives II are limonene derivatives of the formula II
(II), (II)
wobei in which
R9 = H und R10 = CH2OH und R1 1 = H, oder R9 = H and R10 = CH 2 OH and R1 1 = H, or
R9 = H und R10 = CH2OH und R1 1 = CR7R80H, oder R9 = H and R10 = CH 2 OH and R1 = 1 CR7R80H, or
R9 = CH2OH und R10 = H und R1 1 = H, R9 = CH2 OH and R10 = H and R1 = 1 H,
und wobei and where
R12 = H und R13 = CH2OH und R14 = H, oder R12 = H and R13 = CH 2 OH and R14 = H, or
R12 = H und R13 = CH2OH und R14 = CR7R80H, oder R12 = H and R13 = CH 2 OH and R14 = CR7R80H, or
R12 = CH2OH und R13 = H und R14 = H,  R12 = CH2OH and R13 = H and R14 = H,
und wobei and where
R7 und R8 jeweils unabhängig voneinander ein H-Atom oder eine Ci-C4-Alkylgruppe, vorzugsweise ein H-Atom, sind. Bei den Limonen-Derivaten IIA handelt es sich um Limonen-Derivate der Formel II in der Variante A mit der folgenden Spezifikation der Reste:  R7 and R8 are each independently an H atom or a C1-C4 alkyl group, preferably an H atom. The limonene derivatives IIA are limonene derivatives of the formula II in variant A with the following specification of the radicals:
R9 = H und R10 = CH2OHund R1 1 = H, oder R9 = H and R10 = CH 2 OH and R1 1 = H, or
R9 = CH2OH und R10 = H und R1 1 = H,  R9 = CH2OH and R10 = H and R1 = H,
und and
R12 = H und R13 = CH2OH und R14 = H, oder R12 = H and R13 = CH 2 OH and R14 = H, or
R12 = CH2OH und R13 = H und R14 = H.  R12 = CH2OH and R13 = H and R14 = H.
Bei den Limonen-Derivaten IIA handelt es sich um Diole. The limonene derivatives IIA are diols.
Bei den Limonen-Derivaten IIB handelt es sich um Limonen-Derivate der Formel II in der Vari- ante B mit der folgenden Spezifikation der Reste: The limonene derivatives IIB are limonene derivatives of the formula II in the variant B with the following specification of the radicals:
R9 = H und R10 = CH2OH und R1 1 = H, oder R9 = H and R10 = CH 2 OH and R1 1 = H, or
R9 = H und R10 = CH2OH und R1 1 = CR7R80H, oder R9 = H and R10 = CH 2 OH and R1 = 1 CR7R80H, or
R9 = CH2OH und R10 = H und R1 1 = H,  R9 = CH2OH and R10 = H and R1 = H,
und and
R12 = H und R13 = CH2OH und R14 = H, oder R12 = H and R13 = CH 2 OH and R14 = H, or
R12 = H und R13 = CH2OH und R14 = CR7R80H, oder R12 = H and R13 = CH 2 OH and R14 = CR7R80H, or
R12 = CH2OH und R13 = H und R14 = H, wobei R12 = CH2OH and R13 = H and R14 = H, in which
R7 und R8 jeweils unabhängig voneinander ein H-Atom oder eine Ci-C4-Alkylgruppe, vorzugsweise ein H-Atom, sind, und  R7 and R8 are each independently an H atom or a C1-C4 alkyl group, preferably an H atom, and
R1 1 und R14 nicht beide gleichzeitig ein H-Atom sind.  R1 1 and R14 are not both simultaneously an H atom.
Bei den Limonen-Derivaten I IB handelt es sich um drei- und vierwertige Alkohole (Polyole). The limonene derivatives I IB are trihydric and tetrahydric alcohols (polyols).
Bei der Glycidylierungsreaktion entsteht in der Regel ein Gemisch aus monomerem und oligo- merem Glycidylether. Die monomeren Glycidylether können mittels dem Fachmann bekannten Trennmethoden wie beispielsweise chromatographische, extraktive oder destillative Verfahren von den oligomeren Glycidylether getrennt werden. The glycidylation reaction generally produces a mixture of monomeric and oligomeric glycidyl ether. The monomeric glycidyl ethers can be separated from the oligomeric glycidyl ethers by means of separation methods known to those skilled in the art, such as, for example, chromatographic, extractive or distillative processes.
Verzugsweise erfolgt die erfindungsgemäße Umsetzung der Limonen-Derivate II , IIA bzw. I I B zu den entsprechenden Glycidylethern mit 1 bis 20, vorzugsweise mit 1 bis 10 Äquivalenten Epichlorhydrin bei einer Temperatur in einem Bereich von 20 bis 180 °C, vorzugsweise von 70 bis 150 °C in Gegenwart einer Lewis-Säure als Katalysator, vorzugsweise in Gegenwart von Zinn(IV)chlorid. Anschließend wird das Reaktionsgemisch mit einer Base (bspw. verdünnte Natronlauge) versetzt und für eine weitere Zeitspanne (bspw. 1 bis 5 h) erhitzt (bspw. unter Rück- fluss). Danach kann das Produkt mittels Phasentrennung und Waschschritten mit Wasser isoliert werden. Preferably, the reaction according to the invention of the limonene derivatives II, IIA or IIB is carried out to the corresponding glycidyl ethers with 1 to 20, preferably with 1 to 10 equivalents of epichlorohydrin at a temperature in a range from 20 to 180 ° C, preferably from 70 to 150 ° C in the presence of a Lewis acid as a catalyst, preferably in the presence of stannic chloride. Subsequently, the reaction mixture is mixed with a base (for example dilute sodium hydroxide solution) and heated for a further period of time (for example 1 to 5 h) (for example under reflux). Thereafter, the product can be isolated by means of phase separation and washing steps with water.
In einer alternativen Variante werden 1 bis 20 Äquivalenten, bevorzugt 2 bis 10 Äquivalente Epichlorhydrin für die Herstellung der erfindungsgemäßen Glycidylether eingesetzt. Die Reaktion erfolgt üblicherweise in einem Temperaturbereich von -10 °C bis 120 °C, bevorzugt 20 °C bis 60 °C. Zur Beschleunigung der Umsetzung können Basen wie wässrige oder alkoholische Lö- sungen bzw. Dispersionen anorganischer Salze, wie z.B. LiOH, NaOH, KOH, Ca(OH)2 oder Ba(OH)2 zugegeben werden. Darüber hinaus können geeignete Katalysatoren wie tertiäre Amine eingesetzt werden. In an alternative variant, 1 to 20 equivalents, preferably 2 to 10 equivalents of epichlorohydrin are used for the preparation of the glycidyl ethers according to the invention. The reaction is usually carried out in a temperature range from -10 ° C to 120 ° C, preferably 20 ° C to 60 ° C. To accelerate the reaction, bases such as aqueous or alcoholic solutions or dispersions of inorganic salts, such as, for example, sodium salts, can be used. LiOH, NaOH, KOH, Ca (OH) 2 or Ba (OH) 2 are added. In addition, suitable catalysts such as tertiary amines can be used.
Die Limonen-Derivate I IA bzw. I I B lassen sich gemäß dem folgenden Reaktionsschema aus Limonen herstellen. Dazu wird in einem ersten Schritt Limonen mittels Hydroformylierung (HF) mit Kohlenmonoxid (CO) und Wasserstoff (H2) in die entsprechenden Dicarbonylverbindungen umgesetzt. Diese kann dann entweder direkt zu den Diolen (Limonen-Derivate I IA), oder nach einer Aldolreaktion (AD) mit bspw. Formaldehyd (H2CO) zu den Polyolen (Limonen-Derivate I IB) hydriert (Hyd) werden, bspw. mit Wasserstoff (H2). Die Aldolreaktion ist nur möglich, wenn an dem zur Carbonylgruppe alpha-ständigen C-Atom ein Wasserstoffatom gebunden ist. Die Limonen-Derivate I I entsprechen der Gesamtheit der Gruppe aus Limonen-Derivate I IA und I I B. Limonen-Derivate I IA sowie deren Herstellung sind auch in DE 3228719 A1 beschrieben. The limonene derivatives I IA and IIB can be prepared from limonene according to the following reaction scheme. In a first step, limonene is converted into the corresponding dicarbonyl compounds by hydroformylation (HF) with carbon monoxide (CO) and hydrogen (H2). This can then either hydrogenated directly to the diols (limonene derivatives I IA), or after an aldol reaction (AD) with, for example, formaldehyde (H2CO) to the polyols (limonene derivatives I IB), for example with hydrogen (H2). The aldol reaction is only possible if a hydrogen atom is bonded to the carbon atom alpha-permanent carbon atom. The limonene derivatives II correspond to the entirety of the group of limonene derivatives I IA and II B. Limonene derivatives I IA and their preparation are also described in DE 3228719 A1.
CH,OH CH OH CH2OH CH, OH CH OH CH 2 OH
Die Umsetzung des Limonens zu den entsprechenden Dialdehyden erfolgt üblicherweise mittels Hydroformylierung. Dabei wird das Limonen mit einer Mischung aus Kohlenmonoxid und Wasserstoff (Synthesegas) in Gegenwart eines Hydroformylierungs-Katalysators (bspw. metallorga- nische Kobalt- oder Rhodiumverbindungen) bei erhöhtem Druck (bspw. 10 bis 100 bar Überdruck) und bei Temperaturen im Bereich von bspw. 40 bis 200 °C zu den entsprechenden Dialdehyden umgesetzt.  The reaction of limonene to the corresponding dialdehydes is usually carried out by means of hydroformylation. The limonene is reacted with a mixture of carbon monoxide and hydrogen (synthesis gas) in the presence of a hydroformylation catalyst (for example organometallic cobalt or rhodium compounds) at elevated pressure (for example 10 to 100 bar overpressure) and at temperatures in the range of, for example 40 to 200 ° C converted to the corresponding dialdehydes.
Die Dialdehyd-Derivate des Limonens können direkt zu den entsprechenden Diolen (Limonen- Derivate IIA) hydriert werden. Eine solche Hydrierung kann bspw. mittels Wasserstoff unter erhöhtem Druck in Gegenwart eines Hydrierkatalysators erfolgen. The dialdehyde derivatives of limonene can be hydrogenated directly to the corresponding diols (limonene derivatives IIA). Such hydrogenation can be carried out, for example, by means of hydrogen under elevated pressure in the presence of a hydrogenation catalyst.
Alternativ können die Dialdehyd-Derivate des Limonens auch zu den entsprechenden Polyolen (Limonen-Derivate IIB) umgesetzt werden. Dazu werden die Dialdehyd-Derivate des Limonens, soweit sie über ein H-Atom in alpha-Position zur Aldehyd-Gruppe (C,H-acide Verbindung) verfügen, zunächst durch Aldolreaktion mit einer Carbonylverbindung der Formel R7R8C=0, verzugsweise mit Formaldehyd (R7 = H und R8 = H), unter Ausbildung einer neuen C-C-Bindung zum beta-Hydroxyaldehyd umgesetzt. Anschließend können die Aldehydgruppen wie oben für die Dialdehyd-Derivate des Limonens beschrieben reduziert werden. Gegenstand der Erfindung ist somit ein Verfahren zur Herstellung von Glycidylether IA, umfassend (i) die Hydroformylierung von Limonen mit einer Mischung aus Kohlenmonoxid und Wasserstoff in Gegenwart eines Hydroformylierungs-Katalysators bei erhöhtem Druck zu den entsprechenden Dialdehyden, und (ii) die katalytische Hydrierung der Dialdehyde aus der Hydro- formylierung zu den entsprechenden Diolen, und (iii) die Umsetzung der Diole aus der katalyti- schen Hydrierung mit Epichlohydrin zu den entsprechenden Glycidylethern IA. Alternatively, the dialdehyde derivatives of limonene can also be converted to the corresponding polyols (limonene derivatives IIB). For this purpose, the dialdehyde derivatives of limonene, provided they have an H atom in the alpha position to the aldehyde group (C, H-acidic compound), first by Aldolreaktion with a carbonyl compound of the formula R7R8C = 0, preferably with formaldehyde ( R7 = H and R8 = H) to form a new CC bond to the beta-hydroxy aldehyde. Subsequently, the aldehyde groups can be reduced as described above for the dialdehyde derivatives of limonene. The invention thus provides a process for the preparation of glycidyl ether IA comprising (i) the hydroformylation of limonene with a mixture of carbon monoxide and hydrogen in the presence of a hydroformylation catalyst at elevated pressure to the corresponding dialdehydes, and (ii) the catalytic hydrogenation of Dialdehydes from the hydroformylation to the corresponding diols, and (iii) the reaction of the diols from the catalytic hydrogenation with epichlorohydrin to give the corresponding glycidyl ethers IA.
Gegenstand der Erfindung ist somit auch ein Verfahren zur Herstellung von Glycidylether IB, umfassend (i) die Hydroformylierung von Limonen mit einer Mischung aus Kohlenmonoxid und Wasserstoff in Gegenwart eines Hydroformylierungs-Katalysators bei erhöhtem Druck zu den entsprechenden Dialdehyden, und (ii) die Aldolreaktion der Dialdehyde aus der Hydroformylierung mit einer Carbonylverbindung der Formel R7R8C=0 unter Ausbildung einer neuen C-C- Bindung zu den entsprechenden beta-Hydroxyaldehyden, (iii) die katalytische Hydrierung der beta-Hydroxyaldehyden aus der Aldolreaktion zu den entsprechenden drei- und vierwertigen Alkoholen, und (iv) die Umsetzung der drei- und vierwertigen Alkoholen aus der katalytischen Hydrierung mit Epichlohydrin zu den entsprechenden Glycidylethern IB. The invention thus also provides a process for the preparation of glycidyl ether IB comprising (i) the hydroformylation of limonene with a mixture of carbon monoxide and hydrogen in the presence of a hydroformylation catalyst at elevated pressure to the corresponding dialdehydes, and (ii) the aldol reaction of Dialdehydes from the hydroformylation with a carbonyl compound of the formula R7R8C = 0 to form a new CC bond to the corresponding beta-hydroxyaldehydes, (iii) the catalytic hydrogenation of the beta-hydroxyaldehydes from the aldol reaction to the corresponding trihydric and tetrahydric alcohols, and ( iv) the reaction of the tri- and tetrahydric alcohols from the catalytic hydrogenation with epichlorohydrin to the corresponding glycidyl ethers IB.
Gegenstand der Erfindung sind auch die Limonen-Derivate IIB, die als Zwischenprodukt bei der Herstellung der erfindungsgemäßen Glycidylether IB dienen. The invention also relates to the limonene derivatives IIB, which serve as an intermediate in the preparation of the glycidyl ether IB according to the invention.
Die vorliegende Erfindung betrifft weiter Verfahren zur Herstellung von Oligomeren, die auf Glycidylether I, IA oder IB basieren, durch Umsetzung von monomerem Glycidylether I, IA, bzw. IB mit Diolen (Kettenverlängerung). Dazu wird monomerer Glycidylether I, IA, bzw. IB oder ein Gemisch von monomerem Glycidylether I, IA, bzw. IB und entsprechendem oligomerem Gly- cidylether I, IA, bzw. IB umgesetzt mit einem oder mehreren Diolen. Vorzugsweise weist dabei der oligomere Glycidylether I, IA, bzw. IB einen geringen Oligomerisierungsgrad, insbesondere einen Oligomerisierungsgrad von 5 bis 10 auf. Vorzugsweise werden dazu 0,01 bis 0,95, besonders bevorzugt 0,05 bis 0,8, insbesondere 0,1 bis 0,4 Äquivalente des Diols bezogen auf den oder die eingesetzten Glycidylether eingesetzt. Vorzugsweise wird durch einen unterstöch- iometrischen Einsatz des Diols bzw. der Diole erreicht, dass das resultierende Oligomer, das auf Glycidylether I, IA, bzw. IB basiert, im Mittel mehr als 1 , bevorzugt mehr als 1 ,5, besonders bevorzugt mehr als 1 ,9 Epoxidgruppen pro Molekül aufweist. Die Reaktion erfolgt üblicherweise in einem Temperaturbereich von 50 °C bis 200 °C, bevorzugt von 60 °C bis 160 °C. Geeignete Diole sind typischerweise aromatische, cycloaliphatische oder aliphatische Dihydroxyverbin- düngen, beispielsweise Furandimethanol, kernhydriertes Bisphenol A, kernhydriertes Bisphenol F, Neopentylglykol, Bisphenol A, Bisphenol F oder Bisphenol S, bevorzugt Furandimethanol, kernhydriertes Bisphenol A oder kern hydriertes Bisphenol F. The present invention further relates to processes for the preparation of oligomers based on glycidyl ether I, IA or IB, by reacting monomeric glycidyl ether I, IA, and IB with diols (chain extension). For this, monomeric glycidyl ether I, IA, or IB or a mixture of monomeric glycidyl ether I, IA, or IB and corresponding oligomeric glycidyl ether I, IA, or IB is reacted with one or more diols. The oligomeric glycidyl ether I, IA or IB preferably has a low degree of oligomerization, in particular a degree of oligomerization of from 5 to 10. Preference is given to 0.01 to 0.95, more preferably 0.05 to 0.8, in particular 0.1 to 0.4 equivalents of the diol based on the glycidyl ether or used used. It is preferably achieved by substoichiometric use of the diol or diols that the resulting oligomer based on glycidyl ethers I, IA or IB has an average of more than 1, preferably more than 1.5, more preferably more than 1, 9 epoxide groups per molecule. The reaction is usually carried out in a temperature range from 50 ° C to 200 ° C, preferably from 60 ° C to 160 ° C. Suitable diols are typically aromatic, cycloaliphatic or aliphatic dihydroxy compounds, for example furandimethanol, ring-hydrogenated bisphenol A, ring-hydrogenated bisphenol F, neopentyl glycol, bisphenol A, bisphenol F or bisphenol S, preferably furandimethanol, ring-hydrogenated bisphenol A or ring-hydrogenated bisphenol F.
Entsprechend sind Gegenstand der vorliegenden Erfindung auch Oligomeren, die auf Gly- cidylether I, IA, bzw. IB basieren, die erhältlich sind bzw. erhalten werden, durch Umsetzung eines monomeren Glycidylethers I, IA, bzw. IB oder des entsprechenden oligomeren Gly- cidylethers oder eines Gemisches von monomerem Glycidylether I, IA, bzw. IB und dem ent- sprechenden oligomeren Glycidylether mit einem oder mehreren Diolen. Vorzugsweise weist dabei der oligomere Glycidylether I, IA, bzw. IB einen geringen Oligomerisierungsgrad, insbesondere einen Oligomerisierungsgrad von 5 bis 10 auf. In einer besonderen Ausführungsform sind die eingesetzten ein oder mehreren Diole nicht identisch ist mit den Limonen-Derivaten IIA, wodurch Mischoligomere, die auf Glycidylether I, IA, bzw. IB basieren, erhältlich sind bzw. erhalten werden. In einer besonderen Ausführungsform sind die eingesetzten ein oder mehreren Diole identisch mit den Limonen-Derivaten IIA, wodurch Oligomere, die auf Glycidylether I, IA, bzw. IB basieren, erhältlich sind bzw. erhalten werden. In analoger Weise können auch gezielt höhermolekulare oligomere Glycidylether I, IA, bzw. IB ausgehend von oligomeren Glycidylether I, IA, bzw. IB mit geringerem Oligomerisierungsgrad hergestellt werden. Accordingly, the subject of the present invention are also oligomers based on glycidyl ether I, IA, or IB, which are obtainable or obtainable, by reacting a monomeric glycidyl ether I, IA, or IB or the corresponding oligomeric glycidyl ether or a mixture of monomeric glycidyl ether I, IA, or IB and the speaking oligomeric glycidyl ether with one or more diols. The oligomeric glycidyl ether I, IA or IB preferably has a low degree of oligomerization, in particular a degree of oligomerization of from 5 to 10. In a particular embodiment, the one or more diols used are not identical to the limonene derivatives IIA, whereby mixed oligomers based on glycidyl ethers I, IA or IB are obtainable or obtainable. In a particular embodiment, the one or more diols used are identical to the limonene derivatives IIA, whereby oligomers based on glycidyl ethers I, IA or IB are obtainable or obtainable. In an analogous manner, higher molecular weight oligomeric glycidyl ethers I, IA or IB can also be prepared starting from oligomeric glycidyl ethers I, IA or IB with a lower degree of oligomerization.
Die vorliegende Erfindung betrifft auch härtbare Epoxidharz-Zusammensetzungen, umfassend eine Härterkomponente, die mindestens einen Härter enthält, und eine Harzkomponente, die mindestens eine Polyepoxidverbindung enthält, ausgewählt aus der Gruppe bestehend aus monomerem Glycidylether I, IA bzw. IB, oligomerem Glycidylether I, IA bzw. IB und Oligomer, das auf Glycidylether I, IA bzw. IB basiert. The present invention also relates to curable epoxy resin compositions comprising a hardener component containing at least one curing agent and a resin component containing at least one polyepoxide compound selected from the group consisting of monomeric glycidyl ether I, IA or IB, oligomeric glycidyl ether I, IA or IB and oligomer based on glycidyl ethers I, IA and IB, respectively.
Die vorliegende Erfindung betrifft auch härtbare Epoxidharz-Zusammensetzungen, umfassend eine Härterkomponente, die mindestens einen Härter enthält, und eine Harzkomponente, die mindestens eine Polyepoxidverbindung enthält, ausgewählt aus der Gruppe bestehend aus monomerem Glycidylether I, IA bzw. IB, oligomerem Glycidylether I, IA bzw. IB und Mischoligo- mer, das auf Glycidylether I, IA bzw. IB basiert. The present invention also relates to curable epoxy resin compositions comprising a hardener component containing at least one curing agent and a resin component containing at least one polyepoxide compound selected from the group consisting of monomeric glycidyl ether I, IA or IB, oligomeric glycidyl ether I, IA or IB and Mischoligo- mer, which is based on glycidyl ethers I, IA and IB.
Vorzugsweise betrifft die vorliegende Erfindung härtbare Epoxidharz-Zusammensetzungen, umfassend eine Härterkomponente, die mindestens einen Härter enthält, und eine Harzkomponente, die mindestens eine Polyepoxidverbindung enthält, ausgewählt aus der Gruppe bestehend aus monomerem Glycidylether I und oligomerem Glycidylether I. Insbesondere betrifft die vorliegende Erfindung härtbare Epoxidharz-Zusammensetzungen, umfassend eine Härterkomponente, die mindestens einen Härter enthält, und eine Harzkomponente, die mindestens eine Polyepoxidverbindung enthält ausgewählt aus der Gruppe bestehend aus monomerem Glycidylether IA, monomerem Glycidylether IB, oligomerem Glycidylether IA und oligomerem Glycidylether IB. Preferably, the present invention relates to curable epoxy resin compositions comprising a hardener component containing at least one curing agent and a resin component containing at least one polyepoxide compound selected from the group consisting of monomeric glycidyl ether I and oligomeric glycidyl ether I. More particularly, the present invention relates to curable resins Epoxy resin compositions comprising a hardener component containing at least one curing agent and a resin component containing at least one polyepoxide compound selected from the group consisting of monomeric glycidyl ether IA, monomeric glycidyl ether IB, oligomeric glycidyl ether IA and oligomeric glycidyl ether IB.
In einer besonderen Ausführungsform betrifft die vorliegende Erfindung härtbare Epoxidharz- Zusammensetzungen umfassend eine Härterkomponente, die mindestens einen Härter enthält, und eine Harzkomponente, die mindestens eine Polyepoxidverbindung ausgewählt aus der Gruppe bestehend aus oligomerem Glycidylether IA und oligomerem Glycidylether IB enthält, wobei das Epoxidäquivalent (EEW) der eingesetzten oligomeren Glycidylether im statistischen Mittel zwischen 130 und 6000 g/mol, insbesondere zwischen 140 und 1000 g/mol liegt. In a particular embodiment, the present invention relates to curable epoxy resin compositions comprising a hardener component containing at least one curing agent and a resin component containing at least one polyepoxide compound selected from the group consisting of oligomeric glycidyl ether IA and oligomeric glycidyl ether IB, wherein the epoxide equivalent (EEW ) of the oligomeric glycidyl ethers used in the statistical average between 130 and 6000 g / mol, in particular between 140 and 1000 g / mol.
Vorzugsweise weist die erfindungsgemäße härtbare Epoxidharz-Zusammensetzung weniger als 40 Gew.-%, bevorzugt weniger als 10 Gew.-%, besonders bevorzugt weniger als 5 Gew.-%, insbesondere weniger als 1 Gew.-% Bisphenol A oder F basierte Verbindungen bezogen auf die gesamte Harzkomponente auf. Bevorzugt ist die erfindungsgemäße härtbare Epoxidharz- Zusammensetzung frei von Bisphenol A oder F basierten Verbindungen. Bisphenol A oder F basierte Verbindungen im Sinne der vorliegenden Erfindung sind Bisphenol A und F selbst, de- ren Diglycidylether, sowie darauf basierende Oligo- oder Polymere. The curable epoxy resin composition according to the invention preferably has less than 40% by weight, preferably less than 10% by weight, particularly preferably less than 5% by weight, in particular less than 1% by weight of bisphenol A or F based compounds based on the total resin component. Preferably, the curable epoxy resin composition of the invention is free of bisphenol A or F based compounds. Bisphenol A or F based compounds in the context of the present invention are bisphenol A and F themselves, their diglycidyl ethers, and oligomers or polymers based thereon.
In einer bevorzugten Ausführungsform der erfindungsgemäßen härtbaren Epoxidharz- Zusammensetzung machen die erfindungsgemäßen Polyepoxidverbindungen insgesamt einen Anteil von mindestens 40 Gew.-%, bevorzugt mindestens 60 Gew.-%, insbesondere mindes- tens 80 Gew.-% bezogen auf die gesamte Harzkomponente aus. In a preferred embodiment of the curable epoxy resin composition according to the invention, the polyepoxide compounds according to the invention overall make up a proportion of at least 40% by weight, preferably at least 60% by weight, in particular at least 80% by weight, based on the total resin component.
In einer bevorzugten Ausführungsform der erfindungsgemäßen härtbaren Epoxidharz- Zusammensetzung macht die gesamte Harzkomponente mindesten 10 Gew.-%, insbesondere mindestens 25 Gew.-% bezogen auf die gesamte härtbare Epoxidharz-Zusammensetzung aus. In a preferred embodiment of the curable epoxy resin composition according to the invention, the total resin component makes up at least 10% by weight, in particular at least 25% by weight, based on the total curable epoxy resin composition.
Im Sinne der vorliegenden Erfindung sind alle Epoxidverbindungen und nur die Epoxidverbin- dungen der härtbaren Epoxidharz-Zusammensetzung der Harzkomponente zuzurechnen. Epoxidverbindungen im Sinne der vorliegenden Erfindung sind Verbindungen mit mindestens einer Epoxidgruppe, also beispielsweise auch entsprechende Reaktivverdünner. For the purposes of the present invention, all epoxy compounds and only the epoxide compounds of the curable epoxy resin composition of the resin component are attributable. Epoxide compounds in the context of the present invention are compounds having at least one epoxide group, that is, for example, also corresponding reactive diluents.
Vorzugsweise weisen die Epoxidverbindungen der Harzkomponente im statistischen Mittel mindestens 1 ,1 , bevorzugt mindestens 1 ,5, insbesondere mindestens 1 ,9 Epoxidgruppen pro Molekül auf. Härter im Sinne der Erfindung sind Verbindungen, die geeignet sind, eine Vernetzung der erfindungsgemäßen Polyepoxidverbindungen zu bewirken. The epoxy compounds of the resin component preferably have on statistical average at least 1.1, preferably at least 1.5, in particular at least 1.9 epoxide groups per molecule. Hardeners in the context of the invention are compounds which are suitable for effecting crosslinking of the polyepoxide compounds according to the invention.
Durch Umsetzung mit Härtern können Polyepoxidverbindungen in nicht schmelzbare, dreidimensional "vernetzte", duroplastische Materialien überführt werden. By reaction with hardeners, polyepoxide compounds can be converted into non-fusible, three-dimensionally "crosslinked", duroplastic materials.
Bei der Härtung von Epoxidharzen unterscheidet man zwischen zwei Härtungstypen. Im ersten Fall weist der Härter wenigstens zwei funktionellen Gruppen auf, welche mit den Oxiran- und/oder Hydroxygruppen der Polyepoxidverbindungen unter Ausbildung kovalenter Bindungen reagieren können (Polyadditionsreaktion). Beim Aushärten kommt es dann zur Ausbildung ei- nes polymeren Netzwerkes aus miteinander kovalent verknüpften von den Polyepoxidverbindungen abstammenden Einheiten und von den Härtermolekülen abstammenden Einheiten, wobei der Grad der Vernetzung über die relativen Mengen der funktionellen Gruppen im Härter und in der Polyepoxidverbindung gesteuert werden kann. Im zweiten Fall wird eine Verbindung eingesetzt, welche die Homopolymerisation von Polyepoxidverbindungen untereinander be- wirkt. Derartige Verbindungen werden häufig auch als Initiator oder Katalysator bezeichnet. Homopolymerisation induzierende Katalysatoren sind Lewis-Basen (anionische Homopolymerisation; anionisch härtende Katalysatoren) oder Lewis-Säuren (kationische Homopolymerisation; kationisch härtenden Katalysatoren). Sie bewirken die Ausbildung von Etherbrücken zwischen den Epoxidverbindungen. Es wird angenommen, dass der Katalysator mit einer ersten Epoxid- gruppe unter Ringöffnung reagiert, wobei eine reaktive Hydroxygruppe entsteht, die wiederum mit einer weiteren Epoxidgruppe unter Ausbildung einer Etherbrücke reagiert, was zu einer neuen reaktiven Hydroxygruppe führt. Aufgrund dieses Reaktionsmechanismus genügt der un- terstöchiometrische Einsatz solcher Katalysatoren zur Aushärtung. Imidazol ist ein Beispiel für einen Katalysator, der eine anionische Homopolymerisation von Epoxidverbindungen induziert. Bortrifluorid ist ein Beispiel für einen Katalysator, der eine kationische Homopolymerisation auslöst. Auch Mischungen aus verschiedenen Polyadditionsreaktion eingehenden Härtern und Mi- schungen aus Homopolymerisation induzierenden Härtern, sowie Mischungen aus Polyadditionsreaktion eingehenden und Homopolymerisation induzierenden Härtern können zur Härtung von Polyepoxidverbindungen eingesetzt werden. When curing epoxy resins, a distinction is made between two types of curing. In the first case, the curing agent has at least two functional groups which can react with the oxirane and / or hydroxyl groups of the polyepoxide compounds to form covalent bonds (polyaddition reaction). Curing then results in the formation of a polymeric network of covalently linked units derived from the polyepoxide compounds and units derived from the hardener molecules, the degree of crosslinking being controllable via the relative amounts of the functional groups in the hardener and in the polyepoxide compound. In the second case, a compound is used which effects the homopolymerization of polyepoxide compounds with one another. Such compounds are often referred to as initiator or catalyst. Homopolymerization inducing catalysts are Lewis bases (anionic homopolymerization, anionic curing catalysts) or Lewis acids (cationic homopolymerization; cationic curing catalysts). They cause the formation of ether bridges between the epoxide compounds. It is believed that the catalyst reacts with a first epoxide group to ring opening to form a reactive hydroxy group, which in turn reacts with another epoxide group to form an ether bridge, resulting in a new reactive hydroxy group. Due to this reaction mechanism, the sub-stoichiometric use of such catalysts for curing is sufficient. Imidazole is an example of a catalyst that induces anionic homopolymerization of epoxide compounds. Boron trifluoride is an example of a catalyst that initiates cationic homopolymerization. It is also possible to use mixtures of various polyaddition reaction hardeners and mixtures of homopolymerization-inducing hardeners, as well as mixtures of polyaddition reaction-inducing and homopolymerization-inducing hardeners for curing polyepoxide compounds.
Geeignete funktionelle Gruppen, die mit den Oxirangruppen von Polyepoxidverbindungen (Epo- xidharzen) eine Polyadditionsreaktion eingehen können, sind beispielsweise Aminogruppen, Hydroxygruppen, Thioalkohole bzw. Derivate davon, Isocyanate und Carboxylgruppen bzw. Derivate davon, wie Anhydride. Dementsprechend werden üblicherweise als Härter für Epoxidharze aliphatische, cycloaliphatische und aromatische Polyamine, Carbonsäureanhydride, Po- lyamidoamine, Aminoplaste wie z.B. Formaldehydkondensationsprodukte von Melamin, Harn- stoff, Benzoguanamin oder Phenoplaste wie z.B. Novolake, eingesetzt. Auch oligomere oder polymere Härter auf Acrylatbasis mit Hydroxy- oder Glycidylfunktionen in der Seitenkette sowie Epoxyvinylesterharze werden verwendet. Dem Fachmann ist bekannt, für welche Anwendungen ein schnell oder langsam wirkender Härter eingesetzt wird. So wird er beispielsweise für lagerstabile Einkomponenten-Formulierungen einen sehr langsam (bzw. erst bei höherer Tem- peratur) wirkenden Härter verwenden. Gegebenenfalls wird man einen Härter verwenden, der erst unter Anwendungsbedingungen als aktive Form freigesetzt wird, beispielsweise Ketimine oder Aldimine. Bekannte Härter besitzen eine lineare oder höchstens schwach vernetzte Struktur. Sie sind beispielsweise in Ullmann's Encyclopedia of Industrial Chemistry, 5. Auflage auf CD-ROM, 1997, Wiley-VCH, Kapitel "Epoxy Resins" beschrieben, worauf hiermit in vollem Um- fang Bezug genommen wird. Suitable functional groups which can undergo a polyaddition reaction with the oxirane groups of polyepoxide compounds (epoxy resins) are, for example, amino groups, hydroxy groups, thioalcohols or derivatives thereof, isocyanates and carboxyl groups or derivatives thereof, such as anhydrides. Accordingly, as curing agents for epoxy resins, aliphatic, cycloaliphatic and aromatic polyamines, carboxylic anhydrides, polyamidoamines, aminoplasts, e.g. Formaldehyde condensation products of melamine, urea, benzoguanamine or phenoplasts, such as e.g. Novolak, used. Also acrylate-based oligomeric or polymeric curing agents having hydroxy or glycidyl functions in the side chain as well as epoxy vinylester resins are used. The skilled worker knows for which applications a fast or slow-acting hardener is used. For example, for storage-stable one-component formulations, it will use a hardener which acts very slowly (or only at a relatively high temperature). Optionally, one will use a hardener which is released as an active form only under conditions of use, for example ketimines or aldimines. Known hardeners have a linear or at most weakly crosslinked structure. They are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition on CD-ROM, 1997, Wiley-VCH, Chapter "Epoxy Resins", which is hereby incorporated by reference in its entirety.
Geeignete Härter für die erfindungsgemäße härtbare Epoxidharz-Zusammensetzung sind beispielsweise Polyphenole, Polycarbonsäuren, Polymerkaptane, Polyamine, primäre Monoamine, Sulfonamide, Aminophenole, Aminocarbonsäuren, Carbonsäureanyhdride, phenolische Hydro- xygruppen enthaltende Carbonsäuren, Sulfanilamide, sowie Mischungen davon. Im Rahmen dieser Erfindung sei unter den jeweiligen Poly-Verbindungen (z.B. Polyamin) auch die entsprechenden Di-Verbindungen (z.B. Diamin) zu verstehen. Suitable hardeners for the curable epoxy resin composition according to the invention are, for example, polyphenols, polycarboxylic acids, polymercaptans, polyamines, primary monoamines, sulfonamides, aminophenols, aminocarboxylic acids, carboxylic anhydrides, phenolic hydroxy-containing carboxylic acids, sulfanilamides, and mixtures thereof. In the context of this invention, the respective poly compounds (for example polyamine) are also to be understood as the corresponding di compounds (for example diamine).
Bevorzugte Härter für die erfindungsgemäße härtbare Epoxidharz-Zusammensetzung sind Aminohärter und Phenolharze. In einer besonderen Ausführungsform beinhaltet die erfindungsgemäße härtbare Epoxidharz- Zusammensetzung einen Aminohärter als Härter. Für die Polyadditionsreaktion geeignete Ami- nohärter sind Verbindungen, die mindestens zwei sekundäre oder mindestens eine primäre Aminogruppe besitzen. Durch die Verknüpfung der Aminogruppen des Aminohärters mit den Epoxidgruppen der Polyepoxidverbindung bilden sich Polymere, deren Einheiten von den Ami- nohärtern und den Polyepoxidverbindungen stammen. Aminohärter werden daher in der Regel im stöchiometrischem Verhältnis zu den Epoxidverbindungen eingesetzt. Wenn der Aminohärter beispielsweise zwei primäre Aminogruppen hat, also mit bis zu vier Epoxidgruppen koppeln kann, können vernetzte Strukturen entstehen. Preferred hardeners for the curable epoxy resin composition of the present invention are amino hardeners and phenolic resins. In a particular embodiment, the curable epoxy resin composition of the invention includes an amino hardener as a curing agent. Amino hardeners suitable for the polyaddition reaction are compounds which have at least two secondary or at least one primary amino group. Linkage of the amino groups of the amino hardener with the epoxide groups of the polyepoxide compound forms polymers whose units derive from the amino hardeners and the polyepoxide compounds. Amino hardeners are therefore usually used in a stoichiometric ratio to the epoxy compounds. If, for example, the amino hardener has two primary amino groups, ie can couple with up to four epoxide groups, crosslinked structures can be formed.
Die Aminohärter der erfindungsgemäßen härtbaren Epoxidharz-Zusammensetzung besitzen mindestens eine primäre Aminogruppe oder zwei sekundäre Aminogruppen. Ausgehend von Polyepoxidverbindungen mit mindestens zwei Epoxidgruppen kann mit einer Aminoverbindung mit mindestens zwei Aminofunktionen eine Härtung durch eine Polyadditionsreaktion (Ketten- Verlängerung) erfolgen. Dabei entspricht die Funktionalität einer Aminoverbindung ihrer Anzahl an NH-Bindungen. Eine primäre Aminogruppe hat somit eine Funktionalität von 2, während eine sekundäre Aminogruppe eine Funktionalität von 1 hat. Durch die Verknüpfung der Aminogruppen des Aminohärters mit den Epoxidgruppen der Polyepoxidverbindung bilden sich Polymere aus dem Aminohärter und der Polyepoxidverbindung, wobei die Epoxidgruppen zu freien OH- Gruppen umgesetzt werden. Bevorzugt werden Aminohärter verwendet, mit einer Funktionalität von mindestens 3 (beispielsweise mindestens 3 sekundäre Aminogruppen oder mindestens eine primäre und eine sekundäre Aminogruppe), insbesondere solche mit zwei primären Aminogruppen (Funktionalität von 4). Bevorzugte Aminohärter sind Dimethyldicykan (DMDC), Dicyandiamid (DICY), Isophorondiamin (IPDA), Diethylentriamin (DETA), Triethylentetramin (TETA), Bis(p-aminocyclohexyl)methan (PACM), Methylendianilin (bspw. 4,4'-Methylendianilin), Polyetheramine, bspw. Polyetheramin D230, Diaminodiphenylmethan (DDM), Diaminodiphenylsulfon (DDS), 2,4-Toluoldiamin, 2,6- Toluoldiamin, 2,4-Diamino-1 -methylcyclohexan, 2,6-Diamino-1 -methylcyclohexan, 2,4-Diamino- 3,5-diethyltoluol, 2,6-Diamino-3,5-diethyltoluol, 1 ,2-Diaminobenzol, 1 ,3-Diaminobenzol, 1 ,4- Diaminobenzol, Diaminodiphenyloxid, 3,3',5,5'-Tertramethyl-4,4'-diaminodiphenyl und 3,3'- Dimethyl4,4'-diaminodiphenyl, sowie Aminoplaste wie z.B. Kondensationsprodukte von Aldehyden wie Formaldehyd, Acetaldehyd, Crotonaldehyd oder Benzaldehyd mit Melamin, Harnstoff oder Benzoguanamin sowie Gemisch davon. Besonders bevorzugte Aminohärter für die erfin- dungsgemäße härtbare Zusammensetzung sind Dimethyldicykan (DMDC), DicyandiamidThe amino hardeners of the curable epoxy resin composition of the present invention have at least one primary amino group or two secondary amino groups. Starting from polyepoxide compounds having at least two epoxide groups, hardening by a polyaddition reaction (chain extension) can be carried out with an amino compound having at least two amino functions. The functionality of an amino compound corresponds to their number of NH bonds. A primary amino group thus has a functionality of 2 while a secondary amino group has a functionality of 1. By linking the amino groups of the amino hardener with the epoxide groups of the polyepoxide compound, polymers of the amino hardener and the polyepoxide compound are formed, the epoxide groups being converted to free OH groups. Preference is given to using amino hardeners having a functionality of at least 3 (for example at least 3 secondary amino groups or at least one primary and one secondary amino group), especially those having two primary amino groups (functionality of 4). Preferred amino hardeners are dimethyldicykan (DMDC), dicyandiamide (DICY), isophoronediamine (IPDA), diethylenetriamine (DETA), triethylenetetramine (TETA), bis (p-aminocyclohexyl) methane (PACM), methylenedianiline (for example 4,4'-methylenedianiline) Polyetheramines, for example polyetheramine D230, diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), 2,4-toluenediamine, 2,6-toluenediamine, 2,4-diamino-1-methylcyclohexane, 2,6-diamino-1-methylcyclohexane, 2,4-diamino-3,5-diethyltoluene, 2,6-diamino-3,5-diethyltoluene, 1, 2-diaminobenzene, 1, 3-diaminobenzene, 1, 4-diaminobenzene, diaminodiphenyloxide, 3,3 ', 5 , 5'-Tertramethyl-4,4'-diaminodiphenyl and 3,3'-dimethyl4,4'-diaminodiphenyl, and aminoplasts such as Condensation products of aldehydes such as formaldehyde, acetaldehyde, crotonaldehyde or benzaldehyde with melamine, urea or benzoguanamine and mixtures thereof. Particularly preferred amino hardeners for the curable composition according to the invention are dimethyl dicykan (DMDC), dicyandiamide
(DICY), Isophorondiamin (IPDA) und Methylendianilin (bspw. 4,4'-Methylendianilin) sowie Aminoplaste wie z.B. Kondensationsprodukte von Aldehyden wie Formaldehyd, Acetaldehyd, Crotonaldehyd oder Benzaldehyd mit Melamin, Harnstoff oder Benzoguanamin. Vorzugsweise werden bei der erfindungsgemäßen härtbaren Epoxidharz-Zusammensetzung Polyepoxidverbindung und Aminohärter in einem bezogen auf die Epoxid- bzw. die Aminofunk- tionalität in etwa stöchiometrischem Verhältnis eingesetzt. Besonders geeignete Verhältnisse von Epoxidgruppen zu Aminofunktionalität sind beispielsweise 1 : 0,8 bis 0,8 : 1 . (DICY), isophorone diamine (IPDA) and methylenedianiline (for example 4,4'-methylenedianiline) and aminoplasts such as condensation products of aldehydes such as formaldehyde, acetaldehyde, crotonaldehyde or benzaldehyde with melamine, urea or benzoguanamine. In the case of the curable epoxy resin composition according to the invention, it is preferable to use polyepoxide compound and amino hardener in a relative to the epoxide or amino-functional compound. used in about stoichiometric ratio. Particularly suitable ratios of epoxide groups to amino functionality are, for example, 1: 0.8 to 0.8: 1.
In einer besonderen Ausführungsform beinhaltet die erfindungsgemäße härtbare Epoxidharz- Zusammensetzung ein Phenolharz als Härter. Für die Polyadditionsreaktion geeignete Phenolharze besitzen mindestens zwei Hydroxylgruppen. Durch die Verknüpfung der Hydroxylgruppen des Phenolharzes mit den Epoxidgruppen der Polyepoxidverbindung bilden sich Polymere, deren Einheiten von den Phenolharzen und den Polyepoxidverbindungen stammen. Phenolharze können in der Regel sowohl im stochiometrischen als auch im substochiometrischen Verhältnis zu den Epoxidverbindungen eingesetzt. Bei Einsatz substöchiometrischer Mengen des Phenolharzes wird durch Einsatz geeigneter Katalysatoren die Reaktion der sekundären Hydroxygrup- pen des bereits entstandenen Epoxidharzes mit Epoxidgruppen begünstigt. In a particular embodiment, the curable epoxy resin composition of the present invention includes a phenolic resin as a curing agent. Phenol resins suitable for the polyaddition reaction have at least two hydroxyl groups. By linking the hydroxyl groups of the phenolic resin with the epoxide groups of the polyepoxide compound, polymers are formed whose units are derived from the phenolic resins and the polyepoxide compounds. Phenolic resins can typically be used in both stoichiometric and substoichiometric proportions to the epoxy compounds. When substoichiometric amounts of the phenolic resin are used, the use of suitable catalysts promotes the reaction of the secondary hydroxyl groups of the already formed epoxy resin with epoxide groups.
Geeignete Phenolharze sind beispielsweise Novolake, phenolische Resole, allgemein Konden- sationsprodukte von Aldehyden (bevorzugt Formaldehyd und Acetaldehyd) mit Phenolen. Bevorzugte Phenole sind Phenol, Cresol, Xylenole, p-Phenylphenol, p-tert.butyl-Phenol, p- tert.amyl-Phenol, Cyclopentylphenol, p-Nonyl- und p-Octylphenol. Suitable phenolic resins are, for example, novolacs, phenolic resoles, generally condensation products of aldehydes (preferably formaldehyde and acetaldehyde) with phenols. Preferred phenols are phenol, cresol, xylenols, p-phenylphenol, p-tert.-butyl-phenol, p-tert.amyl-phenol, cyclopentylphenol, p-nonyl and p-octylphenol.
Die erfindungsgemäße härtbare Epoxidharz-Zusammensetzung kann auch einen Beschleuniger für die Härtung umfassen. Geeignete Härtungsbeschleuniger sind beispielsweise Imidazol oder Imidazol-Derivate oder Harnstoffderivate (Urone), wie beispielsweise 1 ,1 -Dimethyl-3- phenylharnstoff (Fenuron). Auch die Verwendung von tertiären Aminen wie beispielsweise Triethanolamin, Benzyldimethylamin, 2,4,6-Tris(dimethylaminomethyl)phenol und Tetramethyl- guanidin als Härtungsbeschleuniger ist beschrieben (US 4,948,700). Bekanntermaßen kann beispielsweise die Härtung von Epoxidharzen mit DICY durch Zugabe von Fenuron beschleunigt werden. The curable epoxy resin composition of the invention may also comprise an accelerator for curing. Examples of suitable curing accelerators are imidazole or imidazole derivatives or urea derivatives (urones), for example 1,1-dimethyl-3-phenylurea (fenuron). The use of tertiary amines such as triethanolamine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol and tetramethyl guanidine as curing accelerator is described (US 4,948,700). As is known, for example, the curing of epoxy resins with DICY can be accelerated by the addition of fenuron.
Die erfindungsgemäße härtbare Epoxidharz-Zusammensetzung kann auch ein Verdünnungsmittel beinhalten. The curable epoxy resin composition of the present invention may also include a diluent.
Verdünnungsmitteln im Sinne dieser Erfindung sind konventionelle Verdünnungsmittel oder Reaktivverdünner. Durch die Zugabe von Verdünnungsmittel zu einer härtbaren Epoxidharz- Zusammensetzung wird üblicherweise deren Viskosität gesenkt. Konventionelle Verdünnungsmittel sind typischerweise organische Lösungsmittel oder Mischungen davon, beispielsweise Ketone wie Aceton, Methylethylketon, Methylisobutylketon (MIBK), Diethylketon oder Cyclohexanon, Ester aliphatischer Carbonsäuren wie Ethylacetat, Propylacetat, Methoxypropylacetat oder Butylacetat, Glykole wie Ethylenglykol, Diethylenglykol, Triethylenglykol oder Propylenglykol etc., Glykolderivate wie Ethoxyethanol, Ethoxyethano- lacetat, Ethylen- oder Propylenglycolmono- oder dimethylether, aromatische Kohlenwasserstoffe wie Toluol oder Xylole, aliphatische Kohlenwasserstoffe wie beispielsweise Heptan, sowie Alkanole wie Methanol, Ethanol, n- oder Isopropanol oder Butanole. Während des Aushärtens des Epoxidharzes verdampfen sie aus der Harzmasse. Dies kann zu einer unerwünschten Volumenreduktion des Harzes (Schrumpfung) oder zur Porenbildung führen, und so mechanische Eigenschaften des ausgehärteten Materials wie beispielsweise die Bruchfestigkeit aber auch die Oberflächeneigenschaften nachteilig beeinflussen. Diluents for the purposes of this invention are conventional diluents or reactive diluents. The addition of diluent to a curable epoxy resin composition usually lowers its viscosity. Conventional diluents are typically organic solvents or mixtures thereof, for example ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), diethyl ketone or cyclohexanone, esters of aliphatic carboxylic acids such as ethyl acetate, propyl acetate, methoxypropyl acetate or butyl acetate, glycols such as ethylene glycol, diethylene glycol, triethylene glycol or propylene glycol, etc. Glycol derivatives such as ethoxyethanol, ethoxyethanol acetate, ethylene or propylene glycol mono- or dimethyl ethers, aromatic hydrocarbons such as toluene or xylenes, aliphatic hydrocarbons such as heptane, and alkanols such as methanol, ethanol, n- or isopropanol or butanols. During curing of the epoxy resin they evaporate from the resin composition. This can lead to an undesirable reduction in volume of the resin (shrinkage) or to pore formation, and thus adversely affect mechanical properties of the cured material such as the breaking strength but also the surface properties.
Reaktivverdünner sind niedermolekulare Substanzen, die im Unterscheid zu konventionellen Lösungsmitteln funktionelle Gruppen, in der Regel Oxirangruppen, aufweisen, welche mit den Hydroxygruppen des Harzes und/oder den funktionellen Gruppen des Härters unter Ausbildung kovalenter Bindungen reagieren können. Reaktivverdünner im Sinne der vorliegenden Erfin- dung sind aliphatische oder cycloaliphatische Verbindungen. Sie verdampfen während des Aushärtens nicht, sondern werden während des Aushärtens kovalent in die sich bildende Harzmatrix eingebunden. Geeignete Reaktivverdünner sind beispielsweise mono- oder polyfunktionelle Oxirane. Beispiele für monofunktionelle Reaktivverdünner sind Glycidylether aliphatischer und cycloaliphatischer Monohydroxyverbindungen mit in der Regel 2 bis 20 C- Atomen wie z. B. Ethylhexylglycidylether sowie Glycidylester aliphatischer oder cycloaliphatischer Monocarbonsäuren mit in der Regel 2 bis 20 C-Atomen. Beispiele für polyfunktionelle Reaktivverdünner sind insbesondere Glycidylether polyfunktioneller Alkohole mit in der Regel 2 bis 20 C-Atomen, die im Mittel typischerweise 1 ,5 bis 4 Glycidylgruppen aufweisen, wie 1 ,4- Butandioldiglycidylether, 1 ,6-Hexandioldiglycidylether, Diethylenglykoldiglycidylether oder die Glycidylether des Trimethylolpropans oder Pentaerythritols. Bisher beschriebene Reaktivverdünner verbessern zwar die Viskositätseigenschaften der Epoxidharzzusammensetzungen, vielfach verschlechtern sie aber die Härte des ausgehärteten Harzes und führen zu einer geringeren Lösungsmittelbeständigkeit. Des Weiteren ist bekannt, dass die Reaktivverdünner die Reaktivität der damit formulierten Epoxidharz-Zusammensetzungen verringern, was längere Härtungszeiten zur Folge hat. Reactive diluents are low molecular weight substances which, in contrast to conventional solvents, have functional groups, generally oxirane groups, which can react with the hydroxy groups of the resin and / or the functional groups of the hardener to form covalent bonds. Reactive diluents for the purposes of the present invention are aliphatic or cycloaliphatic compounds. They do not evaporate during curing, but are covalently bonded into the forming resin matrix during curing. Suitable reactive diluents are, for example, mono- or polyfunctional oxiranes. Examples of monofunctional reactive diluents are glycidyl ethers of aliphatic and cycloaliphatic monohydroxy compounds having generally 2 to 20 carbon atoms, such as. B. Ethylhexylglycidylether and glycidyl esters of aliphatic or cycloaliphatic monocarboxylic acids with usually 2 to 20 carbon atoms. Examples of polyfunctional reactive diluents are, in particular, glycidyl ethers of polyfunctional alcohols having generally 2 to 20 C atoms which typically have on average 1.5 to 4 glycidyl groups, such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether or the glycidyl ethers of Trimethylolpropane or pentaerythritol. Although the reactive diluents described so far improve the viscosity properties of the epoxy resin compositions, they often worsen the hardness of the cured resin and lead to lower solvent resistance. Furthermore, it is known that the reactive diluents reduce the reactivity of the epoxy resin compositions formulated therewith, resulting in longer cure times.
Die erfindungsgemäße härtbare Epoxidharz-Zusammensetzung kann auch Füllstoffe, beispielsweise Pigmente, beinhalten. Geeignete Füllstoffe sind Metalloxide wie Titandioxid, Zinkoxid und Eisenoxid oder Hydroxide, Sulfate, Carbonate, Silicate dieser oder anderer Metalle, beispielsweise Calciumcarbonat, Aluminiumoxid, Aluminiumsilicate. Weitere geeignete Füllstoffe sind beispielsweise Siliziumdioxid, pyrogene oder Fällungskieselsäure sowie Ruß, Talk, Baryt oder andere nichttoxische Pigmente. Auch Mischungen der Füllstoffe können eingesetzt werden. Den Gewichtsanteil der Füllstoffe an der Beschichtung, ihre Partikelgröße, -härte sowie ihren Formfaktor (aspect ratio) wird ein Fachmann je nach den Anwendungserfordernissen wählen. The curable epoxy resin composition of the present invention may also include fillers, for example, pigments. Suitable fillers are metal oxides such as titanium dioxide, zinc oxide and iron oxide or hydroxides, sulfates, carbonates, silicates of these or other metals, for example calcium carbonate, aluminum oxide, aluminum silicates. Further suitable fillers are, for example, silicon dioxide, pyrogenic or precipitated silica and also carbon black, talc, barite or other nontoxic pigments. It is also possible to use mixtures of the fillers. The proportion by weight of the fillers in the coating, their particle size, hardness and their aspect ratio will be selected by a person skilled in the art according to the application requirements.
Die erfindungsgemäße härtbare Epoxidharz-Zusammensetzung kann weitere Additive je nach den Erfordernissen enthalten, beispielsweise Entschäumer, Dispergiermittel, Netzmittel, Emul- gatoren, Verdicker, Biocide, Co-Solventien, Basen, Korrosionsinhibitoren, Flammschutzmittel, Trennmittel und/oder Wachse. Die erfindungsgemäße härtbare Epoxidharz-Zusammensetzung kann auch Verstärkungsfasern wie Glasfasern oder Carbonfasern enthalten. Diese können beispielsweise als kurze Faserstücke von wenigen mm bis cm Länge, sowie als Endlosfasern, Wickel oder Gewebe vorliegen. Die vorliegende Erfindung betrifft weiter ein Verfahren zur Herstellung eines gehärteten Epoxidharzes, umfassend die Härtung der härtbaren Epoxidharz-Zusammensetzung. The curable epoxy resin composition according to the invention may contain further additives as required, for example defoamers, dispersants, wetting agents, emulsifiers, thickeners, biocides, co-solvents, bases, corrosion inhibitors, flame retardants, release agents and / or waxes. The curable epoxy resin composition of the present invention may also contain reinforcing fibers such as glass fibers or carbon fibers. These can be present for example as short fiber pieces of a few mm to cm in length, and as continuous fibers, wound or tissue. The present invention further relates to a process for producing a cured epoxy resin comprising curing the curable epoxy resin composition.
Die Härtung kann bei Normaldruck und bei Temperaturen kleiner 250 °C, insbesondere bei Temperaturen kleiner 235 °C, vorzugsweise bei Temperaturen kleiner 220 °C erfolgen, insbe- sondere in einem Temperaturbereich von 40 °C bis 220 °C. The curing can be carried out at normal pressure and at temperatures below 250 ° C., in particular at temperatures below 235 ° C., preferably at temperatures below 220 ° C., in particular in a temperature range from 40 ° C. to 220 ° C.
Die Härtung der härtbaren Epoxidharz-Zusammensetzung zu Formkörpern erfolgt üblicherweise in einem Werkzeug, bis Formstabilität erreicht ist und das Werkstück aus dem Werkzeug entnommen werden kann. Der sich anschließende Prozess zum Abbau von Eigenspannungen des Werkstücks und/oder zum Vervollständigen der Vernetzung des gehärteten Epoxidharzes wird Tempern genannt. Grundsätzlich ist es auch möglich, den Temperprozess auch vor Entnahme des Werkstückes aus dem Werkzeug durchzuführen, etwa zur Vervollständigung der Vernetzung. Der Temperprozess findet üblicherweise bei Temperaturen an der Grenze der Formsteifigkeit statt (Menges et. al.,„Werkstoffkunde Kunststoffe" (2002), Hanser-Verlag, 5. Auflage, S. 136). Üblicherweise wird bei Temperaturen von 120 °C bis 220 °C, bevorzugt bei Temperaturen von 150 °C bis 220 °C getempert. Üblicherweise wird das gehärtete Werkstück für einen Zeitraum von 30 bis 240 min den Temperbedingungen ausgesetzt. Abhängig von den Abmessungen des Werkstücks, können auch längerer Temperzeiten angebracht sein. Bei der Härtung der härtbaren Epoxidharz-Zusammensetzung zu Beschichtungen wird zunächst das zu beschichtende Substrat mit der härtbaren Epoxidharz-Zusammensetzung beaufschlagt und anschließend die härtbaren Epoxidharz-Zusammensetzung auf dem Substrat gehärtet. Das Beaufschlagen der härtbaren Epoxidharz-Zusammensetzung kann vor oder nach demThe curing of the curable epoxy resin composition to moldings is usually carried out in a tool until dimensional stability is achieved and the workpiece can be removed from the tool. The subsequent process for reducing residual stresses of the workpiece and / or completing the crosslinking of the cured epoxy resin is called tempering. In principle, it is also possible to carry out the annealing process before removing the workpiece from the tool, for example to complete the cross-linking. The tempering process usually takes place at temperatures at the limit of the stiffness of the mold (Menges et al., "Werkstoffkunde Kunststoffe" (2002), Hanser-Verlag, 5th edition, page 136.) Usually at temperatures of 120 ° C. to 220 ° C. ° C., preferably tempered at temperatures of 150 ° C. to 220 ° C. The hardened workpiece is usually exposed to the annealing conditions for a period of 30 to 240 minutes Depending on the dimensions of the workpiece, longer annealing times may also be appropriate For example, as the curable epoxy resin composition is coated, the curable epoxy resin composition is first applied to the substrate to be coated, followed by curing of the curable epoxy resin composition on the substrate
Formen des gewünschten Artikels durch Tauchen, Spritzen, Aufwalzen, Aufstreichen, Aufrakeln oder dergleichen bei flüssigen Formulierungen oder durch Aufbringen eines Pulverlacks erfolgen. Das Aufbringen kann auf Einzelstücke (z.B. Dosenteile) oder auf prinzipiell endlose Substrate, beispielsweise auf Bandrollen aus Stahl beim Coil Coating, erfolgen. Geeignete Substra- te sind üblicherweise aus Stahl, Weißblech (verzinnter Stahl) oder Aluminium (z.B. für Getränkedosen). Das Aushärten der härtbaren Epoxidharz-Zusammensetzung nach Aufbringen auf dem Substrat findet üblicherweise im Temperaturbereich von 20 °C bis 250 °C, bevorzugt von 50 °C bis 220 °C, besonders bevorzugt von 100 °C bis 220 °C statt. Die Zeit beträgt üblicherweise 0,1 bis 60 min, bevorzugt 0,5 bis 20 min, besonders bevorzugt 1 bis 10 min. Molds of the desired article by dipping, spraying, rolling, brushing, doctoring or the like in liquid formulations or by applying a powder coating done. The application can be carried out on individual pieces (for example can parts) or on basically endless substrates, for example steel rolls in coil coating. Suitable substrates are usually steel, tinplate (tinned steel) or aluminum (for example for beverage cans). The curing of the curable epoxy resin composition after application to the substrate usually takes place in the temperature range from 20 ° C to 250 ° C, preferably from 50 ° C to 220 ° C, more preferably from 100 ° C to 220 ° C instead. The time is usually 0.1 to 60 minutes, preferably 0.5 to 20 minutes, more preferably 1 to 10 minutes.
Eine ausführliche Beschreibung der gängigen Typen von Metallverpackungen und ihrer Herstellung, verwendete Metalle und Legierungen und Beschichtungsmethoden wird in P.K.T. Oldring und U. Nehring: Packaging Materials, 7. Metal Packaging for Foodstuffs, ILSI Report, 2007, gegeben, worauf hiermit Bezug genommen wird. A detailed description of common types of metal packaging and their manufacture, metals and alloys used and coating methods will be available in PKT Oldring and U. Nehring: Packaging Materials, 7th Metal Packaging for Foodstuffs, ILSI Report, 2007, which is hereby incorporated by reference.
Die vorliegende Erfindung betrifft weiter die durch Härtung der erfindungsgemäßen härtbaren Epoxidharz-Zusammensetzung erhältlichen bzw. erhaltenen gehärteten Epoxidharze, insbesondere in Form von Beschichtungen auf metallischen Substraten. The present invention further relates to the cured epoxy resins obtainable or obtained by curing the curable epoxy resin composition according to the invention, in particular in the form of coatings on metallic substrates.
Die vorliegende Erfindung betrifft weiter die Verwendung von erfindungsgemäßen monomeren oder oligomeren Glycidylether I, IA oder IB oder von Oligomeren, die auf Glycidylether I, IA oder IB basieren, bzw. der erfindungsgemäßen härtbaren Epoxidharz-Zusammensetzung zur Herstellung von Klebstoffen, Verbundwerkstoffen, Formkörpern und Beschichtungen, insbesondere von Beschichtungen, vorzugsweise von Behältern, insbesondere von Behältern für die Lagerung von Lebensmitteln. Die Erfindung wird nun durch die nachfolgenden, nichtlimitierenden Beispiele näher erläutert. Beispiel 1 The present invention further relates to the use of monomeric or oligomeric glycidyl ethers I, IA or IB according to the invention or of oligomers based on glycidyl ether I, IA or IB or of the curable epoxy resin composition according to the invention for the production of adhesives, composites, moldings and coatings , in particular of coatings, preferably of containers, in particular of containers for the storage of foodstuffs. The invention will now be explained in more detail by the following nonlimiting examples. example 1
Herstellung von Limonen-Derivaten IIA Limonen kann bspw. nach versetzen mit einem alkoholischen Lösungsmittel und einem Rh- haltigen Hydroformylierungskatalysator in einem Autoklaven bei erhöhter Temperatur von bspw. 70 bis 150 °C und Aufpressen von Synthesegas (CO/H2 (1 :1 )) zu einem Reaktionsdruck von bspw. 150 bis 300 bar unter Rühren zu den entsprechenden Dialdehyden umgesetzt werden. Das so erhaltene Reaktionsgemisch, das die entsprechenden Dialdehyde enthält, kann nach Entspannen auf Normaldruck und Versetzen mit destilliertem Wasser und einem Hydrierkatalysator wie bspw. Raney-Nickel und nach Aufpressen von Wasserstoff zu einem Reaktionsdruck von bspw. 50 bis 200 bar bei erhöhter Temperatur von bspw. 70 bis 150 °C im Autoklaven unter Rühren hydriert werden. Das so erhaltene Reaktionsgemisch, das die entsprechenden Diole enthält, kann nach Entspannen auf Nomaldruck anschließend mittels Filterung vom Hydrierka- talysator und mittels destillativer Abtrennung vom Lösungsmittel befreit und anschließend zur Reinigung fraktioniert destilliert werden, um so das Limonen-Derivat IIA, das eine Mischung der verschiedenen Diole ist, zu erhalten.  Preparation of Limone Derivatives IIA limonene can, for example, after addition of an alcoholic solvent and a Rh-containing hydroformylation catalyst in an autoclave at elevated temperature of, for example, 70 to 150 ° C and pressing on synthesis gas (CO / H2 (1: 1)) to a reaction pressure of, for example, 150 to 300 bar, with stirring, to the corresponding dialdehydes. The reaction mixture thus obtained, which contains the corresponding dialdehydes, after depressurization to atmospheric pressure and admixing with distilled water and a hydrogenation catalyst such as Raney nickel and after pressing hydrogen to a reaction pressure of, for example, 50 to 200 bar at elevated temperature of eg 70 to 150 ° C in an autoclave are hydrogenated with stirring. The reaction mixture thus obtained, which contains the corresponding diols, can then be freed by distillation from the hydrogenation catalyst and by distillative removal from the solvent and then fractionally distilled for purification to give the limonene derivative IIA, which is a mixture of different diols is to get.
Beispiel 2 Example 2
Herstellung von Divinylbenzol-Derivat IIB Preparation of divinylbenzene derivative IIB
Die Herstellung von Limonen-Derivat IIB aus Limonen kann entsprechend Beispiel 1 erfolgen, wobei das Reaktionsgemisch aus der Umsetzung mit Synthesegas (Hydroformylierungs- Produkt), das die entsprechenden Dialdehyde enthält, vor der Durchführung des Hydrierungs- schritts zunächst einer Aldolreaktion mit bspw. Formaldehyd unterzogen wird. Dazu kann das Dialdehyd-haltige Reaktionsgemisch aus der Hydroformylierungsreaktion, ggf. nach zuvor durchgeführter destillativer Aufreinigung, bspw. mit einem molaren Überschuss an wässrigem Formaldehyd (36,5%tig) werden, worauf diesem Reaktionsgemisch dann einer katalytischen Menge von Triethanolamin langsam zudosiert wird, und es anschließend nach erfolgter Aldolre- aktion mit Ameisensäure (98%tig) neutralisiert wird. Das so hergestellte Reaktionsgemisch kann, ggf. nach destillativer Aufreinigung einer Hydrierung wie in Beispiel 1 beschrieben unter- zogen werden, so dass Divinylbenzol-Derivat IIB, das eine Mischung der verschiedenen Polyole ist, erhältlich ist. The preparation of limonene derivative IIB from limonene can be carried out according to Example 1, wherein the reaction mixture from the reaction with synthesis gas (hydroformylation product) containing the corresponding dialdehydes, before performing the hydrogenation step, first an aldol reaction with eg. Formaldehyde subjected becomes. For this purpose, the dialdehyde-containing reaction mixture from the hydroformylation reaction, optionally after previously performed distillative purification, eg. With a molar excess of aqueous Formaldehyde (36.5% strength), whereupon this reaction mixture is then added slowly to a catalytic amount of triethanolamine, and it is then neutralized with formic acid (98% tig) after the aldol reaction. The reaction mixture thus prepared can, if appropriate after distillative purification, be subjected to a hydrogenation as described in Example 1, so that divinylbenzene derivative IIB, which is a mixture of the different polyols, can be obtained.
Beispiel 3 Example 3
Herstellung von monomerem und/oder oligomerem Glycidylether IA  Preparation of monomeric and / or oligomeric glycidyl ether IA
Limonen-Derivat IIA (0,7 mol, 136 g, gemäß Bsp. 1 ), das bspw. eine Mischung der verschiedenen Diolen ist, die sich aus der Hydroformylierung und anschließenden Hydrierung von Unionen ergeben kann auf 90 °C erhitzt und mit Zinn(IV)chlorid (7,6 mmol, 2 g) versetzt werden. Anschließend kann portionsweise Epichlorhydrin (1 ,4 mol, 129,5 g) zugetropft werden, wobei die Temperatur bspw. nicht über 140 °C steigen und nicht unter 85 °C fallen sollte. Nach beendeter Zugabe kann noch solange bei bspw. 90 °C gerührt werden bis kein Epoxidgehalt mehr messbar ist. Nach Abkühlen auf Raumtemperatur kann bspw. mit 25%iger Natronlauge (1 ,4 mol, 224 g) versetzt und einmal zum Sieden erhitzt werden. Zum Aufarbeiten kann das Produkt mit Wasser gewaschen werden. Limonene derivative IIA (0.7 mol, 136 g, according to Ex. 1), which is, for example, a mixture of the various diols which results from the hydroformylation and subsequent hydrogenation of unions, heated to 90 ° C. and treated with tin ( IV) chloride (7.6 mmol, 2 g) are added. Subsequently, epichlorohydrin (1.4 mol, 129.5 g) may be added dropwise in portions, the temperature, for example, should not rise above 140 ° C and should not fall below 85 ° C. After completion of the addition, it is possible to stir at 90 ° C., for example, until an epoxide content can no longer be measured. After cooling to room temperature, for example, with 25% sodium hydroxide solution (1, 4 mol, 224 g) and heated once to boiling. For working up, the product can be washed with water.
Der monomere Glycidylether IA kann destillativ von den Oligomeren gereinigt werden. The monomeric glycidyl ether IA can be purified by distillation from the oligomers.
Beispiel 4 Example 4
Herstellung von monomerem und/oder oligomerem Glycidylether IB Preparation of monomeric and / or oligomeric glycidyl ether IB
Ausgehend von dem Limonen-Derivat IIB (gemäß Bsp. 2) kann der Glycidylether IB analog zu Beispiel 3 durch Umsetzung mit Epichlohydrin hergestellt werden. Dabei wird vorzugsweise die molare Menge an eingesetztem Epichlohydrin bezogen auf die Anzahl Hydroxylgruppen des Limonen-Derivats IIB im Vergleich zu dem Limonen-Derivat IIA angepasst. Starting from the limonene derivative IIB (according to Ex. 2), the glycidyl ether IB can be prepared analogously to Example 3 by reaction with epichlorohydrin. In this case, the molar amount of epichlorohydrin used is preferably adjusted based on the number of hydroxyl groups of the limonene derivative IIB in comparison with the limonene derivative IIA.
Der monomere Glycidylether IB kann destillativ von den Oligomeren gereinigt werden. The monomeric glycidyl ether IB can be purified by distillation from the oligomers.
Beispiel 5 Example 5
Herstellung von gehärtetem Epoxidharz aus monomerem und/oder oligomerem Glycidylether IA Preparation of cured epoxy resin from monomeric and / or oligomeric glycidyl ether IA
Glycidylether IA aus Beispiel 3 kann unmittelbar nach der Herstellung und ohne weitere Aufreinigung mit einer stöchiometrischen Menge eines aminischen Härters gemischt. Als Härter kann bspw. eingesetzt werden IPDA, TETA oder Polyetheramin D230. Zum Vergleich können ent- sprechende stöchiometrische Mischungen aus Bisphenol-A basiertem Epoxidharz (BADGE;Glycidyl ether IA from Example 3 can be mixed immediately after the preparation and without further purification with a stoichiometric amount of an amine hardener. As hardener can be used, for example. IPDA, TETA or polyetheramine D230. For comparison, corresponding stoichiometric mixtures of bisphenol A-based epoxy resin (BADGE;
Epilox A19-03 der Firma LEUNA Harze, EEW 182 g/eq) und den aminischen Härten hergestellt werden. Die Mischungen können für die Theologischen Charakterisierung bei bspw. 23 °C, 40 °C oder 75 °C inkubiert werden. Epilox A19-03 from LEUNA resins, EEW 182 g / eq) and amine hardening become. The mixtures can be incubated for theological characterization at, for example, 23 ° C., 40 ° C. or 75 ° C.
Die Theologischen Messungen zur Untersuchung des Reaktivitätsprofils können an einem schubspannungsgesteuerten Platte-Platte Rheometer (MCR 301 der Firma Anton Paar) mit einem Plattendurchmesser von bspw. 15 mm und einem Spaltabstand von bspw. 0,25 mm bei den unterschiedlichen Temperaturen durchgeführt werden. The rheological measurements for investigating the reactivity profile can be carried out on a shear stress controlled plate-plate rheometer (MCR 301 from Anton Paar) with a plate diameter of, for example, 15 mm and a gap spacing of, for example, 0.25 mm at the different temperatures.
Die Messung der Gelierzeit kann rotierend-oszillierend an dem oben genannten Rheometer bei bspw. 23 °C und 75 °C durchgeführt werden. Der Schnittpunkt von Verlustmodul (G") und Speichermodul (G') liefert die Gelierzeit. Die mittlere Viskosität während 2 bis 5 min nach Herstellen der Mischung kann als Anfangsviskosität erachtet werden. The measurement of the gelling time can be carried out in a rotationally oscillating manner on the abovementioned rheometer at, for example, 23 ° C. and 75 ° C. The intersection of loss modulus (G ") and storage modulus (G ') provides the gelation time The average viscosity for 2 to 5 minutes after preparation of the mixture may be considered as initial viscosity.
Die Messung der Glasübergangstemperatur (Tg) kann mittels DSC-Untersuchung (Differential Scanning Calorimetry) der Härtungsreaktion nach ASTM D 3418 beim 2ten Durchlauf bestimmt werden. The measurement of the glass transition temperature (Tg) can be determined by DSC (Differential Scanning Calorimetry) of the curing reaction according to ASTM D 3418 at the second pass.
Beispiel 6 Example 6
Herstellung von gehärtetem Epoxidharz aus monomerem und/oder oligomerem Glycidylether IB  Preparation of cured epoxy resin from monomeric and / or oligomeric glycidyl ether IB
Glycidylether IB aus Beispiel 4 kann entsprechend Beispiel 5 eingesetzt und charakterisiert werden. Glycidyl ether IB from Example 4 can be used and characterized according to Example 5.

Claims

Patentansprüche claims
1 . Glycidylether ausgewählt aus der Gruppe bestehend aus Gylcidylether der Formel I 1 . Glycidyl ether selected from the group consisting of glycidyl ether of the formula I.
(i) und (i) and
oligomere Glycidylether davon,  oligomeric glycidyl ethers thereof,
wobei  in which
R1 = H und R2 = CH2OA und R3 = H, oder R1 = H and R2 = CH 2 OA and R3 = H, or
R1 = H und R2 = CH2OA und R3 = CR7R80A, oder R1 = H and R2 = CH 2 OA and R3 = CR7R80A, or
R1 = CH2OA und R2 = H und R3 = H, R1 = CH 2 OA and R2 = H and R3 = H,
und wobei  and where
R4 = H und R5 = CH2OA und R6 = H, oder R4 = H and R5 = CH 2 OA and R6 = H, or
R4 = H und R5 = CH2OA und R6 = CR7R80A, oder R4 = H and R5 = R6 = CH 2 OA and CR7R80A, or
R4 = CH2OA und R5 = H und R6 = H,  R4 = CH2OA and R5 = H and R6 = H,
und wobei  and where
A eine Glycidylgruppe oder ein H-Atom ist, und  A is a glycidyl group or an H atom, and
R7 und R8 jeweils unabhängig voneinander ein H-Atom oder eine C1-C4- Alkylgruppe sind,  R7 and R8 are each independently an H atom or a C1-C4 alkyl group,
und wobei  and where
mindestens 2 A-Reste jeweils eine Glycidylgruppe sind,  at least 2 A radicals are each a glycidyl group,
und wobei  and where
der oligomere Glycidylether durch die intermolekulare Reaktion von glycidylierten Resten mit nicht-glycidylierten, Hydroxylgruppen enthaltenden Resten des monomeren Glycidylethers der Formel I und deren partiell oder nicht glycidylierten Derivate unter Öffnung des Oxiranrings entstehen, wobei die durch die Ringöffnung des Oxiranrings entstandene Hydroxylgruppe des oligomerer Glycidylethers wiederum auch in glycidylierter Form vorliegen kann, und wobei der oligomerer Glycidylether einen Oligomerisierungs- grad von 2 bis 100 und im Mittel mindestens 1 ,3 Glycidylgruppen aufweist.  the oligomeric glycidyl ethers are formed by the intermolecular reaction of glycidylated residues with non-glycidylated, hydroxyl-containing residues of the monomeric glycidyl ether of the formula I and their partially or non-glycidylated derivatives with opening of the oxirane ring, the hydroxyl group of the oligomeric glycidyl ether formed by the ring opening of the oxirane ring in turn may also be present in glycidylated form, and wherein the oligomeric glycidyl ether has a degree of oligomerization of 2 to 100 and on average at least 1, 3 glycidyl groups.
2. Der Glycidylether gemäß Anspruch 1 , ausgewählt aus der Gruppe bestehend aus Gly- cidylether der Formel I und oligomere Glycidylether davon, 2. The glycidyl ether according to claim 1, selected from the group consisting of glycidyl ethers of the formula I and oligomeric glycidyl ethers thereof,
wobei  in which
R1 = H und R2 = CH2OA und R3 = H, oder R1 = H and R2 = CH 2 OA and R3 = H, or
R1 = CH2OA und R2 = H und R3 = H,  R1 = CH2OA and R2 = H and R3 = H,
und wobei  and where
R4 = H und R5 = CH2OA und R6 = H, oder R4 = CH2OA und R5 = H und R6 = H, R4 = H and R5 = CH 2 OA and R6 = H, or R 4 = CH 2 OA and R5 = H and R6 = H,
und wobei A eine Glycidylgruppe ist,  and wherein A is a glycidyl group,
und wobei  and where
der oligomere Glycidylether durch die intermolekulare Reaktion von glycidylierten Resten mit nicht-glycidylierten, Hydroxylgruppen enthaltenden Resten des monomeren Gly- cidylethers der Formel I und deren partiell oder nicht glycidylierten Derivate unter Öffnung des Oxiranrings entstehen, wobei die durch die Ringöffnung des Oxiranrings entstandene Hydroxylgruppe des oligomerer Glycidylethers wiederum auch in glycidylierter Form vorliegen kann, und wobei der oligomerer Glycidylether einen Oligomerisierungs- grad von 2 bis 100 und im Mittel mindestens 1 ,3 Glycidylgruppen aufweist.  the oligomeric glycidyl ethers are formed by the intermolecular reaction of glycidylated radicals with non-glycidylated, hydroxyl-containing radicals of the monomeric glycidyl ether of the formula I and their partially or non-glycidylated derivatives with opening of the oxirane ring, the hydroxyl group of the oligomeric ring formed by the ring opening of the oxirane ring Glycidyl ether may also be present in glycidylated form, and wherein the oligomeric glycidyl ether a degree of oligomerization of 2 to 100 and on average at least 1, 3 glycidyl groups.
Der Glycidylether gemäß Anspruch 1 , ausgewählt aus der Gruppe bestehend aus Glycidylether der Formel I und oligomere Glycidylether davon, The glycidyl ether according to claim 1, selected from the group consisting of glycidyl ethers of the formula I and oligomeric glycidyl ethers thereof,
wobei  in which
R1 = H und R2 = CH2OA und R3 = H, oder R1 = H and R2 = CH 2 OA and R3 = H, or
R1 = H und R2 = CH2OA und R3 = CR7R80A, oder R1 = H and R2 = CH 2 OA and R3 = CR7R80A, or
R1 = CH2OA und R2 = H und R3 = H,  R1 = CH2OA and R2 = H and R3 = H,
und wobei  and where
R4 = H und R5 = CH2OA und R6 = H, oder R4 = H and R5 = CH 2 OA and R6 = H, or
R4 = H und R5 = CH2OA und R6 = CR7R80A, oder R4 = H and R5 = R6 = CH 2 OA and CR7R80A, or
R4 = CH2OA und R5 = H und R6 = H,  R4 = CH2OA and R5 = H and R6 = H,
und wobei  and where
A eine Glycidylgruppe oder ein H-Atom ist, und  A is a glycidyl group or an H atom, and
R7 und R8 jeweils unabhängig voneinander ein H-Atom oder eine C1-C4- Alkylgruppe sind, und  R7 and R8 are each independently an H atom or a C1-C4 alkyl group, and
R3 und R6 nicht beide gleichzeitig ein H-Atom sind,  R3 and R6 are not both simultaneously an H atom,
und wobei mindestens 2 A-Reste jeweils eine Glycidylgruppe sind,  and wherein at least 2 A radicals are each a glycidyl group,
und wobei  and where
der oligomere Glycidylether durch die intermolekulare Reaktion von glycidylierten Resten mit nicht-glycidylierten, Hydroxylgruppen enthaltenden Resten des monomeren Glycidylethers der Formel I und deren partiell oder nicht glycidylierten Derivate unter Öffnung des Oxiranrings entstehen, wobei die durch die Ringöffnung des Oxiranrings entstandene Hydroxylgruppe des oligomerer Glycidylethers wiederum auch in glycidylierter Form vorliegen kann, und wobei der oligomerer Glycidylether einen Oligomerisierungs- grad von 2 bis 100 und im Mittel mindestens 1 ,3 Glycidylgruppen aufweist.  the oligomeric glycidyl ethers are formed by the intermolecular reaction of glycidylated residues with non-glycidylated, hydroxyl-containing residues of the monomeric glycidyl ether of the formula I and their partially or non-glycidylated derivatives with opening of the oxirane ring, the hydroxyl group of the oligomeric glycidyl ether formed by the ring opening of the oxirane ring in turn may also be present in glycidylated form, and wherein the oligomeric glycidyl ether has a degree of oligomerization of 2 to 100 and on average at least 1, 3 glycidyl groups.
Verfahren zur Herstellung von Glycidylether nach Anspruch 2, umfassend A process for producing glycidyl ether according to claim 2, comprising
die Hydroformylierung von Limonen mit einer Mischung aus Kohlenmonoxid und Wasserstoff in Gegenwart eines Hydroformylierungs-Katalysators bei erhöhtem Druck zu den entsprechenden Dialdehyden, und the hydroformylation of limonene with a mixture of carbon monoxide and hydrogen in the presence of a hydroformylation catalyst at elevated pressure to the corresponding dialdehydes, and
die katalytische Hydrierung der Dialdehyde aus der Hydroformylierung zu den entsprechenden Diolen, und die Umsetzung der Diole aus der katalytischen Hydrierung mit Epichlohydrin zu den entsprechenden Glycidylethern gemäß Anspruch 2. the catalytic hydrogenation of the dialdehydes from the hydroformylation to the corresponding diols, and the reaction of the diols from the catalytic hydrogenation with epichlorohydrin to the corresponding glycidyl ethers according to claim 2.
Verfahren zur Herstellung von Glycidylether nach Anspruch 3, umfassend A process for producing glycidyl ether according to claim 3, comprising
die Hydroformylierung von Limonen mit einer Mischung aus Kohlenmonoxid und Wasserstoff in Gegenwart eines Hydroformylierungs-Katalysators bei erhöhtem Druck zu den entsprechenden Dialdehyden, und the hydroformylation of limonene with a mixture of carbon monoxide and hydrogen in the presence of a hydroformylation catalyst at elevated pressure to the corresponding dialdehydes, and
die Aldolreaktion der Dialdehyde aus der Hydroformylierung mit einer Carbonylverbindung der Formel R7R8C=0 unter Ausbildung einer neuen C-C-Bindung zu den entsprechenden beta-Hydroxyaldehyden, the aldol reaction of the dialdehydes from the hydroformylation with a carbonyl compound of the formula R7R8C = 0 to form a new C-C bond to the corresponding beta-hydroxyaldehydes,
die katalytische Hydrierung der beta-Hydroxyaldehyden aus der Aldolreaktion zu den entsprechenden drei- und vierwertigen Alkoholen, und the catalytic hydrogenation of the beta-hydroxy aldehydes from the aldol reaction to the corresponding trihydric and tetrahydric alcohols, and
die Umsetzung der drei- und vierwertigen Alkoholen aus der katalytischen Hydrierung mit Epichlohydrin zu den entsprechenden Glycidylethern gemäß Anspruch 3. the reaction of the tri- and tetrahydric alcohols from the catalytic hydrogenation with epichlorohydrin to the corresponding glycidyl ethers according to claim 3.
Limon -Derivate der Formel II Limone derivatives of the formula II
wobei  in which
R9 = H und R10 = CH2OH und R1 1 = H, oder R9 = H and R10 = CH 2 OH and R1 1 = H, or
R9 = H und R10 = CH2OH und R1 1 = CR7R80H, oder R9 = H and R10 = CH 2 OH and R1 = 1 CR7R80H, or
R9 = CH2OH und R10 = H und R1 1 = H, R9 = CH2 OH and R10 = H and R1 = 1 H,
und wobei  and where
R12 = H und R13 = CH2OH und R14 = H, oder R12 = H and R13 = CH 2 OH and R14 = H, or
R12 = H und R13 = CH2OH und R14 = CR7R80H, oder R12 = H and R13 = CH 2 OH and R14 = CR7R80H, or
R12 = CH2OH und R13 = H und R14 = H,  R12 = CH2OH and R13 = H and R14 = H,
und wobei  and where
R7 und R8 jeweils unabhängig voneinander ein H-Atom oder eine C1-C4- Alkylgruppe sind, und  R7 and R8 are each independently an H atom or a C1-C4 alkyl group, and
R1 1 und R14 nicht beide gleichzeitig ein H-Atom sind.  R1 1 and R14 are not both simultaneously an H atom.
Oligomer, das erhältlich ist durch Umsetzung von Glycidylether der Formel I gemäß einem der Ansprüche 1 bis 3 mit einem oder mehreren Diolen. Härtbare Epoxidharz-Zusammensetzung, umfassend eine Härterkomponente, die mindestens einen Härter enthält, und eine Harzkomponente, die mindestens eine Polyepoxidver- bindung enthält, ausgewählt aus der Gruppe bestehend aus einem Glycidylether der Formel I nach einem der Ansprüche 1 bis 3, einem oligomeren Glycidylether nach einem der Ansprüche 1 bis 3 und einem Oligomer nach Anspruch 7. Oligomer obtainable by reacting glycidyl ether of the formula I according to one of claims 1 to 3 with one or more diols. A curable epoxy resin composition comprising a hardener component containing at least one curing agent and a resin component containing at least one polyepoxide compound selected from the group consisting of a glycidyl ether of the formula I according to any one of claims 1 to 3, an oligomeric glycidyl ether one of claims 1 to 3 and an oligomer according to claim 7.
Die härtbare Epoxidharz-Zusammensetzung gemäß Anspruch 8, umfassend eine Härterkomponente, die mindestens einen Härter enthält, und eine Harzkomponente, die mindestens eine Polyepoxidverbindung enthält, ausgewählt aus der Gruppe bestehend aus einem Glycidylether der Formel I nach einem der Ansprüche 1 bis 3 und einem oligomeren Glycidylether nach einem der Ansprüche 1 bis 3. The curable epoxy resin composition according to claim 8, comprising a hardener component containing at least one curing agent, and a resin component containing at least one polyepoxide compound selected from the group consisting of a glycidyl ether of the formula I according to any one of claims 1 to 3 and an oligomeric one Glycidyl ether according to one of claims 1 to 3.
Die härtbare Epoxidharz-Zusammensetzung gemäß Anspruch 8 oder 9, wobei der mindestens eine Härter ausgewählt ist aus der Gruppe bestehend aus Aminohärter und Phenolharz. The curable epoxy resin composition according to claim 8 or 9, wherein the at least one curing agent is selected from the group consisting of amino hardener and phenolic resin.
1 1 . Die härtbare Epoxidharz-Zusammensetzung gemäß einem der Ansprüche 8 bis 10, wobei die Polyepoxidverbindungen insgesamt einen Anteil von mindestens 40 Gew.-% bezogen auf die gesamte Harzkomponente ausmachen. 1 1. The curable epoxy resin composition according to any one of claims 8 to 10, wherein the polyepoxide compounds make up an overall content of at least 40% by weight based on the total resin component.
12. Die härtbare Epoxidharz-Zusammensetzung gemäß einem der Ansprüche 8 bis 1 1 , wobei die härtbare Epoxidharz-Zusammensetzung einen Anteil von weniger als 40 Gew.-% Bisphenol A oder F basierte Verbindungen bezogen auf die gesamte Harzkomponente aufweist. 12. The curable epoxy resin composition according to any one of claims 8 to 1 1, wherein the curable epoxy resin composition has a content of less than 40 wt .-% of bisphenol A or F based compounds based on the total resin component.
13. Verfahren zur Herstellung eines gehärteten Epoxidharzes, umfassend die Härtung der härtbaren Epoxidharz-Zusammensetzung nach einem der Ansprüche 8 bis 12. A process for producing a cured epoxy resin comprising curing the curable epoxy resin composition of any one of claims 8 to 12.
14. Gehärtetes Epoxidharz erhältlichen durch Härtung der härtbaren Epoxidharz- Zusammensetzung nach einem der Ansprüche 8 bis 12. A cured epoxy resin obtainable by curing the curable epoxy resin composition according to any one of claims 8 to 12.
15. Verwendung der härtbaren Epoxidharz-Zusammensetzung nach einem der Ansprüche 8 bis 12 zur Herstellung von Klebstoffen, Verbundwerkstoffen, Formkörpern oder Beschich- tungen. 15. Use of the curable epoxy resin composition according to any one of claims 8 to 12 for the production of adhesives, composites, moldings or coatings.
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