EP3033319A1 - Glycidéthers de dérivés de limonène et leurs oligomères s'utilisant comme résines époxydes durcissables - Google Patents

Glycidéthers de dérivés de limonène et leurs oligomères s'utilisant comme résines époxydes durcissables

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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Withdrawn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
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German (de)
English (en)
Inventor
Ulrich Karl
Monika CHARRAK
Hans-Josef Thomas
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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/fr
Publication of EP3033319A1 publication Critical patent/EP3033319A1/fr
Withdrawn legal-status Critical Current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.

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

Abstract

Les résines époxydes durcies sont largement répandues, de par leurs remarquables propriétés mécaniques et chimiques. On utilise habituellement des résines époxydes à base de diglycidyléther de bisphénol A ou de bisphénol F dont l'utilisation peut néanmoins être difficile dans de nombreux domaines, en raison de leurs effets sur le système endocrinien. L'invention concerne des diols et/ou polyols à base de glycidyléthers de limonène ainsi que des compositions de résines époxydes durcissables, s'utilisant comme solution de rechange au diglycidyléther de bisphénol A ou de bisphénol F ou aux compositions de résines époxydes à base desdites substances.
EP14749745.7A 2013-08-14 2014-07-30 Glycidéthers de dérivés de limonène et leurs oligomères s'utilisant comme résines époxydes durcissables Withdrawn EP3033319A1 (fr)

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PCT/EP2014/066327 WO2015022188A1 (fr) 2013-08-14 2014-07-30 Glycidéthers de dérivés de limonène et leurs oligomères s'utilisant comme résines époxydes durcissables
EP14749745.7A EP3033319A1 (fr) 2013-08-14 2014-07-30 Glycidéthers de dérivés de limonène et leurs oligomères s'utilisant comme résines époxydes durcissables

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WO2010100122A1 (fr) 2009-03-05 2010-09-10 Akzo Nobel Coatings International B.V. Polyols d'huiles hydroxylées, et compositions de revêtement élaborées à partir de polyols d'huiles hydroxylées
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