Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/28—Phosphorus compounds with one or more P—C bonds
  • C07F9/50—Organo-phosphines
  • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
• • 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
• • 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
  • C08G59/26—Di-epoxy compounds heterocyclic
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
  • C09K5/08—Materials not undergoing a change of physical state when used
  • C09K5/14—Solid materials, e.g. powdery or granular
• • H—ELECTRICITY
  • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
  • H02K—DYNAMO-ELECTRIC MACHINES
  • H02K3/00—Details of windings
  • H02K3/30—Windings characterised by the insulating material

Definitions

• the present invention relates to epoxy-based polymeric compositions.
• the present invention relates to a two component epoxy thermoset epoxy resin system.
• Epoxy resins for example bisphenol resins
• potting resins and adhesives such as, for example, one-component / two-component hot-curing potting resins or adhesives and room-temperature-curing two-component potting resins or adhesives.
• oxide resins are widely used as resin constituents of composite materials, in particular fiber composite materials, in coatings (so-called coatings) and as potting compound, for example for the encapsulation of electronic components.
• Heat-curing two-component epoxy resins based on acid anhydride hardeners are frequently used as insulating material and / or adhesive because of their good impregnation behavior in the field of low-voltage, medium-voltage and high-voltage engineering.
• DE 38 24 251 discloses an insulating tape for producing an impregnated with a thermosetting epoxy resin-acid anhydride mixture insulating sleeve for an electrical conductor.
• the epoxy acid anhydride mixture includes, for example, a glycidyl ether of bisphenol A and methylhexahydrophthalic anhydride.
• US 2014/287173 discloses a reactive hot melt adhesive having two separately present components.
• the first component may contain polymers with epoxide-functional groups and the second component acid anhydrides, such as maleic anhydride.
• US 5,574,112 discloses a coating process in which a mixture of an epoxy group-containing synthetic resin, a crosslinker and a polyol is used.
• the crosslinker comprises a compound that is at least two
• cycloaliphatic epoxy resin hexahydro-4-methylphthalic anhydride as a curing agent, a boron-containing catalyst and a curing rate-modifying agent.
• the epoxy resin compositions are used to make solid state devices such as LEDs.
• Acid anhydrides have long been known for their respiratory sensitizing properties. Since December 2012, the cycloaliphatic acid anhydrides hexahydro-4-methylphthalic anhydride and cyclohexane-1,2-dicarboxylic anhydride have been added to the list of substances of very high concern (SVHC list) according to the REACH Regulation of the European Chemicals Agency (ECHA). Since almost all acid anhydride hardeners have respiratory sensitizing properties, a processing ban of this substance class may occur in the future.
• the object of the present invention is to provide a polymeric composition based on epoxy resin, in which no acid anhydride is used as a curing agent. Another object of the present invention is to provide an epoxy resin-based polymeric composition in which basically no acid anhydrides are used. A further object of the present invention is to provide a two-component epoxy resin curing system that does not use ingredients which have attained ECHA status as being of high concern. Another object of the present invention is to provide an epoxy resin system of the type mentioned, which is easy and safe to handle and is characterized by a good storage stability.
• the two-component thermosetting epoxy resin system has the following components: a first component comprising an epoxy resin; and a second component separate from the first component, characterized in that the second component comprises a homopolymerization catalyst and a reactive diluent.
• thermoset epoxy resin system as a cast resin, fiber composite component, corrosion inhibitor or adhesive.
• thermosetting resin a mixture for a thermosetting resin
• a two-part epoxy resin system provided comprising: a homopolymerization catalyst, and a reactive diluent.
• the present inventors have found that epoxy resins undergo homopolymerization in the presence of certain catalysts.
• the difficulty with these one component epoxy resins is their limited storage stability.
• the present invention is now based on providing the catalyst in a second component and thereby dissolving the catalyst in a reactive diluent and adding this second component to the first component only shortly before processing.
• epoxy group or "epoxy group” is hereinafter a single, double or triple substituted oxirane / ethylene oxide of the general formula 0 (CHR 1 ) (CR 2 R 3 ) wherein R 1; R 2 and R 3 may be the same or different radicals.
• glycol ether or "glycidyl ether” ethers of 2,3-epoxy-1-propanol (glycidol) and derivatives thereof are referred to.
• the homopolymerization catalyst itself is not part of the reaction product and thus acts only catalytically.
• a “homopolymerization catalyst” thus differs from a “hardener” and a “cross-linker”.
• the homopolymerization catalyst is heat-curing and thus causes the polymerization only above the room temperature and / or the storage temperature, for example from a temperature of at least 50 ° C, preferably at least 55 ° C, at least 60 ° C, at least 65 ° C, at least 70 ° C, at least 75 ° C, at least 80 ° C, at least 85 ° C, at least 90 ° C, at least 95 ° C, at least 80 ° C, at least 100 ° C, at least 1 10 ° C, or at least 120 ° C.
• Suitable homopolymerization catalysts are familiar to the person skilled in the art. In particular, suitable mixtures of a homopolymerization catalyst and reactive diluent can be prepared and tested.
• Functionalities ie functional groups of one or more compounds, catalyze with one or more components of the system according to the invention. It is clear that this reaction of other functionalities also takes place at room temperature and / or the storage temperature or at temperatures above room temperature and / or the storage temperature.
• the components of the two-part epoxy thermosetting epoxy resin system of the invention and the two-part epoxy type thermosetting epoxy resin mixture are selected to catalyze only the epoxide group / n reaction.
• the homopolymerization catalyst reacts at room temperature and generally
• the component containing the homopolymerization catalyst and a reactive diluent can be readily stored for a period of at least one week, preferably at least two weeks, at least one month, at least two months, at least three months, at least four months, at least five months, or at least six months without affecting the reactivity with the component containing the epoxy resin.
• hardener refers to a chemical compound which
• Curing of an epoxy resin and / or reactive thinner causes.
• the curing agent effects the polymerization of the epoxy resin and / or reactive diluent and, moreover, participates in the reaction in the manner of a cross-linker.
• Polyamines and acid anhydrides are examples of hardeners.
• neither the reactive diluent, the epoxy resin nor any other constituent of the thermosetting two-component epoxy resin system of the present invention or the mixture for a two-component epoxy resin thermosetting system has a hardening property.
• the reactive diluent contains no acid anhydride component.
• a hardener is not included.
• crosslinker refers to a chemical compound which effects only cross-linking in a polymerization reaction
• the cross-linker has no functional group capable of causing polymerization of the epoxy resin and / or reactive diluent
• one or more crosslinkers are present
• suitable cross-linkers are glycidyl ethers having at least two, preferably three, four, six or eight, epoxy groups.
• room temperature refers to a temperature of 20 ° C to 25 ° C, preferably 21 ° C to 24 ° C, 22 ° C to 23 ° C, more preferably 22 ° C ,
• storage temperature refers to the temperature at which
• the storage temperature refers to a temperature at which polymerization of the reactive diluent alone is substantially completely prevented.
• An essentially complete suppression of a polymerization of the reactive diluent here means that, for example, less than 1%, preferably less than 0.1%, of all the functional groups present in the reactive diluent reach the reaction within the storage period.
• the storage temperature corresponds to the room temperature.
• the storage temperature can also be below the room temperature. This may be necessary, for example, when using reactive homopolymerization catalysts in order to substantially prevent their reaction with the reactive diluent at the storage temperature.
• the first component may be present in a first vessel and the second component in a second vessel.
• the homopolymerization catalyst is characterized in that only the functional groups containing one another in the epoxy resin, the reaction of the epoxy resin with the reactive diluent and, if the first component also has a reactive diluent, catalyzes the reaction of this reactive diluent with a reactive diluent of the second component become.
• the homopolymerization catalyst therefore preferably does not catalyze a reaction of further constituents which are optionally present in the first and / or the second components of the epoxy resin system.
• the homopolymerization catalyst merely catalyzes the reaction of the epoxy resin or reactive diluent and does not even take part in the optionally occurring crosslinking and thus differs from a curing agent.
• the crosslinking is provided only by the epoxy resin and optionally the reactive diluent.
• the homopolymerization catalyst does not comprise any functional groups such as acid anhydride groups and / or multiple amine functionalities (in particular polyfunctional amines) which can simultaneously function as a polymerization catalyst and as a cross-linker.
• Component is present and only by mixing the second component with the first component, the reaction is catalyzed.
• the homopolymerization catalyst preferably catalyzes only the reaction of an epoxide group.
• the reaction of an epoxide group with a hydroxyl group and / or amino group can be catalyzed.
• a suitably suitable homopolymerization catalyst thus depends on the structure, in particular the functional groups, of the epoxy resin, of the reactive diluent (s) and other optional constituents.
• the acid or base strength of the catalyst used as the Lewis acid or Lewis base is particularly important.
• the suitable acid or base strength can be qualitatively described by means of the HSAB principle.
• Hard and soft acids and bases are described based on the Lewis definition of acids and bases. This may be, for example, R.G. Pearson, Chem. Brit., Vol. 3 (1967), pp. 103-107 and R.G. Pearson, J. Chem. Ed., 45 (1968), pp. 581-587; R.G. Pearson, J. Chem. Ed., 45 (1968), pp. 643-648, the contents of which are hereby incorporated by reference.
• Lewis acids such as metal salts, including aluminum trichloride and boron trifluoride
• Lewis bases such as trimethylamine.
• Suitable Lewis acids and Lewis bases are known in the art.
• Particularly suitable homopolymerization catalysts comprise organic complexes of Lewis acids, such as, for example, trichloro (N, N-dimethyloctylamine) boron, which, owing to the organic constituent, have a reduced reactivity with respect to the corresponding Lewis acid, in the case of trichloro (N, N-dimethyloctylamine) boron, the stronger Lewis acid boron trifluoride.
• Other such latent-reactive catalysts known in the art can be used.
• the present homopolymerization catalysts are Lewis acids having an acid strength according to the HSAB principle, which corresponds at least to a compound of the type BX 3 (NR) 3 , such as trichloro (N, N-dimethyloctylamine) boron.
• X can be a halide, for example fluorine, chlorine, bromine or iodine.
• X is preferably fluorine or chlorine. It is clear that different radicals X may be present in the compound of the type BX 3 (NR) 3 .
• Lewis acids examples include BF 3 , B (OR) 3 , FeCl 3 and AlCl 3
• the present homopolymerization catalysts are Lewis bases having a base strength according to the HSAB principle which is at least equal to that of NH (R) 2 .
• Lewis bases include R 3 N.
• the aforementioned R of the compounds may be the same or different, include linear or branched alkyl, alkylene and alkynyl groups and have a molecular weight of the compound of 650 g / mol, preferably 600 g / mol, 500 g / mol, 400 g / mol, or 300 g / mol.
• R 3 N may be, for example, N (CH 3 ) 3 , N (CH 3 ) 2 (C 2 H 5 ) or N (CH 3 ) (C 2 H 5 ) (C 2 H 4 ).
• Epoxy resins are either monomers or prepolymers (for example, dimers,
• the epoxy resin is usually used only in the first component and usually includes terminal epoxide groups as a reactive component.
• the epoxy resin and / or the reactive diluent may have further functional groups which undergo a reaction only when mixing both components and / or at a temperature corresponding to or above the polymerization temperature.
• these functional groups include hydroxyl groups. If more than one reactive diluent is used in a component, they are preferably of the same type, i. they either comprise only epoxide groups or epoxide groups and hydroxyl groups. A reaction of the constituents of a particular component with one another at the storage temperature does not take place.
• the individual components can be heated independently, which not only accelerates the polymerization process after mixing the individual components, but optionally also give better solubility and due to an improved end product good homogeneity.
• the second component may be heated to a temperature below the polymerization temperature, whereas the first component is not subject to such a limitation.
• suitable epoxy resins include bisphenol-based epoxy resins, such as
• bisphenol A for example, bisphenol A, novolak epoxy resins such as phenol or cresol novolaks, aliphatic epoxy resins, and halogenated epoxy resins, and combinations thereof.
• Diglycidyl ethers of bisphenol A (DGEBA), bisphenol F and bisphenol A / F (The designation A / F refers to a mixture of acetone with formaldehyde, which is used as starting material in its preparation) can be used.
• Such liquid resins are available, for example, as Araldite (Huntsman) or D.E.R (Dow) or Epikote (Hexion).
• bisphenol AF bisphenol AF
• Degree of crosslinking of the epoxy resin influence and as a result of the properties, in particular the strength, of the epoxy resin can be influenced in a targeted manner.
• the reaction rate can be influenced in a targeted manner by the type and amount of glycidyl ether used.
• Suitable glycidyl ethers include poly (tetramethylene oxide) diglycidyl ether, hexanediol diglycidyl ether, 2-ethylhexyl glycidyl ether, polyoxypropylene glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, neopentyl glycol diglycidyl ether and 1,4-butanediol diglycidyl ether. Preference is given to poly (tetramethylene oxide) diglycidyl ethers, hexanediol diglycidyl ethers and 1,4-butanediol diglycidyl ethers.
• Other suitable glycidyl ethers, as well as their representation, are known in the art.
• glycidyl ethers of aliphatic and arylaliphatic mono- and polyalcohols allyl and methallyl glycidyl ethers, phenyl glycidyl ethers and their alkylation products and certain epoxidized hydrocarbons, such as, for example, styrene oxide, vinylcyclohexene dioxide, limonene dioxide, octene oxide and epoxidized terpenes, are used.
• Epoxide-free reactive diluents include, for example, polymethoxyacetals or triphenyl phosphite.
• Glycidyl ethers of aliphatic and arylaliphatic mono- and polyalcohols are preferred.
• the first component based on 100% by weight of the first component, between 0 and 20% by weight of reactive diluents are used, preferably 1 to 19% by weight of reactive diluents, more preferably 5 to 18% by weight of reactive diluents, From 6 to 17% by weight of reactive diluents, 7 to 16% by weight of reactive diluents, 8 to 15% by weight of reactive diluents, 9 to 14% by weight of reactive diluents, 10 to 13% by weight of reactive diluents or 11 to 12% by weight .-% reactive diluent.
• the second component based on 100 wt .-% of the second component, are preferably between 50 to 95 wt .-% of reactive diluents for use, such as 60 to 90 wt .-% reactive diluent, 65 to 85 wt .-% reactive diluents, more preferably 70 to 80% by weight of reactive diluent, 71 to 79% by weight of reactive diluent, 72 to 78% by weight of reactive diluent, 73 to 77% by weight of reactive diluent, 74 to 76% by weight of reactive diluent or 76% by weight.
• reactive diluents for use, such as 60 to 90 wt .-% reactive diluent, 65 to 85 wt .-% reactive diluents, more preferably 70 to 80% by weight of reactive diluent, 71 to 79% by weight of reactive diluent, 72 to 78% by weight of reactive dil
• Reactive diluents of the second component can be selected independently of one another from the abovementioned reactive diluents.
• thermally conductive particles may include, for example, aluminum hydroxide or aluminum oxide.
• fillers are with regard to the polymerization reaction means chemical inert substances or compounds, ie compounds which do not participate in the polymerization reaction and also do not dissolve in the heated mixture of the first component and / or the second component.
• fillers include, for example, particulate high melting temperature polymers.
• a preferred filler is quartz.
• dyes may be added to impart a desired color to the epoxy resin system. Dyes can be added in the form of a pigment paste.
• Siloxane can be included as a suitable deaerator in the first component and / or the second component. Flame retardant substances may also be included in the first component and / or second component.
• first component and the second component further components, for example a third component or a third and fourth component, may be present.
• One or more optional constituents for example a reactive diluent or filler, may, for example, be present in another vessel and mixed simultaneously with the first component and the second component.
• compositions consisting of or consisting essentially of denotes a partially closed list of designated compositions which, in addition to the constituents mentioned, only contain further constituents which do not materially alter the character of the composition or which are present in quantities that do not materially alter the character of the composition.
• compositions when a composition is described using the term "comprising", it expressly includes compositions consisting of or consisting essentially of said constituents.
• FIG. 1 shows the mixing viscosity of the epoxy resin system according to the invention in comparison with the mixing viscosity of an acid anhydride-based epoxy resin system over time at 80 ° C.
• the epoxy resin is selected from the group consisting of a bisphenol-based epoxy resin, a novolak epoxy resin, an aliphatic epoxy resin, a halogenated epoxy resin, and combinations thereof.
• the above-mentioned epoxy resins have in common that they have at least two epoxide groups, for example 3, 4, 5, 6, 7, 8, 9, 10 epoxide groups.
• the epoxy resins Preferably, the epoxy resins have only two terminal epoxide groups.
• two or more hydroxyl groups such as 3, 4, 5, 6, 7, 8, 9, 10 or more hydroxyl groups are included.
• a higher number of epoxide groups and / or hydroxyl groups will result in improved cross-linkability of the epoxy resin system and, as a result, increased strength of the final product. It is clear here that this effect can be further enhanced but also reduced, in particular by the choice of reactive diluent (s).
• the first component comprises a reactive diluent.
• This reactive diluent can be chosen from the abovementioned reactive diluents
• glycidyl ethers selected from poly (tetramethylene oxide) diglycidyl ether, hexanediol diglycidyl ether and 1,4-butanediol diglycidyl ether.
• poly (tetramethylene oxide) diglycidyl ether hexanediol diglycidyl ether and 1,4-butanediol diglycidyl ether.
• a hydroxyl-containing and / or amino-containing reactive diluent may also be used.
• an epoxy resin can be selected as a reactive diluent.
• the reactive diluent of the first component may be the reactive diluent of the second
• one or more reactive diluents such as 2, 3, 4, 5, 6, 7, 8, 9, 10 or more reactive diluents are used. Regardless of this, preferably at least one reactive diluent, such as, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10 or more reactive diluents, is used in the second component.
• the reactive diluents of the first component and of the second component are selected independently of one another, although preferably only epoxide-functional reactive diluents are used in the case of a large number of reactive diluents in one component. It is excluded that the homopolymerization catalyst already causes a polymerization of the reactive diluent or the reactive diluent of the second component.
• an epoxy resin can also be used as a reactive diluent.
• the homopolymerization catalyst is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
• Lewis acids selected from the group consisting of Lewis acids, Lewis bases and combinations thereof.
• the homopolymerization catalyst is present only in the second component.
• a mixture of different homopolymerization catalysts such as 2, 3, 4, 5 or more homopolymerization catalysts, may be used.
• the homopolymerization catalyst preferably catalyzes only the reaction of epoxide groups.
• the reaction of a Epoxy group with a hydroxyl group or the reaction of an epoxide group are catalyzed with an amino group.
• the catalyst has no crosslinking activity.
• compounds such as polyfunctional amines which can catalyze the polymerization as both Lewis bases, as well as by the presence of multiple amine functionalities, not homopolymerization catalysts in the context of the present invention.
• Lewis acids in the context of the present application represent electron pair acceptors and include primarily partial salts or salts of semimetals.
• suitable Lewis acids include titanium tetrachloride, boron trihalide, boric acid, trialkylborane and aluminum trihalide.
• boron trihalide include BF 3 , BCI 3 and BBr 3 .
• aluminum trihalide include AIF 3 , AICI 3 and AIBr 3 .
• trialkylboranes examples include trialkylboranes having the same or different alkyl radicals, wherein the molecular weight of the trialkyl borane does not exceed 650 g / mol, preferably 600 g / mol, 500 g / mol, 400 g / mol, or 300 g / mol.
• Preferred trialkylboranes are trimethylborane, triethylborane, tri-n-propylborane and trichloro (N, N-dimethyloctylamine) boron.
• Lewis bases are electron pair donors and therefore have at least one free electron pair.
• Suitable examples of Lewis bases include, for example, trimethylamine. Polyfunctional amines and acid anhydrides are excluded since they are also involved in the reaction with epoxide groups in addition to the catalysis of the reaction of epoxide groups. Examples of suitable Lewis bases include R 2 NH and R 3 N.
• the R radicals of the compounds R 2 NH, R 3 N may be the same or different, include linear or branched alkyl, alkylene and alkynyl radicals and have a molecular weight of the compound which does not exceed 650 g / mol, preferably 600 g / mol, 500 g / mol, 400 g / mol, or 300 g / mol. Trimethylamine is preferred.
• the homopolymerization catalysts used are a Lewis acid having an acid strength according to the HSAB principle, the acid strength corresponding at least to that of a compound of the BX 3 (NR) 3 type.
• the homopolymerization catalyst used is a Lewis base having a base strength according to the HSAB principle, the base strength corresponding to at least that of a compound of the NH (R) 2 type.
• X can be a halide, for example fluorine, chlorine, bromine or iodine. X is preferably fluorine or chlorine. It is clear that different radicals X may be present in the compound of the type BX 3 (NR) 3 .
• R radicals of the compounds may be the same or different, include linear or branched alkyl, alkylene and allykynyl radicals, and have a molecular weight of the compound of 650 g / mol, preferably 600 g / mol, 500 g / mol, 400 g / mol, or 300 g / mol.
• the first component and / or second component comprises an ingredient selected from the group consisting of a thermally conductive particle, filler, dye, and combinations thereof. It is clear that other ingredients may be present. Furthermore, it is clear that the thermally conductive particle, the filler, the dye or another ingredient is neither a homopolymerization catalyst nor a reactive diluent, an epoxy resin or epoxide of the present invention.
• the first component comprises 30 to 40% by weight.
• Epoxy resin 5 to 10 wt .-% reactive diluent, 40 to 60 wt .-% fillers and 0.5 to 1, 5 wt .-% pigment paste based on 100 wt .-% total weight of the first component.
• the second component comprises 70 to 90% by weight of reactive diluent and 10 to 30% by weight of homopolymerization catalyst, based on 100% by weight total weight of the second component.
• the hot-curing two-component epoxy resin system may contain, for example, 100% by weight of the first component and 10% by weight of the second component, based on 1 to 10% by weight total weight of the two-component epoxy resin thermosetting system.
• volume, viscosity and other properties of the first component and / or the second component are significantly influenced by the choice of reactive diluent, its amount and / or optional ingredients, as well as their amount.
• the chemical and physical properties of the hot-curing two-component epoxy resin according to the invention can be controlled by selectively influencing the mixing ratios of the first and second components and / or their respective constituents / constituents.
• the first component may be stored at a temperature of 15 to 25 ° C for a period of 6 months or longer, preferably at least 8 months, at least 10 months, more preferably for at least 12 months.
• the second component may be stored at a temperature of 15 to 25 ° C for a period of 3 months or longer, preferably at least 4 months, at least 5 months, more preferably for at least 6 months.
• the storage of the first or second component for the periods listed above does not lead to any measurable deterioration in the quality of the cured epoxy Resin system compared to a corresponding epoxy resin system, which was produced by direct mixing of both components.
• the viscosity of the first component at a temperature of 22 ° C is 20,000 - 100,000 mPa s, preferably 30,000 - 90,000 mPa s, 40,000 - 80,000 mPa s, 50,000 - 75,000 mPa s, more preferably 60,000 - 70,000 mPa s ,
• the viscosity can in this case be determined with a viscometer, for example Haake Viskotester T550E100, for example at stage 4.
• the viscosity can be determined in this case with a viscometer, for example Haake Viskotester T550E100, for example at stage 8.
• the viscosity can be determined here with a viscometer, for example Haake Viskotester T550E100.
• the density of the first component is 1, 60-1, 90 g / cm 3 , preferably 65- 1, 85 g / cm 3 , 1, 70-1, 80 g / cm 3 , more preferably 1, 72 - 1, 76 g / cm 3 .
• the density can be determined with a pycnometer, for example Elcometer 50 ml stainless steel.
• the density of the second component is 0.90-1.15 g / cm 3 , preferably 0.95-0.1 g / cm 3 , 1.00-0.06 g / cm 3 , more preferably
• the density can be determined with a pycnometer, for example Elcometer 50 ml stainless steel.
• the Shore D hardness of the cured epoxy resin system is 70-90, preferably 72-88, 74-86, 76-84, more preferably 78-82.
• the Shore D hardness can be determined by ISO 868 or DIN Be determined 53505.
• the two-component thermosetting epoxy resin system is used as a cast resin, fiber composite component, i. Component in composites, used as corrosion protection or as an adhesive.
• the particular configuration as a cast resin, fiber composite component, corrosion protection or adhesive determines the chemical and physical properties of the epoxy resin system, such as its viscosity, and other properties.
• the respective embodiments, in particular properties and ingredients, are familiar to the person skilled in the art.
• thermosetting epoxy resin system comprising a homopolymerization catalyst and a reactive diluent.
• the homopolymerization catalyst and the reactive diluent here are as
• the reactive diluent may be an epoxy resin.
• the above amounts can be used for a homopolymerization catalyst and reactive diluent. For example, 10 to 30 wt .-% homopolymerization catalyst and 70 to 90 wt .-% reactive diluents may be included.
• VP GE 7314 / 6-3, WEVOPOX VP GE 06-2012 / 4-6 and WEVODUR VP GE 06-2012 / 4-6 are commercially available from WEVO-CHEMIE GmbH, Ostfildern-Kemnat, Germany. example 1
• a mineral filled electrocasting resin based on epoxy resins is provided.
• the resin component contains mineral fillers. Halogenated flame retardants or acid anhydrides as hardness component are not included. 100% by weight WEVOPOX VP GE 7314 / 6-3 (resin component or first component) are successively heated to 80 ° C. with 10% by weight WEVODUR VP GE 7314 / 6-3 (second component with homopolymerization catalyst and reactive diluent), to reduce the viscosity of the resin component, and then mixed. The mixture can be used directly as potting compound.
• the electrical properties of the finished epoxy resin system can be improved by previously degassing the two components at 1 to 5 mbar. 250 g of the epoxy resin system according to the invention are created.
• the components have the following properties:
• Viscosity (22 ° C): WEVOPOX VP GE 7314 / 6-3 50,000 - 60,000 mPa-s
• Delivery form 30 kg container and 250 kg drum
• shelf life In the original sealed container, in dry storage between 15 ° C and 25 ° C, the first component at least 12 months and the second component at least 6 months
• Example 2 The properties of the heat-curing two-component epoxy resin system according to the invention of 100% by weight WEVOPOX VP GE 7314 / 6-3 and 10% by weight WEVODUR VP GE 7314 / 6-3 according to Example 1 are compared with those of a conventional epoxy resin system.
• the conventional epoxy resin system consisting of 100% by weight WEVOPOX VP GE 06-2012 / 4-6 (epoxy resin-containing component) and 24% by weight WEVODUR VP GE 06-2012 / 4-6 (acid anhydride-containing component) is likewise a two-component system An acid anhydride is used as a curing agent (Comparative Example.
• WEVODUR VP GE 7314 / 6-3 is designated GE 7314 / 6-3, whereas the hardened system is WEVOPOX VP GE 06-2012 / 4-6 and WEVODUR VP GE 06-2012 / 4-6 with GE 06-2012 / 4-6 is called.
• the determination of the viscosity is carried out with a Haake Viskotester T550E100, the density with a Elecometer 50 ml stainless steel, the pot life with a Haake Viskotester T550E100 (measurement of viscosity increase to 8000mPas at 179.6 l / min at 1 10 ° C) and the glass transition temperature or thermal expansion coefficient with a TMA, Seiko Exstar SS6000.
• Epoxy resin systems such as. Polymerization or curing temperature and time, density, Shore D hardness, etc., largely match.
• the epoxy resin system of the present invention thus has similar processing, mechanical and physical data properties compared to an acid anhydride cured epoxy resin system.
• the hot-curing two-component epoxy resin system according to the invention has a
• Both components of the epoxy resin system according to the invention can be used in a variable mixing ratio over a wide range.
• the mechanical properties of the components and those of the finished epoxy resin system can be varied and adjusted as desired.
• the reactivity, and thus the time to complete polymerization can be adjusted via the proportion of the catalyst in the second component.
• fillers such as quartz flour or aluminum trihydroxide, may be used in the epoxy resin system to selectively achieve, for example, flame retardant or improved electrical properties.
• the use of fillers can reduce the shrinkage behavior and the evolution of heat during the exothermic polymerization reaction.
• the physiological advantage of the acid anhydride-free systems is obvious since respiratory sensitizing acid anhydrides are not present.
• Another advantage is the lower moisture sensitivity of the present acid anhydride-free epoxy resin system and the associated higher storage stability.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Life Sciences & Earth Sciences (AREA)
• Power Engineering (AREA)
• Thermal Sciences (AREA)
• Combustion & Propulsion (AREA)
• Physics & Mathematics (AREA)
• Wood Science & Technology (AREA)
• Biochemistry (AREA)
• General Health & Medical Sciences (AREA)
• Molecular Biology (AREA)
• Epoxy Resins (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Artificial Filaments (AREA)
• Processes Of Treating Macromolecular Substances (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=58547476

Family Applications (1)

Country Status (13)

Families Citing this family (1)

Family Cites Families (22)

• 2016
  • 2016-04-01 DE DE102016106031.3A patent/DE102016106031A1/de active Granted
• 2017
  • 2017-03-29 MX MX2018011924A patent/MX2018011924A/es unknown
  • 2017-03-29 JP JP2018551294A patent/JP6753947B2/ja active Active
  • 2017-03-29 KR KR1020187031767A patent/KR102220274B1/ko active IP Right Grant
  • 2017-03-29 EP EP17717337.4A patent/EP3436466A1/de active Pending
  • 2017-03-29 CN CN201780034075.3A patent/CN109415395A/zh active Pending
  • 2017-03-29 SG SG11201808591RA patent/SG11201808591RA/en unknown
  • 2017-03-29 RU RU2018138408A patent/RU2710557C1/ru active
  • 2017-03-29 WO PCT/EP2017/057452 patent/WO2017167825A1/de active Application Filing
  • 2017-03-29 CA CA3019263A patent/CA3019263C/en active Active
  • 2017-03-29 BR BR112018069988-8A patent/BR112018069988A2/pt not_active Application Discontinuation
• 2018
  • 2018-09-28 US US16/146,888 patent/US20190031819A1/en not_active Abandoned
  • 2018-10-03 ZA ZA2018/06573A patent/ZA201806573B/en unknown

Also Published As

Similar Documents

Legal Events