US20170015871A1 - Method for curing an adhesive using microwave irradiation - Google Patents

Method for curing an adhesive using microwave irradiation Download PDF

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US20170015871A1
US20170015871A1 US15/039,129 US201415039129A US2017015871A1 US 20170015871 A1 US20170015871 A1 US 20170015871A1 US 201415039129 A US201415039129 A US 201415039129A US 2017015871 A1 US2017015871 A1 US 2017015871A1
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alkyl
methyl
cycloalkyl
phenyl
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Robert WUTTI
Roland Kalb
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Proionic GmbH
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Proionic GmbH
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic

Definitions

  • the present invention relates to a method for curing an adhesive using microwaves.
  • adhesives are defined, e.g., in the standard DIN EN 923, comprising among others: physically binding adhesives, e.g., hot melt adhesives, solvent containing wet adhesives, contact adhesives, dispersive adhesives, adhesives based on water and plastisol, chemically curing one- or two-component adhesives (reactive adhesives), such as polymerisation adhesives, e.g., cyanoacrylate and methyl methacrylate adhesives, anaerobically curing adhesives, unsaturated polyester resins, radiation curing adhesives, polycondensation adhesives, e.g., phenol-formaldehyde resin adhesives, cross-linked silicone polymers, silane-cross-linked polymer adhesives, polyimide adhesives, polysulfide adhesives, polyaddition adhesives, e.g., epoxy resin adhesives, polyurethane adhesives, silicones, vulcanizing adhesives and adhesives without solidifying mechanism, e.g., pressure sensitive adhesives,
  • use or “application” of adhesives, in the sense of this patent, comprises not only joining and gluing of material parts for the purpose of a mechanic connection but rather also the application as a sealing agent, bonding agent, for the sealing and coating of any kind of surfaces and interfaces.
  • hot melt adhesives which contain a polymer composition and an ionic liquid. Due to the presence of ionic moieties in the ionic liquid, the adhesion behaviour of the polymer composition to polar surfaces or surfaces swollen or dissolved due to the ionic liquids may be improved.
  • both parts to be glued together have to be heated accordingly for the desired period of time, i.e. not only the contact area for adhesion and the immediate surrounding but rather essential parts or the entire workpieces.
  • this will result in significant expenditures of time and energy.
  • it is further not easily possible to very exactly control the duration of heating and, e.g., having a very high temperature only acting thereon for a short period, as the heating and cooling curves will be relatively flat due to the high heat capacity of the workpiece. For this reason, hence, it is also not possible to heat the adhesive area to temperatures above the thermal decomposition temperature of the workpiece in a short-term and local way.
  • Microwave irradiation is defined as electromagnetic radiation in the frequency range of 300 MHz-300 GHz (see, e.g., CD Römpp Chemie Lexikon 1.0) with the common standard frequencies of 2.45 GHz and 915 MHz. In the sense of this application, there are, however, also claimed electromagnetic frequencies out of the range of this definition, in particular such ranging below 300 MHz.
  • microwaves absorbing pigments and (nano-) particles which may be composed of, e.g., graphite, carbon black, metals, ferroelectrics such as ferrite, iron carbonyl, quartz crystal, tourmaline, barium titanate, lithium sulphate, potassium sodium tartrate, ethylene diamintartrate and lead-circonium-titanate.
  • electrically conductive polymers such as polyaniline, polypyrrole, polyalkyl thiophene and poly(4,4′-diphenylendiphenyl vinylene) (see, e.g., Bosman et al. (2003), Appl.
  • the present invention faces the task to provide an adhesive or an adhesive composition, respectively, which does/do not have the disadvantages described, or only to a minor degree, respectively.
  • This task is solved according to the invention by adding an ionic liquid instead of solid particles to the adhesive.
  • the present invention provides a method for curing an adhesive composition using microwaves, characterized in that the adhesive composition contains an ionic liquid [A] + a [B] a ⁇ , wherein [A] + represents a cation, [B] a ⁇ represent an anion and a represents an integer.
  • a method which is provided according to the present invention, is herein also designated as a “method according to the present invention”.
  • “Curing” in a method according to the present invention means achieving a predetermined target rigidity of the adhesive, e.g., in general the curing of the adhesive, regardless of whether chemical, thermal (hot melt adhesive), physical (evaporation of solvent) or in any other form such as the chemical curing of reactive adhesives in the sense of polymerisation or condensation, wherein the adhesive polymers are present already before curing and are not developed only upon the polymerisation of the monomers.
  • [A] + represents an ammonium cation [R 1′ R 1 R 2 R 3 N] + , a phosphonium cation [R 1′ R 1 R 2 R 3 P] 30 , a sulfonium cation [R 1′ R 1 R 2 S] + , a hetero-aromatic cation or a guanidinium cation R 3 R 3′ N(C ⁇ NR 1 R 1′ )NR 2 R 2′ of the formula
  • a heterocycyl residue has the meaning of one of the residues of [A] + , in particular unsaturated and in particular selected from a 5-or a 6-membered hetero-aromatic, which has at least one nitrogen atom as well as optionally an oxygen or sulphur atom and which is unsubstituted or substituted and/or annulated, in particular selected from the group of the formula
  • a ⁇ is selected from:
  • fruit acids may in particular be oxalic acid, benzoic acid, salicylic acid, citric acid, tartaric acid, ascorbic acid, lactic acid and malic acid.
  • saccharic acids may in particular be uronic acids and onic acids such as, e.g., linear and also cyclic tetronic acids, tetruronic acids, pentonic acids, penturonic acids, hexonic acids, hexuronic acids, in particular gluconic acids, glucuronic acids, or protonated anions, respectively, of gluconate, glucoronate, mannonate, mannuronate, galatonate, galacturonate, fructonate, fructuronate, xylonate and similar.
  • uronic acids and onic acids such as, e.g., linear and also cyclic tetronic acids, tetruronic acids, pentonic acids, penturonic acids, hexonic acids, hexuronic acids, in particular gluconic acids, glucuronic acids, or protonated anions, respectively, of gluconate, glucoronate, mannonate, mannuronate, galatonate,
  • amino acids or natural amino acids may in particular be alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutaminic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophane, tyrosine and valine.
  • the fatty acids may be monocarboxylic acids having one to 26 carbon atoms (C1 to C26), wherein the fatty acids may be unsaturated, saturated or mixtures of saturated and/or unsaturated fatty acids.
  • fatty acids may be alkyl carboxylic acids, alkene carboxylic acids, alkadienyl carboxylic acids, in particular formic acid, acetic acid, propionic acid, acrylic acid, methacrylic acid, butyric acid, isobutyric acid, valeric acid, crotonic acid, caproic acid, caprylic acid, capric acid, pelargonic acid, lauric acid, myristic acid, palmitic acid, margaric acid, arachic acid, behenic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, eicosenic acid, cetoleic acid, linolenic acid, linoleic acid, sorbic acid and similar.
  • each individual of the ligands X is independently of each other selected in particular from: fluoride, chloride, bromide, iodide, thiocyanate, dicyanamide, nitrite; nitrate; acetyl acetone; acyl; adenine; 2,2′-azobisisobutyronitrile; alanine; allyl; allyloxycarbonyl; water; aryl; arginine; asparagine; aspartate; BIABN; biotinyl; 2,2′-bis(diphenyl-phosphino)-6,6′-dimethoxy-1,1′-biphenyl; 2,2′-binaphtyldiphenyldiphosphine; 1,2bis[4,5dihydro-3H-binaphtho[1,2c:2′,1′-e]phosphepino]benzol; 1,1′-bis ⁇ 4,5-dihydro-3H-dinap
  • a ⁇ is preferably fluoride, chloride, dicyanamide, thiocyanate; nitrate, sulphate, hydrogen sulphate, methyl carbonate, phosphate; hydrogen phosphate; dihydrogen phosphate; sulfamate, H 2 N—SO 3 ⁇ .
  • anion [B] a ⁇ is a tetra-substituted borate (Va)
  • residues R i to R 1 are identical, wherein these preferably represent fluorine, trifluoromethyl, pentafluoroethyl, phenyl, 3,5-bis(trifluoromethyl)phenyl.
  • tetra-substituted borates (Va) having four identical residues are tetrafluoroborate, tetraphenyl borate and tetral3,5-bis(trifluoromethyl)phenyllborate; or it is also preferably a tetra-substituted borate (Va) having four oxygen atoms directly bound to the boron atom, which are connected in pairs with saturated or unsaturated C2 to C4 alkyl- or alkenyl chains, respectively, which may be substituted or unsubstituted or to which, in the case of the alkenyl chains, an aromatic ring may be annulated, hence forming two identical or different five-, six- or seven-membered rings, preferably bis(mandelato)borate, bis(salicylato)borate, bis(oxalato)borate, bis(glycolato)borate, bis(malonato)borate, bis(succinato)borate
  • the residue R m preferably represents methyl, trifluoromethyl, pentafluoroethyl, p-tolyl or C 9 F 19 .
  • Especially preferred organic sulfonates are trifluoromethane sulfonate (triflate), methane sulfonate, nonadecafluorononansulfonate (nonaflate) and p-toluene sulfonate; especially preferred organic sulphates (Vc) are methyl sulphate, ethyl sulphate, n-propyl sulphate, i-propyl sulphate, butyl sulphate, pentyl sulphate, hexyl sulphate, heptyl sulphate, octyl sulphate, nonyl sulphate and decyl sulphate as well as n-alkyl sulphates having longer chains; benzyl sulphate, alkylaryl sulphate.
  • the residue R n preferably represents hydrogen, trifluoromethyl, pentafluoroethyl, phenyl, hydroxyphenyl methyl, trichloromethyl, dichloromethyl, chloromethyl, trifluoromethyl, difluoromethyl, fluoromethyl or unbranched or branched C 1 -to C 12 -alkyl, such as, for example, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert.-butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-l-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hex
  • Especially preferred carboxylates are formiate, acetate, propionate, butyrate, valeriate, benzoate, mandelate, trichloroacetate, dichloroacetate, chloroacetate, trifluoroacetate, difluoroacetate, fluoroacetate.
  • Vc carboxylates
  • oxalic acid benzoic acid, salicylic acid, citric acid, tartaric acid, ascorbic acid, lactic acid, succinic acid, sulfosuccinic acid, sulfosuccinic acid mono- or dialkyl esters—e.g., sulfosuccinic-bis-2-ethylhexyl ester, gluconic acids, glucuronic acids, mannonic acids, mannuronic acids, galactonic acids, galacturonic acids, fructonic acids, fructuronic acids, xylonic acids, alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutaminic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine,
  • the anion [B] a ⁇ is a (fluoroalkyl)fluorophosphate (Ve) [PF x (C y F 2y+1 ⁇ z H z ) 6 ⁇ x ], then z is preferably 0.
  • the residues R o to R t independently of each other preferably represent hydrogen, trifluoromethyl, pentafluoroethyl, phenyl, trichloromethyl, dichloromethyl, chloromethyl, trifluoromethyl, difluoromethyl, fluoromethyl or unbranched or branched C 1 -to C 12 -alkyl, such as, e.g., methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-l-propyl (isobutyl), 2-methyl-2-propyl (tert.-butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-l-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-l-propyl, 1-he
  • Especially preferred imides (Vf), (Vg) and (Vh) are [F 3 C—SO 2 —N—SO 2 —CF 3 ] ⁇ , [F 3 C—SO 2 -N—CO—CF 3 ] ⁇ , [F 3 C—CO—N—CO—CF 3 ] ⁇ and such, wherein the residues R o to R t independently of each other represent hydrogen, methyl, ethyl, propyl, butyl, phenyl, trifluoromethyl, difluoromethyl or fluoromethyl.
  • the residues R u and R v independently of each other preferably represent methyl, ethyl, n-propyl, iso-propyl, butyl, phenyl and p-tolyl.
  • Especially preferred organic phosphates (Vj) are dimethyl phosphate, diethyl phosphate, dibutyl phosphate, bis(2-ethylhexyl) phosphate, diphenyl phosphate, dibenzyl phosphate.
  • Especially preferred organic phosphonates (Vl) are dimethyl phosphonate and diethyl phosphonate.
  • M ⁇ v is particularily preferably selected from the elements Ag, Al, Cr, Co, Cu, Fe, Mn, Mo, Nd, Ni, Sn, Ti, W, V, of the oxidation numbers Ag + , Al +3 , Cr +2 , Cr +3 , Cr +6 , Co +2 , Co +3 , Cu +1 , Cu +2 , Fe +2 , Fe +3 , Mn +2 , Mn +3 , Mo +2 , Mo +3 , Mo +4 , Mo +5 , Nd +2 , Nd +3 , Ni +2 , Ni +3 , Sn +2 , Sn +4 , Ti +2 , Ti +3 , W +4 , W +5 , V +2 , V +3 , V +4 and V +5 .
  • Each individual one of the ligands X is, independently of each other, especially preferably selected from fluoride, chloride, bromide, iodide, thiocyanate, dicyanamide, acetyl acetone; CO; cyanide; cyclopentadienyl; dimethylglyoxime; ethylene diamintetraacetate; ethylene diamine; succinate; oxalate; porphyrin.
  • Preferred cations [A] + are respectively quaternary or protonated ammonium cations [R 1 ′R 1 R 2 R 3 N] + , phosphonium cations [R 1 ′R 1 R 2 R 3 P] + or guanidinium cations R 3 R 3′ N(C ⁇ NR 1 R 1′ )NR 2 R 2′ with the residues R 1 ,R 1′ , R 2 , R 2′ , R 3 und R 3′ , which independently of each other represent hydrogen, linear or branched (C 1 -C 20 )alkyl, linear or branched (C 2 -C 20 )alkenyl, in particular vinyl and allyl, cyclohexyl, phenyl, benzyl or tolyl.
  • guanidinium protonated guanidine
  • 1,1,3,3-tetramethyl guanidinium, 1,1,2,3,3-pentamethyl guanidinium, 1,1,2,2,3,3-hexamethyl guanidinium methyl ammonium, ethyl ammonium, propyl ammonium, butyl ammonium, hexyl ammonium, octyl ammonium, dimethyl ammonium, diethyl ammonium, dipropyl ammonium, dibutyl ammonium, dihexyl ammonium, dioctyl ammonium, diethyl methyl ammonium, dipropylmethyl ammonium, dibutylmethyl ammonium, trimethyl ammonium, triethyl ammonium, tripropyl ammonium, tributyl ammonium, trihexyl ammonium, trioctyl ammonium, diethyld
  • imidazolium protonated 1,3-diazol
  • 1-methyl-imidazolium 1,2-dimethyl imidazolium, 1-ethyl-imidazolium, 1-vinyl imidazolium, 1-propyl-imidazolium, 1-iso-propyl-imidazolium, 1-allyl-imidazolium, 1-butyl-imidazolium, 1-ethyl-2-methyl imidazolium, 1-butyl-2-methylimidazolium, 1-hexyl-imidazolium, 1-octyl-imidazolium, 1,3-dimethyl-imidazolium, 1,2,3-trimethyl imidazolium, 1-ethyl-3-methyl-imidazolium, 1-vinyl-3-methyl-imidazolium, 1-vinyl-2,3-dimethyl-imidazolium, 1-butyl-3-methyl imidazolium, 1-propyl-3-methyl
  • the protonated forms of the strong bases 1,5-diazabicyclo[4.3.0]non-5-ene (DBN); 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU); 1,4-diazabicyclo-[2.2.2]-octane (DABCO®); 1,8-bis-(dimethylamino)-naphthaline (Proton Sponge®); N,N,N′,N′-tetramethylethylene diamine (TMEDA); 4,5-bis-(dimethyl-amino)-fluorene; 1,8-bis-(hexamethyltriamino phosphazenyl)naphthaline.
  • DBN 1,5-diazabicyclo[4.3.0]non-5-ene
  • DBU 1,8-diazabicyclo[5.4.0]undec-7-ene
  • DBU 1,4-diazabicyclo-[2.2.2]-octane
  • DBU 1,
  • ionic liquids described there may further be added in a method according to the invention 5—95 wt. % metal salts [M] x b+ [B] y a ⁇ , wherein a, b, x, y independently of each other represent the integers 1, 2, 3 or 4 and wherein the product of x and b equals the product of y and a.
  • Preferred metal cations therein are Cr +2 , Cr +3 , Co +2 , Co +3 , Cu +1 , Cu +2 , Fe +2 , Fe+3,Mn +2 , Mn +3 , Ni +2 , Ni +3 , Ti +2 , Ti +3 , Li + , Na + , K + , Cs + , Mg 2+ , Ca 2+ , Ba 2 , Sr 2+ , Zr 4+ , Sn 2+ , Sn 4+ , Ag + , Zn 2+ and Al 3+ , especially preferred ones being Co +2 , Co +3 , Cu 30 1 , Cu +2 , Fe +2 , Fe +3 , Mn +2 , Mn +3 , Ti +2 , Ti +3 , Li + , Na + , K + , Mg 2+ , Ca 2+ , Zn 2+ and Al 3+ .
  • Ionic liquids are—in the sense of acknowledged literature (e.g., Wasserscheid, Peter; Welton, Tom (Eds.); “Ionic Liquids in Synthesis”, Verlag Wiley-VCH 2003; ISBN 3-527-30515-7; Rogers, Robin D.; Seddon, Kenneth R. (Eds.); “Ionic Liquids—Industrial Applications to Green Chemistry”, ACS Symposium Series 818, 2002; ISBN 0841237891”)—liquid organic salts or salt mixtures consisting of organic cations and organic or inorganic anions having melting points of below 100° C. In these salts, there may be dissolved in addition inorganic salts and further also molecular adjuvants.
  • the arbitrarily chosen limit of the melting point of ionic liquids of 100° C. is considered in a wider sense, thus also including molten salts having a melting point well above 100° C. but below 200° C. Apart from that, they do not differ in their characteristics. Ionic liquids have extraordinarily interesting characteristics such as, e.g., a very low to not measurable vapour pressure, a very high liquidus range, good electrical conductivity as well as unusual solvation characteristics. These characteristics predestine for being used in various fields of technical applications.
  • solvents for the organic and inorganic synthesis in general, in the transition metal catalysis, the bio-catalysis, the phase transfer catalysis, in multi-phase reactions, in photochemistry, in the polymer synthesis and the nano-technology
  • extraction agents in the liquid-liquid and liquid-gaseous extraction in general, the desulfurization of raw oil, the removal of heavy metals from waste waters, the liquid membrane extraction
  • electrolytes in batteries, fuel cells, capacitors, solar cells, sensors, for the Galvano technique, in the electro-chemical metal processing, in the electro-chemical synthesis in general, in the electro-organic synthesis, in the nano-technology
  • lubricants as thermal fluids, as gels, as reagents for the organic synthesis, in the “Green Chemistry” (substitute for volatile organic compounds”), as anti-static agents, in special applications of analytics (gas chromatography, mass spectroscopy, capillary electrophoresis), as liquid crystals etc.
  • the optimization of the characteristics for the respective application may be realized within wider boundaries due to a variation of the structure of anion and cation or a variation of the combination thereof, respectively, which has resulted in the ionic liquids being in general referred to as “designer solvents” (see, e.g., Freemantle, M.; Chem. Eng. News, 78, 2000, 37).
  • ionic liquids consist of organic cations and organic or inorganic anions, they have a high concentration of charge carriers and, hence, are electrically conductive. Ionic liquids, for this reason, are extraordinarily good microwave recipients (see Mart ⁇ nez-Palou R., Molecular Diversity (2010), 14, (1), 3-25 and Morris R. E., Angewandte Chemie, International Edition (2008), 47, (3), 442-444) having an extremely high absorption coefficient over a very wide frequency range.
  • FIG. 1 there is shown the result of the irradiation of respectively 3 g EMIM-MeSO 3 and TOMA-MeSO 3 at 10 W microwave power.
  • the upper curve relates to TOMA-MeSO 3 , with the lower one relating to EMIM-MeSO 3 .
  • FIG. 2 there is shown the result of the irradiation of respectively 3 g EMIM-MeSO 3 and TOMA-MeSO 3 at 50W microwave power, wherein upon reaching 300° C. irradiation was stopped.
  • the left curve relates to EMIM-MeSO 3 , with the one to the right relating to TOMA-MeSO 3 .
  • EMIM-MeSO 3 is an ionic liquid well-soluble in water having an aromatic cation and rather low viscosity (11 mPas @ 100° C.)
  • TOMA-MeSO 3 is purely aliphatic, hydrophobic and shows i.e. also due to the large molar mass a significantly higher viscosity (83 mPas @ 100° C.).
  • both ionic liquids in spite of the large difference of the molar masses and viscosities thereof, show the nearly identical excellent microwave coupling behaviour, which, hence, is hardly dependent on the density of the charge carriers and the structure of the cations.
  • FIG. 3 shows the heating profiles of the three samples: the solvent 1,4-dioxane as well as the polymer to which carbon particles were added show moderate microwave coupling.
  • the ionic liquid TOMA-MeSO 3 shows a completely different behaviour, leading to significantly faster heating. This is visible from FIG. 3 , which shows a comparison of the heating profiles of a polymer to which carbon particles (carbon black) have been added and an ionic liquid.
  • the uppermost curve is assigned to the TOMA-MeSO 3 , with the middle curve being assigned to the Pe 193 and the lowermost to the dioxane.
  • a commercially available hot melt adhesive (“UHU Klebepatronen”, article number 47865, UHU GmbH & Co. KG) was liquefied at 200° C. in the drying cabinet and homogenously mixed with 5 wt. % of the same ionic liquid as described in example 1 (EMIM MeSO 3 and TOMA MeSO 3 ).
  • the liquid samples were filled into cylindrical 10 mL-microwave containers and again cooled to room temperature. Then the samples were irradiated in a single-mode microwave device (Monowave 300, Anton Paar GmbH) at a constant microwave power of 50 W for a period of 5 min, the temperature was measured at the external wall of the microwave containers using an IR sensor.
  • EMIM MeSO 3 and TOMA MeSO 3 the same ionic liquid as described in example 1
  • the heating profiles of the individual irradiation experiments after 5 minutes, the temperatures measured at the container wall were 70° C. (untreated hot melt adhesive), 170° C. (5 wt. % EMIM MeSO 3 ) and 105° C. (5 wt. % TOMA MeSO 3 ).
  • the hot melt adhesive may also be heated without any additives using microwave irradiation, it is, however, clearly visible that the addition of ionic liquids will lead to significantly higher heating rates.
  • EMIM MeSO 3 which is present as a liquid at room temperature, the heating rates are even faster than with TOMA MeSO 3 , which will only beginning to melt at about 60° C.
  • the three samples were again conventionally liquefied at 200° C. in the drying cabinet, and there were performed adhesion tests using glass (commercially available specimen slides for optical microscopy) and paper (commercially available photocopying paper), wherein there were respectively applied some drops of the liquid hot melt adhesive between two layers of the sample materials, pressure was applied manually onto the sample materials (pressing) and several minutes had to be waited to obtain cooling.
  • the haptically detectable adhesive power of the hot melt adhesive treated with ionic liquid did not show a difference in comparison with the un-treated original sample.
  • thermoplastic materials In order to examine the microwave-induced welding of thermoplastic materials by means of ionic liquids, there were used commercially available vacuum seal foils, as they are used, for example, for packaging foodstuff under vacuum (thermal vacuum seals, “vacuuming”). For this purpose, there was introduced a droplet of EMIM MeSO 3 between two foil parts (75 ⁇ 25 mm) and fixed between microwave-transparent glass plates in order to impregnate a certain contact pressure and to ensure the foils contacting each other.
  • the schematic illustration of the test set-up is illustrated in FIG. 5 ( ⁇ circle around (1) ⁇ glass plates, ⁇ circle around (2) ⁇ thermoplastic foils, ⁇ circle around (3) ⁇ EMIM MeSO 3 ).
  • the system to be irradiated was irradiated in a home microwave device commercially available (Samsung ME711K, Samsung Electronics U.K. Ltd.), which is operated at a frequency of 2450 MHz.
  • the microwave power of the device may be freely selected between 100 and 800 in increments, with a rotating plate internally arranged in the 20 L-cavity ensuring a rather homogenous distribution of the microwave irradiation onto the samples.
  • the foil parts were brought into contact without any ionic liquid between the two glass plates and irradiated at a magnetron power of 800 W for 150 s seconds.
  • thermoplastic foils were not molten into one another, although the irradiated system as a whole was slightly heated.
  • a droplet of EMIM MeSO 3 was introduced in-between the two foils, which were brought into contact by the two glass plates and which were irradiated for 30 s at the same microwave power as before (800 W).
  • the thermoplastic foils had molten into one another at exactly that area where the droplets of ionic liquid had been applied onto before. It is, hence, possible to heat the droplet of the ionic liquid within a very short period of time selectively so significantly so that the two foil parts will weld into one another.
  • the majority of the ionic liquids is colourless to yellowish and may be included in a homogenous phase, they will not interfere with the optical appearance, in contrast to the mostly black particles.
  • Suitable ionic liquids may be chemically functionalized, wherein in particular those functionalities are interesting, which are identical or analogous to those of the adhesive monomers, so that the functionalized ionic liquid will bind into the cured adhesive matrix, thus being no “filler” but rather part of the matrix and contributing to the rigidity thereof.
  • Such functionalized ionic liquids may potentially also be used as an adhesive monomer in reactive adhesives, so that a polymeric ionic liquid will be developed during the curing process.
  • Especially preferred chemical functionalizations are —OR c , —SR c , —NR c R d , —COR c , —COOR c , —CO—NR c R d , acrylate, methacrylate, cyanoacrylate, epoxide, vinyl, vinyl ether, vinyl ester, styrene, allyl, phenol, alkyl phenol, ketone, amidoamine, urea, urethane, imidazole, benzimidazole, isocyanate, dicarboxylic acid anhydride, resorcinol, melamine, siloxane, alkoxy siloxane, wherein
  • R c and R d independently of each other represent hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -halogenalkyl, cyclopentyl, cyclohexyl, phenyl, tolyl or benzyl.
  • ionic liquids may be added as microwave recipients, as long as these are soluble in the adhesive mixture or may be gelled therein, respectively, thus being homogenously distributed.
  • the ionic liquids may also be dissolved in the adhesive mixture or gelled, they may be present colloidally or in an emulsified form. They may also be suspended as solid particles, if they have, e.g., a melting point above the currently prevailing surrounding temperature, they may, however, liquefy during the adhesive process due to an increase of temperature. This temperature increase may be induced by microwaves, or it may have a conventional reason, or it may have originated in the reaction heat.
  • the ionic liquids may be pure materials or mixtures of various ionic liquids and/or there may additionally be dissolved organic or inorganic salts, e.g., in order to increase the density of charge carriers therein and to increase the microwave coupling behaviour.
  • the ionic liquids may also be applied or introduced or injected, respectively, as a thin layer between to thermoplastic materials to be glued together or a thermoplastic material to be glued and another material in order to cause melting of the thermoplastic/s, hence carrying out a welding process.
  • Adhesive connections may also be realized in inaccessible areas if the adhesives are already “installed”, e.g., during the assembly of a complex workpiece and are only later activated using microwave irradiation.
  • a conventional method of this type is used, e.g., in automobile construction (“spot-welded jointing”), wherein the parts to be glued together with the adhesive are fixed by means of spot-welding, wherein, however, then the entire workpiece has to be heated in order to activate the adhesive process and obtain a high rigidity. Hot melt adhesive joints, later on, may be released quickly and conservingly, without having to heat the entire workpiece.
  • MASER microwave laser

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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)
  • Adhesives Or Adhesive Processes (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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US10774064B2 (en) 2016-06-02 2020-09-15 Cadent Therapeutics, Inc. Potassium channel modulators
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US11718594B2 (en) 2016-09-21 2023-08-08 Celanese International Corporation Acesulfame potassium compositions and processes for producing same
US11724994B2 (en) 2016-09-21 2023-08-15 Celanese International Corporation Acesulfame potassium compositions and processes for producing same
US11724993B2 (en) 2016-09-21 2023-08-15 Celanese International Corporation Acesulfame potassium compositions and processes for producing same
US11731948B2 (en) 2016-09-21 2023-08-22 Celanese International Corporation Acesulfame potassium compositions and processes for producing same
US11993586B2 (en) 2018-10-22 2024-05-28 Novartis Ag Crystalline forms of potassium channel modulators
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US10774064B2 (en) 2016-06-02 2020-09-15 Cadent Therapeutics, Inc. Potassium channel modulators
US11718594B2 (en) 2016-09-21 2023-08-08 Celanese International Corporation Acesulfame potassium compositions and processes for producing same
US11724994B2 (en) 2016-09-21 2023-08-15 Celanese International Corporation Acesulfame potassium compositions and processes for producing same
US11724993B2 (en) 2016-09-21 2023-08-15 Celanese International Corporation Acesulfame potassium compositions and processes for producing same
US11731948B2 (en) 2016-09-21 2023-08-22 Celanese International Corporation Acesulfame potassium compositions and processes for producing same
US9975886B1 (en) 2017-01-23 2018-05-22 Cadent Therapeutics, Inc. Potassium channel modulators
US10351553B2 (en) 2017-01-23 2019-07-16 Cadent Therapeutics, Inc. Potassium channel modulators
US10717728B2 (en) 2017-01-23 2020-07-21 Cadent Therapeutics, Inc. Potassium channel modulators
US11993586B2 (en) 2018-10-22 2024-05-28 Novartis Ag Crystalline forms of potassium channel modulators
US12275742B2 (en) 2020-05-05 2025-04-15 Nuvalent, Inc. Heteroaromatic macrocyclic ether chemotherapeutic agents
CN116285829A (zh) * 2023-04-04 2023-06-23 陕西师范大学 同时耐超低温与有机溶剂的组合类超分子粘合剂

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CA2930343C (en) 2021-06-08
CA2930343A1 (en) 2015-06-04
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EP2997106B1 (de) 2019-03-06
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CN106029804B (zh) 2019-09-24
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