EP4598975A1 - Two-component adhesive composition - Google Patents

Two-component adhesive composition

Info

Publication number
EP4598975A1
EP4598975A1 EP23754911.8A EP23754911A EP4598975A1 EP 4598975 A1 EP4598975 A1 EP 4598975A1 EP 23754911 A EP23754911 A EP 23754911A EP 4598975 A1 EP4598975 A1 EP 4598975A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
polyamine
adhesive
general formula
compound
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.)
Pending
Application number
EP23754911.8A
Other languages
German (de)
French (fr)
Inventor
Sergio Grunder
Maria UZUNSKA
Daniel Schneider
Felix Koch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DDP Specialty Electronic Materials US LLC
Original Assignee
DDP Specialty Electronic Materials US LLC
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by DDP Specialty Electronic Materials US LLC filed Critical DDP Specialty Electronic Materials US LLC
Publication of EP4598975A1 publication Critical patent/EP4598975A1/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/70—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/82—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton with the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/10—Preparation of carboxylic acid amides from compounds not provided for in groups C07C231/02 - C07C231/08
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/003—Polymeric products of isocyanates or isothiocyanates with epoxy compounds having no active hydrogen
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/20—Heterocyclic amines; Salts thereof
    • C08G18/2045—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings
    • C08G18/2063—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings having two nitrogen atoms in the condensed ring system
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/227—Catalysts containing metal compounds of antimony, bismuth or arsenic
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2895—Compounds containing active methylene 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8093—Compounds containing active methylene groups
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/02—Polyureas
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes

Definitions

  • the present invention relates to the field of two-component adhesive compositions.
  • Two-component polyurethane and epoxy adhesives are well-known in the art, and give a broad range of adhesives with widely ranging characteristics, making them suitable for many diverse applications.
  • a two-component polyurethane adhesive typically comprises an isocyanate component, comprising molecules that have isocyanate (NCO) functionality, and a polyol component, comprising molecules that have multiple OH functionalities.
  • the two components are stored separately until use, at which point they are mixed, and curing begins by reaction between the NCO functionalities of the isocyanate component and the OH functionalities of the polyol component, to form urethane linkages. This results in formation of a cured three-dimensional matrix.
  • the isocyanate component may be in the form of a prepolymer, formed by reaction of an excess of NCO groups with a polyol or polyols, resulting in a medium to large molecular weight polymer, terminated with NCO groups.
  • the prepolymer NCO groups react with the OH functionalities of the polyol component after mixing during use, forming a cured network.
  • NCO-terminated prepolymers are useful in many situations, they can be a concern regarding health and safety performance.
  • the monomeric diisocyanates are intrinsically toxic and therefore the adhesives are often labelled as carcinogens. Therefore alternative 2K solutions, that show similar end-properties when cured, but with less severe labelling requirements are needed.
  • CPEE ethyl 2-oxocyclopentane-1 -carboxylate
  • CPEE-terminated prepolymers typically suffer from decreased lap shear strength on curing.
  • the invention provides a compound of general Formula I: where R 1 and R 2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R 3 is Ci to Ce alkyl, and R 4 is a divalent C4-8- alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain.
  • the invention provides a use of a compound of general
  • R 1 and R 2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R 3 is Ci to Ce alkyl, and R 4 is a divalent C4-8- alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain, as a monomer in a polymer.
  • the invention provides a two-part adhesive comprising:
  • R 1 and R 2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R 3 is Ci to Ce alkyl, and R 4 is a divalent C4-8-alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain;
  • Part B a second part (Part B) comprising:
  • (b1 ) at least one polyamine, having two or more primary or secondary amine functionalities; wherein at least one of Part A and Part B comprises a catalyst capable of catalyzing the reaction of an amine with a compound of general Formula I, and wherein Part A and Part B are designed to be mixed together to form an adhesive mixture prior to use.
  • the invention provides a kit for forming an adhesive, comprising:
  • Part A a first part (Part A) comprising:
  • the invention provides an adhered assembly comprising:
  • R 1 and R 2 are independently selected from H and Ci to C4 alkyl, more preferably H and Ci to C2 alkyl, particularly preferably R 1 and R 2 are H.
  • R 3 is Ci to C4 alkyl, more preferably R 3 is Ci to C2 alkyl, particularly preferably R 3 is ethyl.
  • R 4 is a divalent Ce alkylene radical with 2-5 methyl substituents on the alkylene chain. In a more preferred embodiment, R 4 is a Ce alkylene radical with three methyl substituents on the alkylene chain.
  • the compound of general Formula I is of Formula I”:
  • 2,4,4- trimethylhexamethylene diisocyanate (II) is reacted with at least two equivalents of ethyl 2-oxocyclopentane-1 -carboxylate, in the presence of a bismuth and/or zinc catalyst, in particular a mixture of bismuth and/or zinc catalysts:
  • Part A of the adhesive of the invention optionally comprises at least one liquid epoxy resin, by which is meant epoxy resins that are liquid at 23°C.
  • epoxy resin If only a single epoxy resin is present, it is a liquid at 23°C. If two or more epoxy resins are present, the mixture thereof is a liquid at 23°C, although individual epoxy resins within the mixture may be by themselves solids at 23°C.
  • Epoxy novolac resins can be used. Such resins are available commercially as D.E.N.® 354, D.E.N.® 431 , D.E.N.® 438 and D.E.N.® 439 from Olin Corporation.
  • the liquid epoxy resin is preferably present at 2-20 wt%, more preferably 2-10 wt%, particularly preferably 4-8 wt%, based on the total weight of Part A.
  • Part A and/or Part B may comprise a thermally-conductive filler.
  • thermally-conductive filler is not particularly limited. Suitable thermally-conductive fillers are those that have a coefficient of thermal conductivity that is greater than 5 W/m°K, more preferably greater than 10 W/m°K, or particularly preferably greater than 15 WZ m°K.
  • thermally-conductive fillers include alumina, alumina trihydrate or aluminum trihydroxide (ATH), silicon carbide, boron nitride, diamond, and graphite, and mixtures thereof. Particularly preferred are aluminium trihydroxide (ATH), and aluminium oxide, with ATH being the most preferred.
  • Thermally-conductive fillers may be surface treated or non-treated.
  • the thermally-conductive filler is aluminium trihydroxide (ATH), used at a concentration of 30-85 wt%, more preferably 40- 85 wt%, more particularly preferably 60-85 wt%, based on the total weight of the adhesive.
  • ATH aluminium trihydroxide
  • the thermally-conductive filler is bimodally distributed aluminium trihydroxide (ATH), used at a concentration of 30-85 wt%, more preferably 40-85 wt%, more particularly preferably 60-85 wt%, based on the total weight of the adhesive.
  • ATH aluminium trihydroxide
  • the concentration of thermally-conductive filler in Part A is preferably 30-85 wt%, more preferably 40-85 wt%, more particularly preferably 60-85 wt%, based on the total weight of Part A.
  • the thermally-conductive filler is aluminium trihydroxide (ATH), used in Part A and/or Part B at a concentration of 30-85 wt%, more preferably 40-85 wt%, more particularly preferably 60-85 wt%, based on the total weight of Part A or Part B.
  • ATH aluminium trihydroxide
  • the thermally-conductive filler is ATH having a bimodal particle size, used in Part A and/or Part B at a concentration of 30-85 wt%, more preferably 40-85 wt%, more particularly preferably 60-85 wt%, based on the total weight of Part A or Part B.
  • At least one polyamine At least one polyamine
  • Component B comprises at least one polyamine, having two or more primary or secondary amine groups.
  • the at least one polyamine comprises a triamine.
  • the polyamine is a triamine having primary amine groups and having a molecular weight of 2,000-4,000 Da, more preferably 3,000 Da.
  • suitable compounds having primary and/or secondary amino groups include polyoxyalkylene polyamines having 2 or more amine groups per polyamine, 2 to 4 amine groups per polyamine, or 2 to 3 amine groups per polyamine. Particularly preferred are polyether amines having 3 amine groups.
  • the polyoxyalkylene poly-amines may have a weight average molecular weight of at least 400 Da, more preferably at least 1 ,000 Da, more particularly preferably at least 2,000 Da. In a preferred embodiment, the polyoxyalkylene polyamine has a molecular weight of 2,000-4,000 Da, more preferably about 3,000 Da. The polyoxyalkylene polyamine may have a weight average molecular weight of about 5,000 or less or about 3,000 or less.
  • Polyamines based on a propylene oxide polyether backbone examples include:
  • Polyamines based predominantly on a polyethylene oxide polyether backbone are of the general formula: Such as a polyamine of molecular weight 600 g/mol, where y « 9, (x + z) « 3.6;
  • the at least one polyamine comprises or consists of a triamine of approximately 3000 molecular weight, of the formula:
  • the at least one polyamine comprises or consist of a polyetheramine triamine of approximately 440 molecular weight, of the following general structure:
  • suitable polyamines include polyamidoamines, which comprise repetitively branched subunits of amide and amine functionality.
  • suitable polyamidoamines are initiated with ammonia or ethylene diamine, reacted by Michael addition with an acrylate ester (for example methyl acrylate), followed by reaction of the ester functionalities with a diamine (such as ethylene diamine).
  • an acrylate ester for example methyl acrylate
  • a diamine such as ethylene diamine
  • the first “cycle” is represented schematically below using ethylene diamine and methyl acrylate:
  • the at least one polyamine comprises or consists of a mixture of a triamine of approximately 3,000 molecular weight, of the formula: and a polyetheramine triamine of approximately 440 molecular weight, of the following general structure:
  • the at least one polyamine is preferably present in Part B at 8-30 wt%, more preferably 10-20 wt%, more particularly preferably 12-16 wt%, based on the total weight of Part B.
  • the at least one polyamine is preferably present in Part B at 80-99 wt%, more preferably 85-95 wt%, particularly preferably 87-92 wt%, based on the organic content of Part B.
  • the at least one polyamine comprises or consists of a polyether triamine or mixture of polyether triamines, used in Part B at 8- 30 wt%, more preferably 10-20 wt%, more particularly preferably 12-16 wt%, based on the total weight of Part B.
  • the at least one polyamine comprises or consists of a mixture of a polyether triamine of approximately 3,000 Da and a polyether triamine of approximately 440 Da, used in Part B at 8-30 wt%, more preferably 10-20 wt%, more particularly preferably 12-16 wt%, based on the total weight of Part B.
  • the at least one polyamine comprises or consists of a polyether triamine or mixture of polyether triamines, used in Part B at SO- 99 wt%, more preferably 85-95 wt%, particularly preferably 87-92 wt%, based on the organic content of Part B.
  • the at least one polyamine comprises or consists of a mixture of a polyether triamine of approximately 3,000 Da and a polyether triamine of approximately 440 Da, used in Part B at 80-99 wt%, more preferably 85-95 wt%, particularly preferably 87-92 wt%, based on the organic content of Part B.
  • the catalyst is preferably selected from tertiary amine catalysts.
  • Suitable tertiary amines include 2,4,6-fr/s- (dimethylaminomethyl)phenol, tetramethylguanidine, heptamethylisobiguanide, N,N-dimethylbenzylamine, and 1 ,4- Diazabicyclo[2.2.2]octane.
  • the catalyst is 2,4,6-fr/s- (dimethylaminomethyl)phenol.
  • the catalyst may be present in Part A and/or Part B. In a preferred embodiment, it is present in Part B.
  • the catalyst is preferably used at 0.05-0.75 wt%, more preferably 0.1 -0.6 wt%, more particularly preferably 0.45-0.55 wt%, based on the total weight of Part B.
  • the adhesive compositions of the invention may optionally comprise fillers, in addition to any thermally-conductive fillers, which may be present in Part A or B or both, such as carbon black, clay, carbonates (e.g. calcium carbonate), metal hydrates and fumed silica.
  • the fillers are preferably used at from 0-10 wt%, preferably 1-6 wt%, more preferably 2-5 wt%, based on the total weight of the relevant Part.
  • the adhesives of the invention comprise carbon black as filler.
  • the carbon black is not particularly limited. Preferred carbon blacks exhibit an oil absorption number of at least 80, preferably at least 90 and more preferably at least 95 cm 3 of dibutyl phthalate per 100 g of carbon black, as measured according to ASTM D-2414-09.
  • the carbon black desirably has an iodine number of at least 80, determined according to ASTM D1510-11.
  • the adhesive compositions of the invention may optionally comprise calcium carbonate in Part A and/or Part B at 0-5 wt%, more preferably 1 to 3 wt%, particularly preferably 1 .5-2.5 wt%, based on the total weight of the relevant Part.
  • the calcium carbonate particles may be untreated or surface modified by treatment with chemicals, such as organic acids or esters of organic acids.
  • the adhesive compositions of the invention may optionally comprise fumed silica at 0-1 .5 wt%, more preferably 0.5 to 1 wt%, based on the total weight of the adhesive.
  • the particles may be untreated or surface modified by treatment with chemicals, such as chlorosilane, dichlorosilane, alkyltrialkoxysilane or polydimethylsiloxane.
  • the adhesive composition of the invention may optionally comprise talc, which may be present in Component A or B or both.
  • talc is used in Component B at 25 to 40 wt%, more preferably30 to 35 wt%, based on the total weight of Component B.
  • the adhesive composition of the invention may optionally comprise adhesion promoters, which may be present in Component A or B or both.
  • Suitable adhesion promoters include silanes, such as Gamma- Glycidoxypropyltrimethoxysilane.
  • Gamma- Glycidoxypropyltrimethoxysilane is used in Part A, at 0.1 to 1 wt%, preferably 0.3-0.6 wt%, based on the total weight of Part A.
  • the adhesive compositions of the invention may optionally comprise flameretardants and synergists.
  • suitable flame-retardants and synergists include:
  • nitrogen and/or phosphorus containing molecules such as melamine polyphosphate, melamine pyrophosphate, melamine cyanurate;
  • a preferred combination of flame-retardants/synergists is aluminium diethylphosphinate plus melamine polyphosphate.
  • UV light stabilizers include benzophenones and benzotriazoles.
  • Specific UV light absorbers include those from BASF such as TINUVINTM P, TINUVINTM 326, TINUVINTM 213, TINUVINTM 327, TINUVINTM 571 , TINUVINTM 328, and from Cytec such as CYASORBTM UV-9, CYASORBTM UV-24, CYASORBTM UV-1164, CYASORBTM UV-2337, CYASORBTM UV- 2908, CYASORBTM UV-5337, CYASORBTM UV-531 , and CYASORBTM UV- 3638.
  • TINUVINTM 571 is preferred.
  • One or more UV light absorbers may constitute at least 0.1 weight percent, at least 0.2 weight percent or at least 0.3 parts by weight of the weight of the adhesive composition, and may constitute up to 3 weight percent, up to 2 weight percent or up to 1 weight percent thereof.
  • the adhesive composition of the invention may further include one or more visible light stabilizers.
  • Preferred visible light stabilizers included hindered amine visible light stabilizers such as TINUVINTM 144, TINUVINTM 622, TINUVINTM 77, TINUVINTM 123, TINUVINTM 765, CHIMASSORBTM 944 available from Cytec; CYASORBTM UV-500, CYASORBTM UV-3581 , CYASORBTM UV-3346, all available from Ciba-Geigy.
  • TINUVINTM 765 is preferred choice.
  • the visible light stabilizer(s) may constitute at least 0.1 weight percent, at least 0.2 weight percent or at least 0.3 weight percent of the adhesive composition, and may constitute up to 3 weight percent, up to 2 weight percent or up to 1 .5 weight percent thereof.
  • Part A and Part B are made by mixing the ingredients, preferably on a planetary mixer or on a dual asymmetric centrifuge.
  • a first phase the liquid phases are mixed before the solid material is added to the formulation.
  • the formulation was mixed for ca 30 min under vacuum before being filled into cartridges, pails, or drums.
  • the two Parts are stored separately until use, at which point they are mixed.
  • the invention provides a method for adhering two substrates, comprising the steps:
  • Part A a first part (Part A) comprising:
  • R 1 and R 2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R 3 is Ci to Ce alkyl, and R 4 is a divalent C4-8-alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain;
  • Part B a second part (Part B) comprising:
  • Preferred embodiments of the method use preferred embodiments of the adhesive described herein.
  • Part A and Part B may be mixed in any ratio.
  • the ratio of Part A to Part B is 0.5:1 to 1 :0.5 (v:v), more preferably 1 :1 .5 to 1.5:1 (v:v), particularly preferably 1 :1 (v:v).
  • the adhesive composition of the invention may be applied by any application method, manually or with robotic equipment, including, for example, by spreading, application through a nozzle.
  • a compound of general Formula I where R 1 and R 2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R 3 is Ci to Ce alkyl, and R 4 is a divalent C4-8- alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain.
  • Part A a first part (Part A) comprising:
  • Part B a second part (Part B) comprising:
  • R 1 and R 2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R 3 is Ci to Ce alkyl, and R 4 is a divalent C4-8-alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain;
  • Part B a second part (Part B) comprising:
  • a method for adhering a first substrate and a second substrate comprising the steps:
  • Part A a first part (Part A) comprising:
  • R 1 and R 2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R 3 is Ci to Ce alkyl, and R 4 is a divalent C4-8-alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain;
  • Part A a first part (Part A) comprising:
  • Part B a second part (Part B) comprising:
  • (b1 ) at least one polyamine, having two or more primary or secondary amine functionalities; wherein at least one of Part A and Part B comprises a catalyst capable of catalyzing the reaction of an amine with a compound of general Formula I, and wherein Part A and Part B are designed to be mixed together to form an adhesive mixture prior to use.
  • a kit for forming an adhesive comprising:
  • Part A a first part (Part A) comprising:
  • R 1 and R 2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R 3 is Ci to Ce alkyl, and R 4 is a divalent C4-8-alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain;
  • Part B a second part (Part B) comprising:
  • (b1 ) at least one polyamine, having two or more primary or secondary amine functionalities; wherein at least one of Part A and Part B comprises a catalyst capable of catalyzing the reaction of an amine with a compound of general Formula I, and wherein Part A and Part B are stored isolated from one another, and are designed to be mixed together to form an adhesive mixture prior to use.
  • a method for adhering a first substrate and a second substrate comprising the steps:
  • Part A a first part (Part A) comprising:
  • R 1 and R 2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R 3 is Ci to Ce alkyl, and R 4 is a divalent C4-8-alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain;
  • Part B a second part (Part B) comprising:
  • (b1 ) at least one polyamine, having two or more primary or secondary amine functionalities; wherein at least one of Part A and Part B comprises a catalyst capable of catalyzing the reaction of an amine with a compound of general Formula I, and wherein Part A and Part B are designed to be mixed together to form an adhesive mixture prior to use;
  • An adhered assembly comprising:
  • Part A a first part (Part A) comprising:
  • R 1 and R 2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R 3 is Ci to Ce alkyl, and R 4 is a divalent C4-8-alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain;
  • Part B a second part (Part B) comprising: (b1 ) at least one polyamine, having two or more primary or secondary amine functionalities; wherein at least one of Part A and Part B comprises a catalyst capable of catalyzing the reaction of an amine with a compound of general Formula I; wherein the first and second substrates are in adhesive contact with the adhesive composition sandwiched between them.
  • a method for making a compound of general Formula I comprising reacting a molecule of Formula III with at least two equivalents of a molecule of Formula IV, in the presence of a catalyst: where R 1 and R 2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R 3 is Ci to Ce alkyl, and R 4 is a divalent C4-8-alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain.
  • R 1 and R 2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R 3 is Ci to Ce alkyl, and R 4 is a divalent C4-8-alkylene radical with 2-5 C1-3- alkyl substituents on the akylene chain.
  • the at least one liquid epoxy resin comprises an epoxy resin having an epoxy equivalent weight of 75 to 350 g/eq, preferably 140 to 250 g/eq, more preferably 150 to 225 g/eq.
  • the at least one epoxy resin comprises a reaction product of epichlorohydrin and bisphenol A, having an epoxide equivalent weight of 176-185 g/eq (according to ASTM D-1652), an epoxide percentage of 23.2-24.4 % (according to ASTM D-1652), an epoxide group content of 5,400-5,680 mmol/kg (according to ASTM D-1652), and a viscosity @ 25°C of 7,000-10,000 MPas (according to ASTM D-445), and is present in Part A at 12-50 wt%, more preferably 15-35 wt%, more particularly preferably 20-30 wt%, based on the total organic content of Part A.
  • Part A and/or Part B comprise a thermally-conductive filler selected from those that have a coefficient of thermal conductivity that is greater than 5 W/m°K, more preferably greater than 10 W/m°K, or particularly preferably greater than 15 W/ m°K.
  • Part A and/or Part B comprise a thermally-conductive filler, wherein the thermally- conductive filler is selected from alumina, alumina trihydrate or aluminum trihydroxide (ATH), silicon carbide, boron nitride, diamond, and graphite, and mixtures thereof.
  • ATH aluminum trihydroxide
  • Part A and/or Part B comprise a thermally-conductive filler, and the thermally-conductive filler is selected from aluminium trihydroxide (ATH), and aluminium oxide, with ATH being the most preferred.
  • ATH aluminium trihydroxide
  • the thermally-conductive filler is ATH or aluminium oxide having a broad particle size distribution characterized by a ratio of D901 D50 of at or about 3 or more, most preferably ATH.
  • Part A and/or Part B comprise a thermally-conductive filler
  • the thermally-conductive filler is bimodally distributed aluminium trihydroxide (ATH), having the following particle size distribution (by laser diffraction in deionized water containing a dispersion aid, such as Na4P2O? x 10 H2O, preferably at 1 g/l):
  • Part A and/or Part B comprise a thermally-conductive filler, and the thermally-conductive filler is bimodally distributed aluminium trihydroxide (ATH), used at a concentration of 30-85 wt%, more preferably 40-85 wt%, more particularly preferably 60-85 wt%, based on the total weight of the adhesive.
  • ATH aluminium trihydroxide
  • the thermally-conductive filler is aluminium trihydroxide (ATH), having the following particle size distribution (by laser diffraction in deionized water containing a dispersion aid, such as Na4P2O? x 10 H2O, preferably at 1 g/l):
  • Part A and/or Part B comprise a thermally-conductive filler
  • the thermally-conductive filler is ATH having a bimodal particle size, used in Part A and/or Part B at a concentration of 30-85 wt%, more preferably 40-85 wt%, more particularly preferably 60-85 wt%, based on the total weight of Part A or Part B.
  • the thermally-conductive filler is aluminium trihydroxide (ATH), having the following particle size distribution (by laser diffraction in deionized water containing a dispersion aid, such as Na4P2O?
  • x 10 H2O preferably at 1 g/l: D10 (micron) 0.5 D50 (micron) 8 D90 (micron) 80 used in Part A and/or Part B at a concentration of 30-85 wt%, more preferably 40-85 wt%, more particularly preferably 60-85 wt%, based on the total weight of Part A or Part B.
  • the at least one polyamine comprises a polyamine having a molecular weight of 2,000-4,000 Da, more preferably about 3,000 Da.
  • the at least one polyamine comprises a polyamine having a molecular weight of at least 300 Da, more preferably at least 350 Da, more particularly preferably at least 400 Da.
  • the at least one polyamine comprises a polyamine having a molecular weight of 300-500 Da, more preferably about 400-440 Da.
  • polyamine comprises a triamine having primary amine groups and having a molecular weight of 2,000-4,000 Da, more preferably 3,000 Da.
  • polyamine comprises a polyoxyalkylene polyamine having 2 or more amine groups per polyamine, 2 to 4 amine groups per polyamine, or 2 to 3 amine groups per polyamine.
  • polyamine comprises a polyether amine having 3 amine groups.
  • polyamine comprises a polyamine based on a propylene oxide polyether backbone.
  • any one preceding embodiment, wherein the polyamine comprises a triamine of approximately 3000 molecular weight, of the formula: Any one preceding embodiment, wherein the at least one polyamine comprises or consists of a mixture of a triamine of approximately 3000 molecular weight, of the formula: and a polyether triamine of approximately 440 molecular weight, of the following general structure: Any one preceding embodiment, wherein the at least one polyamine is present in Part B at 8-30 wt%, more preferably 10-20 wt%, more particularly preferably 12-16 wt%, based on the total weight of Part B.
  • the at least one polyamine comprises or consists of a polyether triamine or mixture of polyether triamines, used in Part B at 8-30 wt%, more preferably 10-20 wt%, more particularly preferably 12-16 wt%, based on the total weight of Part B.
  • the at least one polyamine comprises or consists of a mixture of a polyether triamine of approximately 3,000 Da and a polyether triamine of approximately 440 Da, used in Part B at 8-30 wt%, more preferably 10-20 wt%, more particularly preferably 12-16 wt%, based on the total weight of Part B.
  • the at least one polyamine comprises or consists of a polyether triamine or mixture of polyether triamines, used in Part B at 80-99 wt%, more preferably 85-95 wt%, particularly preferably 87-92 wt%, based on the organic content of Part B.
  • the catalyst is used at 0.05- 0.75 wt%, more preferably 0.1 -0.6 wt%, more particularly preferably 0.45-0.55 wt%, based on the total weight of Part B.
  • the catalyst comprises or consists of 2,4,6-fr/s-(dimethylaminomethyl)phenol, used at 0.2 to 0.8 w%, more preferably 0.3 to 0.5 wt%, based on the total weight of Part B.
  • NCO-terminated prepolymer based on diphenylmethane diisocyanate (MDI) and polypropylene glycol), with equivalent weight of 251-274 g/eq, and a functionality of approximately 2.8 Test methods
  • the press-in force is measured with a tensiometer (Zwick).
  • the material is placed on a metal surface.
  • An aluminium piston with 40 mm diameter is placed on top and the material is compressed to 5 mm (initial position).
  • the material is then compressed to 0.3 mm with 1 mm/s velocity and a force deflection curve is recorded.
  • the force (N) at 0.5 mm thickness is considered as the press-in force, and is reported in Table 3.
  • Thermal conductivity is measured according to ASTM 5470-12 on a thermal interface material tester from ZFW Stuttgart. The tests are performed in Spaltplus mode at a thickness of between 1.8-1.2 mm. The material is considered as Type I (viscous liquids) as described in ASTM 5470-12. The upper contact is heated to ca 40°C and the lower contact to ca 10°C, resulting in a sample temperature of ca 25°C. The A and B component are mixed with a static mixer when applied from a manual cartridge system.
  • Aluminium substrates from Novelis, AA6061 T6 1.92mm MF noPT no lub (140 x 25 mm, 1.9 mm thick) (140 x 25 mm, 1.9 mm thick) were used. The substrates were cleaned with isopropanol before use. The adhesive was applied on one substrate, and the second substrate was joined within 5 minutes. The thickness was adjusted to 1 .0 mm, the overlap area was 25 mm x 25 mm. The material was cured and rested for 7 days at 23°C, 50 % relative humidity, before the lap shear tests were performed. The lap shear samples were then mounted in a tensiometer and the lap shear tests were performed using a pull speed of 10 mm/min. The force deflection curve was recorded and the strength at break was reported as lap shear strength.

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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)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Provided herein is a monomer for making polymers, in particular adhesives, and adhesives made with said monomer.

Description

TWO-COMPONENT ADHESIVE COMPOSITION
Field of Invention
The present invention relates to the field of two-component adhesive compositions.
Background of the Invention
Two-component polyurethane and epoxy adhesives are well-known in the art, and give a broad range of adhesives with widely ranging characteristics, making them suitable for many diverse applications.
A two-component polyurethane adhesive typically comprises an isocyanate component, comprising molecules that have isocyanate (NCO) functionality, and a polyol component, comprising molecules that have multiple OH functionalities. The two components are stored separately until use, at which point they are mixed, and curing begins by reaction between the NCO functionalities of the isocyanate component and the OH functionalities of the polyol component, to form urethane linkages. This results in formation of a cured three-dimensional matrix.
Often the isocyanate component may be in the form of a prepolymer, formed by reaction of an excess of NCO groups with a polyol or polyols, resulting in a medium to large molecular weight polymer, terminated with NCO groups. The prepolymer NCO groups react with the OH functionalities of the polyol component after mixing during use, forming a cured network.
While NCO-terminated prepolymers are useful in many situations, they can be a concern regarding health and safety performance. The monomeric diisocyanates are intrinsically toxic and therefore the adhesives are often labelled as carcinogens. Therefore alternative 2K solutions, that show similar end-properties when cured, but with less severe labelling requirements are needed. It is known to modify NCO-terminated polyurethane prepolymers by reacting the terminal NCO functionalities of the prepolymer with a molecule such as ethyl 2-oxocyclopentane-1 -carboxylate (CPEE). This technology shows several advantages: no toxic NCO-labelling is required, similar end-cure properties to NCO-terminated polyurethanes and fast curing kinetics.
However, CPEE-terminated prepolymers typically suffer from decreased lap shear strength on curing.
Summary of the Invention
In a first aspect, the invention provides a compound of general Formula I: where R1 and R2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R3 is Ci to Ce alkyl, and R4 is a divalent C4-8- alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain.
In a second aspect, the invention provides a use of a compound of general
Formula I: where R1 and R2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R3 is Ci to Ce alkyl, and R4 is a divalent C4-8- alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain, as a monomer in a polymer. In a third aspect, the invention provides a two-part adhesive comprising:
(A) a first part (Part A) comprising:
(a1 ) at least one compound of general Formula I: where R1 and R2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R3 is Ci to Ce alkyl, and R4 is a divalent C4-8-alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain;
(B) a second part (Part B) comprising:
(b1 ) at least one polyamine, having two or more primary or secondary amine functionalities; wherein at least one of Part A and Part B comprises a catalyst capable of catalyzing the reaction of an amine with a compound of general Formula I, and wherein Part A and Part B are designed to be mixed together to form an adhesive mixture prior to use.
In a fourth aspect, the invention provides a kit for forming an adhesive, comprising:
(A) a first part (Part A) comprising:
(a1 ) at least one compound of general Formula I: where R1 and R2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R3 is Ci to Ce alkyl, and R4 is a divalent C4-8-alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain;
(B) a second part (Part B) comprising:
(b1 ) at least one polyamine, having two or more primary or secondary amine functionalities; wherein at least one of Part A and Part B comprises a catalyst capable of catalyzing the reaction of an amine with a compound of general Formula I, and wherein Part A and Part B are stored isolated from one another, and are designed to be mixed together to form an adhesive mixture prior to use.
In a fifth aspect, the invention provides a method for adhering a first substrate and a second substrate, comprising the steps:
(1 ) providing a two-part adhesive comprising:
(A) a first part (Part A) comprising:
(a1 ) at least one compound of general Formula I: where R1 and R2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R3 is Ci to Ce alkyl, and R4 is a divalent C4-8-alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain;
(B) a second part (Part B) comprising:
(b1 ) at least one polyamine, having two or more primary or secondary amine functionalities; wherein at least one of Part A and Part B comprises a catalyst capable of catalyzing the reaction of an amine with a compound of general Formula I, and wherein Part A and Part B are designed to be mixed together to form an adhesive mixture prior to use;
(2) mixing Part A and Part B to produce an adhesive mixture; (3) applying the adhesive mixture to the first substrate;
(4) bringing the second substrate into adhesive contact with the first substrate; and
(5) allowing the adhesive mixture to cure.
In a sixth aspect, the invention provides an adhered assembly comprising:
(1 ) a first substrate;
(2) a second substrate;
(3) an adhesive composition resulting from curing a mixture of:
(A) a first part (Part A) comprising:
(a1 ) at least one compound of general Formula I: where R1 and R2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R3 is Ci to Ce alkyl, and R4 is a divalent C4-8-alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain;
(B) a second part (Part B) comprising:
(b1 ) at least one polyamine, having two or more primary or secondary amine functionalities; wherein at least one of Part A and Part B comprises a catalyst capable of catalyzing the reaction of an amine with a compound of general Formula I; wherein the first and second substrates are in adhesive contact with the adhesive composition sandwiched between them.
In a seventh aspect, the invention provides a method for making a compound of general Formula I, comprising reacting a molecule of Formula III with at least two equivalents of a molecule of Formula IV, in the presence of a catalyst: where R1 and R2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R3 is Ci to Ce alkyl, and R4 is a divalent C4-8- alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain.
Detailed Description of the Invention
The inventors have discovered novel monomers of general Formula I for forming polymers, in particular adhesives, on reaction with a polyamine comprising two or more primary or secondary amine groups.
Definitions and abbreviations
MDI Methyleneb/s(phenyl isocyanate)
HDI Hexamethylene diisocyanate
IPDI isophorone diisocyanate
Pll polyurethane
SEC size exclusion chromatography
RH relative humidity
PDI polydispersity index
TMDI 2,4,4-trimethylhexamethylene diisocyanate
CPEE ethyl 2-oxocyclopentane-1 -carboxylate
RH relative humidity
Molecular weights of polymers as reported herein are reported in Daltons (Da) as number or weight average molecular weights, as determined by gel permeation chromatography (GPC).
Compound of general Formula I In a first aspect, the invention provides a compound of general Formula I: where R1 and R2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R3 is Ci to Ce alkyl, and R4 is a divalent C4-8- alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain.
In a preferred embodiment, R1 and R2 are independently selected from H and Ci to C4 alkyl, more preferably H and Ci to C2 alkyl, particularly preferably R1 and R2 are H.
In a preferred embodiment n is 1 .
In a preferred embodiment, R3 is Ci to C4 alkyl, more preferably R3 is Ci to C2 alkyl, particularly preferably R3 is ethyl.
In a preferred embodiment, R4 is a divalent Ce alkylene radical with 2-5 methyl substituents on the alkylene chain. In a more preferred embodiment, R4 is a Ce alkylene radical with three methyl substituents on the alkylene chain.
In a particularly preferred embodiment, the compound of general Formula I is of Formula I”:
Compounds of general Formula I are made by reacting a diisocyanate of
Formula III: OCN - R4 - NCO HI where R4 is as defined above, including the preferred embodiments, with at least two equivalents of a compound of Formula IV: where R1, R2, R3 and n are defined as above, including the preferred embodiments, in the presence of a catalyst capable of catalyzing the reaction between an NCO group and the molecule of general Formula IV. The catalyst is preferably selected from bismuth and/or zinc catalysts. In a preferred embodiment it is selected from bismuth and/or zinc carboxylates. In a particularly preferred embodiment, the catalyst is a mixture of bismuth and zinc carboxylates.
In an example of the synthesis, 2,4,4-Trimethylhexamethylene diisocyanate (II) is reacted with at least two equivalents of a molecule of Formula IV, in the presence of a bismuth and/or zinc catalyst, in particular a mixture of bismuth and/or zinc catalysts:
In another preferred embodiment of the synthesis, 2,4,4- trimethylhexamethylene diisocyanate (II) is reacted with at least two equivalents of ethyl 2-oxocyclopentane-1 -carboxylate, in the presence of a bismuth and/or zinc catalyst, in particular a mixture of bismuth and/or zinc catalysts:
At least one liquid epoxy resin
Part A of the adhesive of the invention optionally comprises at least one liquid epoxy resin, by which is meant epoxy resins that are liquid at 23°C.
Preferably the liquid epoxy resin has a viscosity at 23°C of not more than 50 Pas, more preferably not more than 25 Pas, more particularly preferably not more than 15 Pas, measured on a Kinexus (Bohlin) equipment using a coneplate 20 mm diameter geometry (4 ° cone) at 23 °C through shear rate up/down curve from 0.1 - 20 s’1.
The liquid epoxy resin is preferably non-rubber modified.
If only a single epoxy resin is present, it is a liquid at 23°C. If two or more epoxy resins are present, the mixture thereof is a liquid at 23°C, although individual epoxy resins within the mixture may be by themselves solids at 23°C.
A wide range of epoxy resins can be used, including those described at column 2 line 66 to column 4 line 24 of U.S. Patent 4,734,332, incorporated herein by reference. The epoxy resin should have an average of at least 1 .8, preferably at least 2.0, epoxide groups per molecule. The epoxy equivalent weight may be, for example, 75 to 350, preferably 140 to 250 and in some embodiments 150 to 225. If a mixture of non-rubber-modified epoxy resins is present, the mixture should have an average epoxy functionality of at least 1 .8, preferably at least 2.0, and an epoxy equivalent weight as in the previous sentence, and more preferably each epoxy resin in the mixture has such an epoxy functionality and epoxy equivalent weight.
Suitable epoxy resins include diglycidyl ethers of polyhydric phenol compounds such as resorcinol, catechol, hydroquinone, biphenol, bisphenol A, bisphenol AP (1 ,1-bis(4-hydroxylphenyl)-1 -phenyl ethane), bisphenol F, bisphenol K and tetramethylbiphenol; diglycidyl ethers of aliphatic glycols such as the diglycidyl ethers of C2-24 alkylene glycols; polyglycidyl ethers of phenol-formaldehyde novolac resins (epoxy novolac resins), alkyl substituted phenol-formaldehyde resins, phenol-hydroxybenzaldehyde resins, cresol- hydroxybenzaldehyde resins, dicyclopentadiene-phenol resins and dicyclopentadiene-substituted phenol resins; and any combination of any two or more thereof.
Suitable epoxy resins include diglycidyl ethers of bisphenol A resins such as are sold by Olin Corporation under the designations D.E.R.® 330, D.E.R.® 331 , D.E.R.® 332, D.E.R.® 383, D.E.R. 661 and D.E.R.® 662 resins.
In a preferred embodiment, the at least one epoxy resin comprises or consists of a reaction product of epichlorohydrin and bisphenol A, having an epoxide equivalent weight of 176-185 g/eq (according to ASTM D-1652), an epoxide percentage of 23.2-24.4 % (according to ASTM D-1652), an epoxide group content of 5,400-5,680 mmol/kg (according to ASTM D-1652), and a viscosity @ 25°C of 7,000-10,000 MPas (according to ASTM D-445).
Epoxy novolac resins can be used. Such resins are available commercially as D.E.N.® 354, D.E.N.® 431 , D.E.N.® 438 and D.E.N.® 439 from Olin Corporation.
Other suitable epoxy resins are cycloaliphatic epoxides. A cycloaliphatic epoxide includes a saturated carbon ring having an epoxy oxygen bonded to two vicinal atoms in the carbon ring, as illustrated by the following structure V: wherein R is an aliphatic, cycloaliphatic and/or aromatic group and n is a number from 1 to 10, preferably from 2 to 4. When n is 1 , the cycloaliphatic epoxide is a monoepoxide. Di- or polyepoxides are formed when n is 2 or more. Mixtures of mono-, di- and/or polyepoxides can be used. Cycloaliphatic epoxy resins as described in U.S. Patent No. 3,686,359, incorporated herein by reference, may be used in the present invention. Cycloaliphatic epoxy resins of particular interest are (3,4-epoxycyclohexyl- methyl)-3,4-epoxy-cyclohexane carboxylate, bis-(3,4-epoxycyclohexyl) adipate, vinylcyclohexene monoxide and mixtures thereof.
Other suitable epoxy resins include oxazolidone-containing compounds as described in U. S. Patent No. 5,112,932. In addition, an advanced epoxyisocyanate copolymer such as those sold commercially as D.E.R. 592 and D.E.R. 6508 (Olin Corporation) can be used.
The liquid epoxy resin is preferably present at 2-20 wt%, more preferably 2-10 wt%, particularly preferably 4-8 wt%, based on the total weight of Part A.
The liquid epoxy resin is preferably present at 12-50 wt%, more preferably 15- 35 wt%, more particularly preferably 20-30 wt%, based on the total organic content of Part A.
In a preferred embodiment, the at least one epoxy resin comprises a reaction product of epichlorohydrin and bisphenol A, having an epoxide equivalent weight of 176-185 g/eq (according to ASTM D-1652), an epoxide percentage of 23.2-24.4 % (according to ASTM D-1652), an epoxide group content of 5,400-5,680 mmol/kg (according to ASTM D-1652), and a viscosity @ 25°C of 7,000-10,000 MPas (according to ASTM D-445), and is present in Part A at 2- 20 wt%, more preferably 2-10 wt%, particularly preferably 4-8 wt%, based on the total weight of Part A.
In another preferred embodiment, the at least one epoxy resin comprises a reaction product of epichlorohydrin and bisphenol A, having an epoxide equivalent weight of 176-185 g/eq (according to ASTM D-1652), an epoxide percentage of 23.2-24.4 % (according to ASTM D-1652), an epoxide group content of 5,400-5,680 mmol/kg (according to ASTM D-1652), and a viscosity @ 25°C of 7,000-10,000 MPas (according to ASTM D-445), and is present in Part A at 12-50 wt%, more preferably 15-35 wt%, more particularly preferably 20-30 wt%, based on the total organic content of Part A.
Thermally-conductive filler
In certain preferred embodiments, where it is desired that the cured adhesive have a thermal conductivity, preferably of 1.5 W/mK or more, Part A and/or Part B may comprise a thermally-conductive filler.
The thermally-conductive filler is not particularly limited. Suitable thermally- conductive fillers are those that have a coefficient of thermal conductivity that is greater than 5 W/m°K, more preferably greater than 10 W/m°K, or particularly preferably greater than 15 WZ m°K. Examples of thermally- conductive fillers include alumina, alumina trihydrate or aluminum trihydroxide (ATH), silicon carbide, boron nitride, diamond, and graphite, and mixtures thereof. Particularly preferred are aluminium trihydroxide (ATH), and aluminium oxide, with ATH being the most preferred. Thermally-conductive fillers may be surface treated or non-treated.
In a preferred embodiment, the thermally-conductive filler has a broad particle size distribution characterized by a ratio of D901 D50 of at or about 3 or more. Particularly preferably the thermally-conductive filler is ATH or aluminium oxide having a broad particle size distribution characterized by a ratio of D901 D50 of at or about 3 or more, most preferably ATH. Also preferred are thermally-conductive fillers having a bimodal particle size distribution. A bimodal distribution is when, for example, the ratio D901 D50 is at or about 3 or more, more preferably at or about 5 or more, more particularly preferably at or about 9 or more. For example, particles having a D50 of 5 to 20 microns and a D90 of 70 to 90 microns, particularly a D50 of 7-9 microns and a D90 of 78-82 microns. Particle size can be determined using laser diffraction. For ATH a suitable solvent is deionized water containing a dispersion aid, such as Na4P2O? x 10 H2O, preferably at 1 g/l. Preferred are aluminium oxide and ATH having a bimodal distribution, particularly ATH. In a preferred embodiment, the thermally-conductive filler is ATH having D901 D50 at or about 3 or more, more preferably at or about 5 or more, particularly preferably at or about 9 or more.
In a preferred embodiment, the thermally-conductive filler is bimodally distributed aluminium trihydroxide (ATH), having the following particle size distribution (by laser diffraction in deionized water containing a dispersion aid, such as Na4P2O? x 10 H2O, preferably at 1 g/l):
D10 (micron) 0.5
D50 (micron) 8 D90 (micron) 80.
The thermally-conductive filler is preferably present in the final adhesive, resulting from mixing Part A and Part B, at a concentration of 30-85 wt%, more preferably 40-85 wt%, more particularly preferably 60-85 wt%, based on the total weight of the adhesive.
In a preferred embodiment, the thermally-conductive filler is aluminium trihydroxide (ATH), used at a concentration of 30-85 wt%, more preferably 40- 85 wt%, more particularly preferably 60-85 wt%, based on the total weight of the adhesive.
In another preferred embodiment, the thermally-conductive filler is bimodally distributed aluminium trihydroxide (ATH), used at a concentration of 30-85 wt%, more preferably 40-85 wt%, more particularly preferably 60-85 wt%, based on the total weight of the adhesive.
In another preferred embodiment, the thermally-conductive filler is aluminium trihydroxide (ATH), having the following particle size distribution (by laser diffraction in deionized water containing a dispersion aid, such as Na4P2O? x 10 H2O, preferably at 1 g/l):
D10 (micron) 0.5
D50 (micron) 8
D90 (micron) 80 used at a concentration of 30-85 wt%, more preferably 40-85 wt%, more particularly preferably 60-85 wt%, based on the total weight of the adhesive.
The concentration of thermally-conductive filler in Part A is preferably 30-85 wt%, more preferably 40-85 wt%, more particularly preferably 60-85 wt%, based on the total weight of Part A.
The concentration of thermally-conductive filler in Part B is preferably 30-85 wt%, more preferably 40-85 wt%, more particularly preferably 60-85 wt%, based on the total weight of Part B.
In a preferred embodiment, the thermally-conductive filler is aluminium trihydroxide (ATH), used in Part A and/or Part B at a concentration of 30-85 wt%, more preferably 40-85 wt%, more particularly preferably 60-85 wt%, based on the total weight of Part A or Part B.
In another preferred embodiment, the thermally-conductive filler is ATH having a bimodal particle size, used in Part A and/or Part B at a concentration of 30-85 wt%, more preferably 40-85 wt%, more particularly preferably 60-85 wt%, based on the total weight of Part A or Part B.
In a preferred embodiment, the thermally-conductive filler is aluminium trihydroxide (ATH), having the following particle size distribution (by laser diffraction in deionized water containing a dispersion aid, such as Na4P2O? x 10 H2O, preferably at 1 g/l):
D10 (micron) 0.5
D50 (micron) 8
D90 (micron) 80 used in Part A and/or Part B at a concentration of 30-85 wt%, more preferably 40-85 wt%, more particularly preferably 60-85 wt%, based on the total weight of Part A or Part B.
At least one polyamine
Component B comprises at least one polyamine, having two or more primary or secondary amine groups.
In a preferred embodiment, the at least one polyamine comprises a triamine.
Preferable the at least one polyamine comprises a polyamine having a molecular weight of at least 400 Da, more preferably at least 1 ,000 Da, more particularly preferably at least 2,000 Da. In a preferred embodiment, the at least one polyamine comprises a polyamine having a molecular weight of 2,000-4,000 Da, more preferably about 3,000 Da.
In another preferred embodiment, the at least one polyamine comprises a polyamine having a molecular weight of at least 300 Da, more preferably at least 350 Da, more particularly preferably at least 400 Da. In a preferred embodiment, the at least one polyamine comprises a polyamine having a molecular weight of 300-500 Da, more preferably about 400-440 Da.
In another preferred embodiment, the polyamine is a triamine having primary amine groups and having a molecular weight of 2,000-4,000 Da, more preferably 3,000 Da.
Examples of suitable compounds having primary and/or secondary amino groups include polyoxyalkylene polyamines having 2 or more amine groups per polyamine, 2 to 4 amine groups per polyamine, or 2 to 3 amine groups per polyamine. Particularly preferred are polyether amines having 3 amine groups.
The polyoxyalkylene poly-amines may have a weight average molecular weight of at least 400 Da, more preferably at least 1 ,000 Da, more particularly preferably at least 2,000 Da. In a preferred embodiment, the polyoxyalkylene polyamine has a molecular weight of 2,000-4,000 Da, more preferably about 3,000 Da. The polyoxyalkylene polyamine may have a weight average molecular weight of about 5,000 or less or about 3,000 or less.
Exemplary polyoxyalkylene polyamines include:
1 . Polyamines based on a propylene oxide polyether backbone. Examples include:
A trifunctional primary amine having an average molecular weight of approximately 440. Its amine groups are located on secondary carbon atoms at the ends of aliphatic polyether chains:
A polypropylene oxide diamine having a molecular weight of about 400:
X = 6.1 .
A difunctional, primary amine with average molecular weight of about 2000.
The primary amine groups are located on secondary carbon atoms at the end of the aliphatic polyether chains: x = 33
A triamine of approximately 3000 molecular weight, of the formula: A triamine of approximately 5,000 g/mol, of the formula:
2. Polyamines based predominantly on a polyethylene oxide polyether backbone. Examples are of the general formula: Such as a polyamine of molecular weight 600 g/mol, where y « 9, (x + z) « 3.6;
A polyamine of molecular weight of 900 g/mol, where y « 12.5, (x + z) « 6;
A polyamine of molecular weight 2,000 g/mol, where y « 39, (x + z) « 6; In a particularly preferred embodiment the at least one polyamine comprises or consists of a triamine of approximately 3000 molecular weight, of the formula:
In another preferred embodiment, the at least one polyamine comprises or consist of a polyetheramine triamine of approximately 440 molecular weight, of the following general structure: Other suitable polyamines include polyamidoamines, which comprise repetitively branched subunits of amide and amine functionality. For example, suitable polyamidoamines are initiated with ammonia or ethylene diamine, reacted by Michael addition with an acrylate ester (for example methyl acrylate), followed by reaction of the ester functionalities with a diamine (such as ethylene diamine). This results in a primary amine terminated polyamine, which may be again reacted by Michael addition, followed by reaction again with a diamine. The first “cycle” is represented schematically below using ethylene diamine and methyl acrylate:
Other suitable polyamines include phenalkamines, which are made by a Mannich reaction between cardanol, formaldehyde and at least one polyamine.
In a preferred embodiment, the at least one polyamine comprises or consists of a mixture of a triamine of approximately 3,000 molecular weight, of the formula: and a polyetheramine triamine of approximately 440 molecular weight, of the following general structure:
The at least one polyamine is preferably present in Part B at 8-30 wt%, more preferably 10-20 wt%, more particularly preferably 12-16 wt%, based on the total weight of Part B.
The at least one polyamine is preferably present in Part B at 80-99 wt%, more preferably 85-95 wt%, particularly preferably 87-92 wt%, based on the organic content of Part B.
In a preferred embodiment, the at least one polyamine comprises or consists of a polyether triamine or mixture of polyether triamines, used in Part B at 8- 30 wt%, more preferably 10-20 wt%, more particularly preferably 12-16 wt%, based on the total weight of Part B.
In another preferred embodiment, the at least one polyamine comprises or consists of a mixture of a polyether triamine of approximately 3,000 Da and a polyether triamine of approximately 440 Da, used in Part B at 8-30 wt%, more preferably 10-20 wt%, more particularly preferably 12-16 wt%, based on the total weight of Part B.
In a preferred embodiment, the at least one polyamine comprises or consists of a polyether triamine or mixture of polyether triamines, used in Part B at SO- 99 wt%, more preferably 85-95 wt%, particularly preferably 87-92 wt%, based on the organic content of Part B.
In another preferred embodiment, the at least one polyamine comprises or consists of a mixture of a polyether triamine of approximately 3,000 Da and a polyether triamine of approximately 440 Da, used in Part B at 80-99 wt%, more preferably 85-95 wt%, particularly preferably 87-92 wt%, based on the organic content of Part B.
At least one catalyst
At least one of Part A and Part B comprises a catalyst capable of catalyzing the reaction of an amine with a compound of general Formula I.
The catalyst is preferably selected from tertiary amine catalysts.
Examples of suitable tertiary amines include 2,4,6-fr/s- (dimethylaminomethyl)phenol, tetramethylguanidine, heptamethylisobiguanide, N,N-dimethylbenzylamine, and 1 ,4- Diazabicyclo[2.2.2]octane.
In a preferred embodiment, the catalyst is 2,4,6-fr/s- (dimethylaminomethyl)phenol.
In another preferred embodiment, the catalyst is 1 ,4- Diazabicyclo[2.2.2]octane.
In a preferred embodiment, the catalyst is a mixture of 2,4,6-fr/s- (dimethylaminomethyl)phenol and 1 ,4-Diazabicyclo[2.2.2]octane.
The catalyst may be present in Part A and/or Part B. In a preferred embodiment, it is present in Part B.
The catalyst is preferably used at 0.05-0.75 wt%, more preferably 0.1 -0.6 wt%, more particularly preferably 0.45-0.55 wt%, based on the total weight of Part B.
In a preferred embodiment, the catalyst comprises or consists of 2,4,6-fr/s- (dimethylaminomethyl)phenol, used at 0.2 to 0.8 w%, more preferably 0.3 to 0.5 wt%, based on the total weight of Part B In another preferred embodiment, the catalyst comprises or consists of 1 ,4- Diazabicyclo[2.2.2]octane, used at 0.02-0.35 wt%, more preferably 0.05-0.15 wt%, based on the total weight of Part A.
In a particularly preferred embodiment, the catalyst comprises or consists of a mixture of 2,4,6-fr/s-(dimethylaminomethyl)phenol and 1 ,4- Diazabicyclo[2.2.2]octane, comprising 0.2 to 0.8 w%, more preferably 0.3 to 0.5 wt% 2,4,6-fr/s-(dimethylaminomethyl)phenol, and 0.02-0.35 wt%, more preferably 0.05-0.15 wt% 1 ,4-Diazabicyclo[2.2.2]octane, based on the total weight of Part B.
Optional ingredients
The adhesive compositions of the invention may optionally comprise a plasticizer, which may be present in Part A or B or both. Examples of plasticizers are esters, in particular diesters and triesters, particularly those having vapour pressures of < 10’4 hPa at 23°C. Examples include dialkyl phthalate esters, alkyl esters of fatty acids, phosphate esters (such as trioctyl phosphate). Diisononylphthalate is particularly preferred. If used, the plasticizer is typically present at 10 to 20 wt%, preferably 12 to 18 wt%, based on the total weight of the adhesive composition. In a particularly preferred embodiment, diisononylphthalate is used at 12 to 18 wt%, more preferably at 16-17 wt%, based on the total weight of the adhesive composition.
The adhesive compositions of the invention may optionally comprise fillers, in addition to any thermally-conductive fillers, which may be present in Part A or B or both, such as carbon black, clay, carbonates (e.g. calcium carbonate), metal hydrates and fumed silica. The fillers are preferably used at from 0-10 wt%, preferably 1-6 wt%, more preferably 2-5 wt%, based on the total weight of the relevant Part.
In a preferred embodiment, the adhesives of the invention comprise carbon black as filler. The carbon black is not particularly limited. Preferred carbon blacks exhibit an oil absorption number of at least 80, preferably at least 90 and more preferably at least 95 cm3 of dibutyl phthalate per 100 g of carbon black, as measured according to ASTM D-2414-09. In addition, the carbon black desirably has an iodine number of at least 80, determined according to ASTM D1510-11.
If used, carbon black is used at 5-30 wt%, more preferably 15 to 25 wt%, based on the total weight of the adhesive composition. In a particularly preferred embodiment, carbon black is used at 15 to 25 wt%, preferably 22 to 23 wt%, based on the total weight of the adhesive composition.
The adhesive compositions of the invention may optionally comprise calcium carbonate in Part A and/or Part B at 0-5 wt%, more preferably 1 to 3 wt%, particularly preferably 1 .5-2.5 wt%, based on the total weight of the relevant Part. The calcium carbonate particles may be untreated or surface modified by treatment with chemicals, such as organic acids or esters of organic acids.
The adhesive compositions of the invention may optionally comprise fumed silica at 0-1 .5 wt%, more preferably 0.5 to 1 wt%, based on the total weight of the adhesive.
If fumed silica is used, the particles may be untreated or surface modified by treatment with chemicals, such as chlorosilane, dichlorosilane, alkyltrialkoxysilane or polydimethylsiloxane.
The adhesive composition of the invention may optionally comprise talc, which may be present in Component A or B or both. In a preferred embodiment, talc is used in Component B at 25 to 40 wt%, more preferably30 to 35 wt%, based on the total weight of Component B.
The adhesive composition of the invention may optionally comprise adhesion promoters, which may be present in Component A or B or both. Suitable adhesion promoters include silanes, such as Gamma- Glycidoxypropyltrimethoxysilane. In a preferred embodiment, Gamma- Glycidoxypropyltrimethoxysilane is used in Part A, at 0.1 to 1 wt%, preferably 0.3-0.6 wt%, based on the total weight of Part A.
The adhesive compositions of the invention may optionally comprise flameretardants and synergists. Examples of suitable flame-retardants and synergists include:
1 . aluminium, zinc and titanium salts of diethylphosphinate, in particular aluminium diethylphosphinate;
2. nitrogen and/or phosphorus containing molecules, such as melamine polyphosphate, melamine pyrophosphate, melamine cyanurate;
3. aluminium and/or zinc phosphites
A preferred combination of flame-retardants/synergists is aluminium diethylphosphinate plus melamine polyphosphate.
The adhesive compositions of the invention may optionally comprise one or more additional stabilizers, for example heat, visible light and UV-stabilizers.
Examples of heat stabilizers include alkyl substituted phenols, phosphites, sebacates and cinnamates. If present, a preferred heat stabilizer is an organophosphite and more specifically trisnonylphenyl phosphite as disclosed in U.S. Pat. No. 6,512,033, incorporated herein by reference. The heat stabilizer may constitute at least 0.01 or at least 0.3 weight percent based on the entire weight of the adhesive composition, up to at most 5 weight percent, up to 2 weight percent or up to 1.0 weight percent. The adhesive composition may be devoid of such a heat stabilizer.
For UV light stabilizers, they include benzophenones and benzotriazoles. Specific UV light absorbers include those from BASF such as TINUVIN™ P, TINUVIN™ 326, TINUVIN™ 213, TINUVIN™ 327, TINUVIN™ 571 , TINUVIN™ 328, and from Cytec such as CYASORB™ UV-9, CYASORB™ UV-24, CYASORB™ UV-1164, CYASORB™ UV-2337, CYASORB™ UV- 2908, CYASORB™ UV-5337, CYASORB™ UV-531 , and CYASORB™ UV- 3638. Among these, TINUVIN™ 571 is preferred. One or more UV light absorbers may constitute at least 0.1 weight percent, at least 0.2 weight percent or at least 0.3 parts by weight of the weight of the adhesive composition, and may constitute up to 3 weight percent, up to 2 weight percent or up to 1 weight percent thereof.
The adhesive composition of the invention may further include one or more visible light stabilizers. Preferred visible light stabilizers included hindered amine visible light stabilizers such as TINUVIN™ 144, TINUVIN™ 622, TINUVIN™ 77, TINUVIN™ 123, TINUVIN™ 765, CHIMASSORB™ 944 available from Cytec; CYASORB™ UV-500, CYASORB™ UV-3581 , CYASORB™ UV-3346, all available from Ciba-Geigy. Among these, TINUVIN™ 765 is preferred choice. The visible light stabilizer(s) may constitute at least 0.1 weight percent, at least 0.2 weight percent or at least 0.3 weight percent of the adhesive composition, and may constitute up to 3 weight percent, up to 2 weight percent or up to 1 .5 weight percent thereof.
Method of manufacture of adhesive composition
Part A and Part B are made by mixing the ingredients, preferably on a planetary mixer or on a dual asymmetric centrifuge. In a first phase the liquid phases are mixed before the solid material is added to the formulation. The formulation was mixed for ca 30 min under vacuum before being filled into cartridges, pails, or drums. The two Parts are stored separately until use, at which point they are mixed.
Method of use
The invention provides a method for adhering two substrates, comprising the steps:
(1) providing a two-part adhesive comprising:
(A) a first part (Part A) comprising:
(a1) at least one compound of general Formula I: where R1 and R2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R3 is Ci to Ce alkyl, and R4 is a divalent C4-8-alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain;
(B) a second part (Part B) comprising:
(b1 ) at least one polyamine, having two or more primary or secondary amine functionalities; wherein at least one of Part A and Part B comprises a catalyst capable of catalyzing the reaction of an amine with a compound of general Formula I, and wherein Part A and Part B are designed to be mixed together to form an adhesive mixture prior to use;
(2) mixing Part A and Part B to produce an adhesive mixture;
(3) applying the adhesive mixture to the first substrate;
(4) bringing the second substrate into adhesive contact with the first substrate; and
(5) allowing the adhesive mixture to cure.
Preferred embodiments of the method use preferred embodiments of the adhesive described herein.
As mentioned above, a preferred way of providing the adhesive of the invention is in airtight containers, such as airtight sealed tubes. The containers are opened immediately prior to use, and the two Parts are mixed.
Part A and Part B may be mixed in any ratio. In a preferred embodiment, the ratio of Part A to Part B is 0.5:1 to 1 :0.5 (v:v), more preferably 1 :1 .5 to 1.5:1 (v:v), particularly preferably 1 :1 (v:v). The adhesive composition of the invention may be applied by any application method, manually or with robotic equipment, including, for example, by spreading, application through a nozzle.
In a preferred embodiment one or both of the first and second substrates are selected from aluminium, glass, steel, e-coated metal, powder coated metal, coated metal, and plastic substrates such as poly(ethyleneterephthalate), polyethylene, polypropylene, polyamide, polyimide, polycarbonate, particularly preferably aluminium.
Curing is carried out by allowing the adhered assembly to sit at room temperature. Full cure is typically observed after 1 -2 days, but a 7 day cure period is often used.
Particularly preferred embodiments
The following are particularly preferred embodiments of the adhesive compositions of the invention:
1 . A compound of general Formula I: where R1 and R2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R3 is Ci to Ce alkyl, and R4 is a divalent C4-8- alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain.
2. A use of a compound of general Formula I: where R1 and R2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R3 is Ci to Ce alkyl, and R4 is a divalent C4-8- alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain, as a monomer in a polymer.
3. A two-part adhesive comprising:
(A) a first part (Part A) comprising:
(a1 ) at least one compound of general Formula I: where R1 and R2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R3 is Ci to Ce alkyl, and R4 is a divalent C4-8-alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain;
(B) a second part (Part B) comprising:
(b1 ) at least one polyamine, having two or more primary or secondary amine functionalities; wherein at least one of Part A and Part B comprises a catalyst capable of catalyzing the reaction of an amine with a compound of general Formula I, and wherein Part A and Part B are designed to be mixed together to form an adhesive mixture prior to use.
4. A kit for forming an adhesive, comprising: (A) a first part (Part A) comprising:
(a1 ) at least one compound of general Formula I: where R1 and R2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R3 is Ci to Ce alkyl, and R4 is a divalent C4-8-alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain;
(B) a second part (Part B) comprising:
(b1 ) at least one polyamine, having two or more primary or secondary amine functionalities; wherein at least one of Part A and Part B comprises a catalyst capable of catalyzing the reaction of an amine with a compound of general Formula I, and wherein Part A and Part B are stored isolated from one another, and are designed to be mixed together to form an adhesive mixture prior to use.
5. A method for adhering a first substrate and a second substrate, comprising the steps:
(1 ) providing a two-part adhesive comprising:
(A) a first part (Part A) comprising:
(a1 ) at least one compound of general Formula I: where R1 and R2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R3 is Ci to Ce alkyl, and R4 is a divalent C4-8-alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain;
(B) a second part (Part B) comprising:
(b1 ) at least one polyamine, having two or more primary or secondary amine functionalities; wherein at least one of Part A and Part B comprises a catalyst capable of catalyzing the reaction of an amine with a compound of general Formula I, and wherein Part A and Part B are designed to be mixed together to form an adhesive mixture prior to use;
(2) mixing Part A and Part B to produce an adhesive mixture;
(3) applying the adhesive mixture to the first substrate;
(4) bringing the second substrate into adhesive contact with the first substrate; and
(5) allowing the adhesive mixture to cure.
6. An adhered assembly comprising:
(1 ) a first substrate;
(2) a second substrate;
(3) an adhesive composition resulting from curing a mixture of:
(A) a first part (Part A) comprising:
(a1 ) at least one compound of general Formula I: where R1 and R2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R3 is Ci to Ce alkyl, and R4 is a divalent C4-8-alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain;
(B) a second part (Part B) comprising: (b1 ) at least one polyamine, having two or more primary or secondary amine functionalities; wherein at least one of Part A and Part B comprises a catalyst capable of catalyzing the reaction of an amine with a compound of general Formula I; wherein the first and second substrates are in adhesive contact with the adhesive composition sandwiched between them.
7. A two-part adhesive comprising:
(A) a first part (Part A) comprising:
(a1 ) at least one compound of general Formula I: where R1 and R2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R3 is Ci to Ce alkyl, and R4 is a divalent C4-8-alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain;
(a2) at least one liquid epoxy resin;
(B) a second part (Part B) comprising:
(b1 ) at least one polyamine, having two or more primary or secondary amine functionalities; wherein at least one of Part A and Part B comprises a catalyst capable of catalyzing the reaction of an amine with a compound of general Formula I, and wherein Part A and Part B are designed to be mixed together to form an adhesive mixture prior to use.
8. A kit for forming an adhesive, comprising:
(A) a first part (Part A) comprising:
(a1 ) at least one compound of general Formula I: where R1 and R2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R3 is Ci to Ce alkyl, and R4 is a divalent C4-8-alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain;
(a2) at least one liquid epoxy resin;
(B) a second part (Part B) comprising:
(b1 ) at least one polyamine, having two or more primary or secondary amine functionalities; wherein at least one of Part A and Part B comprises a catalyst capable of catalyzing the reaction of an amine with a compound of general Formula I, and wherein Part A and Part B are stored isolated from one another, and are designed to be mixed together to form an adhesive mixture prior to use.
9. A method for adhering a first substrate and a second substrate, comprising the steps:
(1 ) providing a two-part adhesive comprising:
(A) a first part (Part A) comprising:
(a1 ) at least one compound of general Formula I: where R1 and R2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R3 is Ci to Ce alkyl, and R4 is a divalent C4-8-alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain;
(a2) at least one liquid epoxy resin;
(B) a second part (Part B) comprising:
(b1 ) at least one polyamine, having two or more primary or secondary amine functionalities; wherein at least one of Part A and Part B comprises a catalyst capable of catalyzing the reaction of an amine with a compound of general Formula I, and wherein Part A and Part B are designed to be mixed together to form an adhesive mixture prior to use;
(2) mixing Part A and Part B to produce an adhesive mixture;
(3) applying the adhesive mixture to the first substrate;
(4) bringing the second substrate into adhesive contact with the first substrate; and
(5) allowing the adhesive mixture to cure.
10. An adhered assembly comprising:
(1 ) a first substrate;
(2) a second substrate;
(3) an adhesive composition resulting from curing a mixture of:
(A) a first part (Part A) comprising:
(a1 ) at least one compound of general Formula I: where R1 and R2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R3 is Ci to Ce alkyl, and R4 is a divalent C4-8-alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain;
(a2) at least one liquid epoxy resin;
(B) a second part (Part B) comprising: (b1 ) at least one polyamine, having two or more primary or secondary amine functionalities; wherein at least one of Part A and Part B comprises a catalyst capable of catalyzing the reaction of an amine with a compound of general Formula I; wherein the first and second substrates are in adhesive contact with the adhesive composition sandwiched between them.
11. A method for making a compound of general Formula I, comprising reacting a molecule of Formula III with at least two equivalents of a molecule of Formula IV, in the presence of a catalyst: where R1 and R2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R3 is Ci to Ce alkyl, and R4 is a divalent C4-8-alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain.
12. Any one preceding embodiment, wherein R1 and R2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R3 is Ci to Ce alkyl, and R4 is a divalent C4-8-alkylene radical with 2-5 C1-3- alkyl substituents on the akylene chain.
13. Any one preceding embodiment, wherein R1 and R2 are independently selected from H and Ci to C4 alkyl, more preferably H and Ci to C2 alkyl, particularly preferably R1 and R2 are H.
14. Any one preceding embodiment, wherein n is 1 . Any one preceding embodiment, wherein R3 is Ci to C4 alkyl, more preferably R3 is Ci to C2 alkyl, particularly preferably R3 is ethyl. Any one preceding embodiment, wherein R4 is a divalent Ce alkylene radical with 2-5 methyl substituents on the alkylene chain. Any one preceding embodiment, wherein R4 is a Ce alkylene radical with three methyl substituents on the alkylene chain. Any one preceding embodiment, wherein the compound of general Formula I is of Formula I”: Any one preceding embodiment, wherein the at least one liquid epoxy resin is selected from epoxy resins that are liquid at 23°C. Any one preceding embodiment, wherein the liquid epoxy resin has a viscosity at 23°C of not greater than 50 Pas, more preferably not greater than 25 Pas, particularly preferably not greater than 15 Pas. Any one preceding embodiment, wherein if only a single epoxy resin is present, it is a liquid at 23°C. Any one preceding embodiment, wherein if two or more epoxy resins are present, the mixture thereof is a liquid at 23°C, although individual epoxy resins within the mixture may be by themselves solids at 23°C. 23. Any one preceding embodiment, wherein the at least one liquid epoxy resin has an average of at least 1.8, preferably at least 2.0, epoxide groups per molecule.
24. Any one preceding embodiment, wherein the at least one liquid epoxy resin comprises an epoxy resin having an epoxy equivalent weight of 75 to 350 g/eq, preferably 140 to 250 g/eq, more preferably 150 to 225 g/eq.
25. Any one preceding embodiment, wherein the epoxy resin is selected from diglycidyl ethers of polyhydric phenol compounds such as resorcinol, catechol, hydroquinone, biphenol, bisphenol A, bisphenol AP (1 ,1 -bis(4-hydroxylphenyl)-1 -phenyl ethane), bisphenol F, bisphenol K and tetramethylbiphenol; diglycidyl ethers of aliphatic glycols such as the diglycidyl ethers of C2-24 alkylene glycols; polyglycidyl ethers of phenol-formaldehyde novolac resins (epoxy novolac resins), alkyl substituted phenol-formaldehyde resins, phenol-hydroxybenzaldehyde resins, cresol-hydroxybenzaldehyde resins, dicyclopentadiene-phenol resins and dicyclopentadiene-substituted phenol resins; and any combination of any two or more thereof.
26. Any one preceding embodiment, wherein the at least one epoxy resin comprises or consists of a reaction product of epichlorohydrin and bisphenol A, having an epoxide equivalent weight of 176-185 g/eq (according to ASTM D-1652), an epoxide percentage of 23.2-24.4 % (according to ASTM D-1652), an epoxide group content of 5,400-5,680 mmol/kg (according to ASTM D-1652), and a viscosity @ 25°C of 7,000-10,000 MPas (according to ASTM D-445).
27 Any one preceding embodiment, wherein the liquid epoxy resin is present at 2-20 wt%, more preferably 2-10 wt%, particularly preferably 4-8 wt%, based on the total weight of Part A. 28. Any one preceding embodiment, wherein the liquid epoxy resin is present at 12-50 wt%, more preferably 15-35 wt%, more particularly preferably 20-30 wt%, based on the total organic content of Part A.
29. Any one preceding embodiment, wherein the at least one epoxy resin comprises a reaction product of epichlorohydrin and bisphenol A, having an epoxide equivalent weight of 176-185 g/eq (according to ASTM D-1652), an epoxide percentage of 23.2-24.4 % (according to ASTM D-1652), an epoxide group content of 5,400-5,680 mmol/kg (according to ASTM D-1652), and a viscosity @ 25°C of 7,000-10,000 MPas (according to ASTM D-445), and is present in Part A at 2-20 wt%, more preferably 2-10 wt%, particularly preferably 4-8 wt%, based on the total weight of Part A.
30. Any one preceding embodiment, wherein the at least one epoxy resin comprises a reaction product of epichlorohydrin and bisphenol A, having an epoxide equivalent weight of 176-185 g/eq (according to ASTM D-1652), an epoxide percentage of 23.2-24.4 % (according to ASTM D-1652), an epoxide group content of 5,400-5,680 mmol/kg (according to ASTM D-1652), and a viscosity @ 25°C of 7,000-10,000 MPas (according to ASTM D-445), and is present in Part A at 12-50 wt%, more preferably 15-35 wt%, more particularly preferably 20-30 wt%, based on the total organic content of Part A.
31 . Any one preceding embodiment, wherein Part A and/or Part B comprise a thermally-conductive filler.
32. Any one preceding embodiment, wherein Part A and/or Part B comprise a thermally-conductive filler selected from those that have a coefficient of thermal conductivity that is greater than 5 W/m°K, more preferably greater than 10 W/m°K, or particularly preferably greater than 15 W/ m°K. Any one preceding embodiment, wherein Part A and/or Part B comprise a thermally-conductive filler, wherein the thermally- conductive filler is selected from alumina, alumina trihydrate or aluminum trihydroxide (ATH), silicon carbide, boron nitride, diamond, and graphite, and mixtures thereof. Any one preceding embodiment, wherein Part A and/or Part B comprise a thermally-conductive filler, and the thermally-conductive filler is selected from aluminium trihydroxide (ATH), and aluminium oxide, with ATH being the most preferred. Any one preceding embodiment, wherein Part A and/or Part B comprise a thermally-conductive filler, and the thermally-conductive filler has a broad particle size distribution characterized by a ratio of D90 I D50 of at or about 3 or more. Any one preceding embodiment, wherein Part A and/or Part B comprise a thermally-conductive filler, and the thermally-conductive filler is ATH or aluminium oxide having a broad particle size distribution characterized by a ratio of D901 D50 of at or about 3 or more, most preferably ATH. Any one preceding embodiment, wherein Part A and/or Part B comprise a thermally-conductive filler, and the thermally-conductive filler has a bimodal particle size distribution. Any one preceding embodiment, wherein Part A and/or Part B comprise a thermally-conductive filler, and thermally-conductive filler has ratio D90 1 D50 is at or about 3 or more, more preferably at or about 5 or more, more particularly preferably at or about 9 or more. Any one preceding embodiment, wherein Part A and/or Part B comprise a thermally-conductive filler, and the thermally-conductive filler is bimodally distributed aluminium trihydroxide (ATH), having the following particle size distribution (by laser diffraction in deionized water containing a dispersion aid, such as Na4P2O? x 10 H2O, preferably at 1 g/l):
D10 (micron) 0.5
D50 (micron) 8
D90 (micron) 80. Any one preceding embodiment, wherein Part A and/or Part B comprise a thermally-conductive filler, and the thermally-conductive filler is present in the final adhesive, resulting from mixing Part A and Part B, at a concentration of 30-85 wt%, more preferably 40-85 wt%, more particularly preferably 60-85 wt%, based on the total weight of the adhesive. Any one preceding embodiment, wherein Part A and/or Part B comprise a thermally-conductive filler, and the thermally-conductive filler is aluminium trihydroxide (ATH), used at a concentration of 30-85 wt%, more preferably 40-85 wt%, more particularly preferably 60-85 wt%, based on the total weight of the adhesive. Any one preceding embodiment, wherein Part A and/or Part B comprise a thermally-conductive filler, and the thermally-conductive filler is bimodally distributed aluminium trihydroxide (ATH), used at a concentration of 30-85 wt%, more preferably 40-85 wt%, more particularly preferably 60-85 wt%, based on the total weight of the adhesive. Any one preceding embodiment, wherein Part A and/or Part B comprise a thermally-conductive filler, and the thermally-conductive filler is aluminium trihydroxide (ATH), having the following particle size distribution (by laser diffraction in deionized water containing a dispersion aid, such as Na4P2O? x 10 H2O, preferably at 1 g/l):
D10 (micron) 0.5 D50 (micron) 8 Doo (micron) 80 used at a concentration of 30-85 wt%, more preferably 40-85 wt%, more particularly preferably 60-85 wt%, based on the total weight of the adhesive. Any one preceding embodiment, wherein Part A and/or Part B comprise a thermally-conductive filler, and the concentration of thermally-conductive filler in Part A is 30-85 wt%, more preferably 40- 85 wt%, more particularly preferably 60-85 wt%, based on the total weight of Part A. Any one preceding embodiment, wherein Part A and/or Part B comprise a thermally-conductive filler, and the concentration of thermally-conductive filler in Part B is 30-85 wt%, more preferably 40- 85 wt%, more particularly preferably 60-85 wt%, based on the total weight of Part B. Any one preceding embodiment, wherein Part A and/or Part B comprise a thermally-conductive filler, and the thermally-conductive filler is aluminium trihydroxide (ATH), used in Part A and/or Part B at a concentration of 30-85 wt%, more preferably 40-85 wt%, more particularly preferably 60-85 wt%, based on the total weight of Part A or Part B. Any one preceding embodiment, wherein Part A and/or Part B comprise a thermally-conductive filler, and the thermally-conductive filler is ATH having a bimodal particle size, used in Part A and/or Part B at a concentration of 30-85 wt%, more preferably 40-85 wt%, more particularly preferably 60-85 wt%, based on the total weight of Part A or Part B. Any one preceding embodiment, wherein Part A and/or Part B comprise a thermally-conductive filler, and the thermally-conductive filler is aluminium trihydroxide (ATH), having the following particle size distribution (by laser diffraction in deionized water containing a dispersion aid, such as Na4P2O? x 10 H2O, preferably at 1 g/l): D10 (micron) 0.5 D50 (micron) 8 D90 (micron) 80 used in Part A and/or Part B at a concentration of 30-85 wt%, more preferably 40-85 wt%, more particularly preferably 60-85 wt%, based on the total weight of Part A or Part B.
49. Any one preceding embodiment, wherein the at least one polyamine comprises a polyamine having a molecular weight of at least 400 Da, more preferably at least 1 ,000 Da, more particularly preferably at least 2,000 Da.
50. Any one preceding embodiment, wherein the at least one polyamine comprises a polyamine having a molecular weight of 2,000-4,000 Da, more preferably about 3,000 Da.
51 . Any one preceding embodiment, wherein the at least one polyamine comprises a polyamine having a molecular weight of at least 300 Da, more preferably at least 350 Da, more particularly preferably at least 400 Da.
52. Any one preceding embodiment, wherein the at least one polyamine comprises a polyamine having a molecular weight of 300-500 Da, more preferably about 400-440 Da.
53. Any one preceding embodiment, wherein the polyamine comprises a triamine having primary amine groups and having a molecular weight of 2,000-4,000 Da, more preferably 3,000 Da.
54. Any one preceding embodiment, wherein the polyamine comprises a polyoxyalkylene polyamine having 2 or more amine groups per polyamine, 2 to 4 amine groups per polyamine, or 2 to 3 amine groups per polyamine.
55. Any one preceding embodiment, wherein the polyamine comprises a polyether amine having 3 amine groups.
56. Any one preceding embodiment, wherein the polyamine comprises a polyamine based on a propylene oxide polyether backbone.
57. Any one preceding embodiment, wherein the polyamine comprises a trifunctional primary amine having an average molecular weight of approximately 440.
58. Any one preceding embodiment, wherein the polyamine comprises a polyetheramine having the following structure:
59. Any one preceding embodiment, wherein the polyamine comprises a triamine of approximately 3000 molecular weight, of the formula: Any one preceding embodiment, wherein the at least one polyamine comprises or consists of a mixture of a triamine of approximately 3000 molecular weight, of the formula: and a polyether triamine of approximately 440 molecular weight, of the following general structure: Any one preceding embodiment, wherein the at least one polyamine is present in Part B at 8-30 wt%, more preferably 10-20 wt%, more particularly preferably 12-16 wt%, based on the total weight of Part B. Any one preceding embodiment, wherein the at least one polyamine is present in Part B at 80-99 wt%, more preferably 85-95 wt%, particularly preferably 87-92 wt%, based on the organic content of Part B. Any one preceding embodiment, wherein the at least one polyamine comprises or consists of a polyether triamine or mixture of polyether triamines, used in Part B at 8-30 wt%, more preferably 10-20 wt%, more particularly preferably 12-16 wt%, based on the total weight of Part B.
64. Any one preceding embodiment, wherein the at least one polyamine comprises or consists of a mixture of a polyether triamine of approximately 3,000 Da and a polyether triamine of approximately 440 Da, used in Part B at 8-30 wt%, more preferably 10-20 wt%, more particularly preferably 12-16 wt%, based on the total weight of Part B.
65. Any one preceding embodiment, wherein the at least one polyamine comprises or consists of a polyether triamine or mixture of polyether triamines, used in Part B at 80-99 wt%, more preferably 85-95 wt%, particularly preferably 87-92 wt%, based on the organic content of Part B.
66. Any one preceding embodiment, wherein the at least one polyamine comprises or consists of a mixture of a polyether triamine of approximately 3,000 Da and a polyether triamine of approximately 440 Da, used in Part B at 80-99 wt%, more preferably 85-95 wt%, particularly preferably 87-92 wt%, based on the organic content of Part B.
67. Any one preceding embodiment, wherein the catalyst is selected from tertiary amine catalysts.
68. Any one preceding embodiment, wherein the catalyst is selected from 2,4,6-fr/s-(dimethylaminomethyl)phenol, tetramethylguanidine, heptamethylisobiguanide, N,N-dimethylbenzylamine, 1 ,4- Diazabicyclo[2.2.2]octane, and mixtures of these.
69. Any one preceding embodiment, wherein the catalyst comprises or consists of 2,4,6-fr/s-(dimethylaminomethyl)phenol. Any one preceding embodiment, wherein the catalyst comprises or consists of 1 ,4-Diazabicyclo[2.2.2]octane. Any one preceding embodiment, wherein the catalyst is a mixture of 2,4,6-fr/s-(dimethylaminomethyl)phenol and 1 ,4- Diazabicyclo[2.2.2]octane. Any one preceding embodiment, wherein the catalyst is present in Part A and/or Part B. Any one preceding embodiment, wherein the catalyst is present in Part B. Any one preceding embodiment, wherein the catalyst is used at 0.05- 0.75 wt%, more preferably 0.1 -0.6 wt%, more particularly preferably 0.45-0.55 wt%, based on the total weight of Part B. Any one preceding embodiment, wherein the catalyst comprises or consists of 2,4,6-fr/s-(dimethylaminomethyl)phenol, used at 0.2 to 0.8 w%, more preferably 0.3 to 0.5 wt%, based on the total weight of Part B. Any one preceding embodiment, wherein the catalyst comprises or consists of 1 ,4-Diazabicyclo[2.2.2]octane, used at 0.02-0.35 wt%, more preferably 0.05-0.15 wt%, based on the total weight of Part A. Any one preceding embodiment, wherein the catalyst comprises or consists of a mixture of 2,4,6-fr/s-(dimethylaminomethyl)phenol and 1 ,4-Diazabicyclo[2.2.2]octane, comprising 0.2 to 0.8 w%, more preferably 0.3 to 0.5 wt% 2,4,6-fr/s-(dimethylaminomethyl)phenol, and 0.02-0.35 wt%, more preferably 0.05-0.15 wt% 1 ,4- Diazabicyclo[2.2.2]octane, based on the total weight of Part B. Any one preceding embodiment, wherein Part A and/or Part B comprise a plasticizer. Any one preceding embodiment, wherein Part A and/or Part B comprise fillers, in addition to any thermally-conductive fillers. Any one preceding embodiment, wherein Part A and/or Part B comprise fillers selected from carbon black, clay, carbonates (e.g. calcium carbonate), metal hydrates, fumed silica and mixtures of these. Any one preceding embodiment, wherein Part A and/or Part B comprise fillers used at from 0-10 wt%, preferably 1-6 wt%, more preferably 2-5 wt%, based on the total weight of the relevant Part. Any one preceding embodiment, wherein Part A and/or Part B comprise calcium carbonate at 0-5 wt%, more preferably 1 to 3 wt%, particularly preferably 1 .5-2.5 wt%, based on the total weight of the relevant Part. Any one preceding embodiment, wherein Part A and/or Part B comprise one or more adhesion promoters. Any one preceding embodiment, wherein Part A and/or Part B comprise one or more adhesion promoters in the form of one or more silanes. Any one preceding embodiment, wherein Part A and/or Part B comprise one or more adhesion promoters in the form of one or more aminosilanes, mercaptosilanes and epoxy silanes. Any one preceding embodiment, wherein Part A and/or Part B comprise gamma-glycidoxypropyltrimethoxysilane. Any one preceding embodiment, wherein Part A comprises gamma- glycidoxypropyltrimethoxysilane, at 0.1 to 1 wt%, preferably 0.3-0.6 wt%, based on the total weight of Part A. EXAMPLES
GF210 and GF213 prepolymer preparation (conventional, CPEE-capped prepolymer)
Using the quantities listed in Table 3, the following procedure was carried out: Voranol 1010 was added to a lab reactor and heated under stirring and vacuum to 130°C. When the temperature was reached, the mixture was cooled down with stirring to 70°C. The vacuum was broken and HDI was added. The mixture was stirred for two minutes under nitrogen, and the bismuth catalyst (TiB 718) was added. The mixture was allowed to react for 45 minutes under stirring and nitrogen at 85°C bath temperature. The mixture was then cooled to 60°C under stirring and nitrogen. The CPEE was added, and the mixture was allowed to react for 45 minutes under stirring and nitrogen at 85°C bath temperature. The isocyanate content was checked, and when 0, the mixture was stirred for an additional 20 minutes under vacuum at 85°C. The prepolymer was stored under inert atmosphere until use.
CPEE-functionalized diisocyanate preparation (GF216, GF217, GF 218, GF219)
Using the quantities listed in Table 2, the following procedure was carried out: The diisocyanate and bismuth catalyst (TiB 718) were added to a lab reactor and mixed under nitrogen at 23°C. The CPEE was added portion-wise, taking care that the temperature did not exceed 60°C. After all the CPEE was added the mixture was stirred under vacuum at bath temperature 70°C for 45 minutes. The CPEE-functionalized diisocyanates were stored under inert atmosphere until use.
Discussion of CPEE-functionalised diisocyanates
When MDI is functionalised with CPEE (GF216), the resulting product is solid at room temperature. This is undesirable for a monomer for an adhesive.
The same is true when HDI is functionalised with CPEE (GF217).
When IPDI is functionalised with CPEE (GF218), the result is a liquid, however the viscosity at 23°C is high (310 Pa.s), making it inappropriate for use as a monomer for an adhesive. When 2,4,4-trimethylhexamethylene diisocyanate is functionalised with CPEE, the result is a tractable liquid of suitable viscosity for use as a monomer for an adhesive.
Adhesive formulations Using the ingredients listed in Table 3, the formulations were mixed on a planetary mixer or on a dual asymmetric centrifuge. In a first phase the liquid phases were mixed before the solid material was added to the formulation. The formulation was mixed for ca 30 min under vacuum before being filled into cartridges, pails, or drums.
1 An NCO-terminated prepolymer based on diphenylmethane diisocyanate (MDI) and polypropylene glycol), with equivalent weight of 251-274 g/eq, and a functionality of approximately 2.8 Test methods
Viscosity
Rheology measurements were performed on an Anton Paar MC 302 rheometer with a parallel plate geometry. 25 mm diameter plates were used, the gap was fixed at 0.5 mm. The material is brought between the two plates and then a shear rate test was performed from 0.001 to 20 1/s. The viscosity at 10 s’1 is reported.
Press-in Force
The press-in force is measured with a tensiometer (Zwick). The material is placed on a metal surface. An aluminium piston with 40 mm diameter is placed on top and the material is compressed to 5 mm (initial position). The material is then compressed to 0.3 mm with 1 mm/s velocity and a force deflection curve is recorded. The force (N) at 0.5 mm thickness is considered as the press-in force, and is reported in Table 3.
Thermal conductivity
Thermal conductivity is measured according to ASTM 5470-12 on a thermal interface material tester from ZFW Stuttgart. The tests are performed in Spaltplus mode at a thickness of between 1.8-1.2 mm. The material is considered as Type I (viscous liquids) as described in ASTM 5470-12. The upper contact is heated to ca 40°C and the lower contact to ca 10°C, resulting in a sample temperature of ca 25°C. The A and B component are mixed with a static mixer when applied from a manual cartridge system.
GPC
Molecular Weight data of the polyurethane prepolymers were measured by gel permeation chromatography (GPC) with a Malvern Viscothek GPC max equipment. EMSLIRE - THF (ACS , Reag. Ph EUR for analysis) was used as an eluent, PL GEL MIXED D ( Agilent , 300*7.5 mm , 5 pm ) was used as a column, and MALVERN Viscotek TDA was used as a detector . Lap shear strength
Aluminium substrates (from Novelis, AA6061 T6 1.92mm MF noPT no lub) (140 x 25 mm, 1.9 mm thick) were used. The substrates were cleaned with isopropanol before use. The adhesive was applied on one substrate, and the second substrate was joined within 5 minutes. The thickness was adjusted to 1 .0 mm, the overlap area was 25 mm x 25 mm. The material was cured and rested for 7 days at 23°C, 50 % relative humidity, before the lap shear tests were performed. The lap shear samples were then mounted in a tensiometer and the lap shear tests were performed using a pull speed of 10 mm/min. The force deflection curve was recorded and the strength at break was reported as lap shear strength.
NCO content
NCO measurements were performed according to ASTM D2572 - 97 (Reapproved 2010) (GEX081 ). This test method is applicable for liquids containing isocyanates. There are included monomers (e.g. methylendiphenyldiisocyanate MDI), prepolymers and adhesive formulations. The isocyanate (NCO) sample reacts with an excess of dibutylamine to form the corresponding urea. The NCO content was determined from the amount of dibutylamine consumed in the reaction. The result is reported as percent NCO (weight percent).
Results
As mentioned above, it can be seen from the results in Table 2, of the diisocyanates tested, only the branched aliphatic diisocyanate, TMDI, yielded a reaction product with CPEE that was a liquid with suitable viscosity to be used as a “prepolymer”.
From the data in Table 3, it can be seen that the highest lap shear strength was obtained when a molecule of general Formula I (TMDI-CPEE) was used in Part A, in combination with a liquid epoxy resin (DER 330). In contrast, a conventional polyurethane prepolymer (Desmodur E21 , see CE1 and CE2), gave significantly lower lap shear strength both with (CE2) and without epoxy (CE1 ).

Claims

Claims
1 . A compound of general Formula I: where R1 and R2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R3 is Ci to Ce alkyl, and R4 is a divalent C4-8- alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain. 2. A use of a compound of general Formula I: where R1 and R2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R3 is Ci to Ce alkyl, and R4 is a divalent C4-8- alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain, as a monomer in a polymer.
3. A two-part adhesive comprising:
(A) a first part (Part A) comprising:
(a1 ) at least one compound of general Formula I: where R1 and R2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R3 is Ci to Ce alkyl, and R4 is a divalent C4-8-alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain;
(B) a second part (Part B) comprising:
(b1 ) at least one polyamine, having two or more primary or secondary amine functionalities; wherein at least one of Part A and Part B comprises a catalyst capable of catalyzing the reaction of an amine with a compound of general Formula I, and wherein Part A and Part B are designed to be mixed together to form an adhesive mixture prior to use.
4. A method for adhering a first substrate and a second substrate, comprising the steps:
(1 ) providing a two-part adhesive comprising:
(A) a first part (Part A) comprising:
(a1 ) at least one compound of general Formula I: where R1 and R2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R3 is Ci to Ce alkyl, and R4 is a divalent C4-8-alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain; (B) a second part (Part B) comprising:
(b1 ) at least one polyamine, having two or more primary or secondary amine functionalities; wherein at least one of Part A and Part B comprises a catalyst capable of catalyzing the reaction of an amine with a compound of general Formula I, and wherein Part A and Part B are designed to be mixed together to form an adhesive mixture prior to use;
(2) mixing Part A and Part B to produce an adhesive mixture;
(3) applying the adhesive mixture to the first substrate;
(4) bringing the second substrate into adhesive contact with the first substrate; and
(5) allowing the adhesive mixture to cure.
5. A method for making a compound of general Formula I, comprising reacting a molecule of Formula III with at least two equivalents of a molecule of Formula IV, in the presence of a catalyst: where R1 and R2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R3 is Ci to Ce alkyl, and R4 is a divalent C4-8-alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain.
6. Any one preceding claim, wherein R1 and R2 are independently selected from hydrogen and Ci to Ce alkyl, n is an integer from 1 to 2, R3 is Ci to Ce alkyl, and R4 is a divalent C4-8-alkylene radical with 2-5 Ci-3-alkyl substituents on the akylene chain.
7. Any one preceding claim, wherein R1 and R2 are independently selected from H and Ci to C4 alkyl, more preferably H and Ci to C2 alkyl, particularly preferably R1 and R2 are H.
8. Any one preceding claim, wherein n is 1.
9. Any one preceding claim, wherein R3 is Ci to C4 alkyl, more preferably R3 is Ci to C2 alkyl, particularly preferably R3 is ethyl.
10. Any one preceding claim, wherein R4 is a divalent Ce alkylene radical with 2-5 methyl substituents on the alkylene chain.
11 . Any one preceding claim, wherein R4 is a Ce alkylene radical with three methyl substituents on the alkylene chain.
12. Any one preceding claim, wherein the compound of general Formula I is of Formula I”:
13. Any one preceding claim, wherein the two-part adhesive comprises, in Part A, at least one liquid epoxy resin (a2).
14. Claim 13, wherein the at least one liquid epoxy resin is selected from epoxy resins that are liquid at 23°C.
15. Claim 13 or 14, wherein the at least one epoxy resin comprises or consists of a reaction product of epichlorohydrin and bisphenol A.
16. Claim 13, 14 or 15, wherein the liquid epoxy resin is present at 12-50 wt%, more preferably 15-35 wt%, more particularly preferably 20-30 wt%, based on the total organic content of Part A.
17. Any one preceding claim, wherein the at least one polyamine comprises a polyamine having a molecular weight of at least 400 Da, more preferably at least 1 ,000 Da, more particularly preferably at least 2,000 Da.
18. Any one preceding claim, wherein the at least one polyamine comprises a mixture of a polyamine having a molecular weight of 2,000-4,000 Da, more preferably about 3,000 Da, and a polyamine having a molecular weight of 300-500 Da, more preferably about 400- 440 Da.
19. Any one preceding claim, wherein the at least one polyamine is present in Part B at 80-99 wt%, more preferably 85-95 wt%, particularly preferably 87-92 wt%, based on the organic content of Part B.
20. Any one preceding claim, wherein the catalyst is selected from tertiary amine catalysts.
EP23754911.8A 2022-10-06 2023-07-20 Two-component adhesive composition Pending EP4598975A1 (en)

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US3686359A (en) 1969-12-19 1972-08-22 Union Carbide Corp Curable polyepoxide compositions
CA1259897A (en) 1985-04-02 1989-09-26 Madan M. Bagga Bonding process using curable epoxide resin adhesive
GB8912952D0 (en) 1989-06-06 1989-07-26 Dow Rheinmuenster Epoxy-terminated polyoxazolidones,process for the preparation thereof and electrical laminates made from the epoxy-terminated polyoxazolidones
AU2983200A (en) 1999-02-05 2000-08-25 Dow Chemical Company, The Polyurethane sealant compositions
DE10260299A1 (en) * 2002-12-20 2004-07-01 Bayer Ag Reactive systems, their manufacture and their use
DE102004043342A1 (en) * 2004-09-08 2006-03-09 Bayer Materialscience Ag Blocked polyurethane prepolymers as adhesives
DE102007012908A1 (en) * 2007-03-19 2008-09-25 Momentive Performance Materials Gmbh New polyamide-polysiloxane compounds
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