WO2012134735A1 - Adhésifs structuraux à base de méthacrylate et exempts de peroxyde - Google Patents

Adhésifs structuraux à base de méthacrylate et exempts de peroxyde Download PDF

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Publication number
WO2012134735A1
WO2012134735A1 PCT/US2012/027865 US2012027865W WO2012134735A1 WO 2012134735 A1 WO2012134735 A1 WO 2012134735A1 US 2012027865 W US2012027865 W US 2012027865W WO 2012134735 A1 WO2012134735 A1 WO 2012134735A1
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Prior art keywords
carbon atoms
adhesive system
structural adhesive
methacrylate
substrates
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PCT/US2012/027865
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English (en)
Inventor
Frank Tran
Surendar N. Kaul
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Huntsman Advanced Materials Americas Llc
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Publication of WO2012134735A1 publication Critical patent/WO2012134735A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C08F255/023—On to modified polymers, e.g. chlorinated polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate

Definitions

  • the present invention is directed to multipart structural adhesives which are capable of safely and sufficiently bonding substrates. More particularly, the present invention relates to two-part, peroxide-free structural adhesive systems that exhibit high stability without impairing adhesion properties.
  • Structural adhesives including acrylic adhesive compositions, have been used in a variety of applications to bond various substrates, such as metal or plastic. These structural adhesives are generally supplied as two components that are mixed just prior to application. Structural adhesives known in the industry include, for example:
  • U.S. Pat. Nos. 4,112,013 and 3,890,407 which disclose two-part adhesives that may contain (A) a solution of a polymerizable vinyl monomer in either chlorosulfonated polyethylene or sulfonyl chloride + chlorinated polyethylene and (B) a peroxide;
  • U.S. Pat. No. 4,403,058 which is directed to a two-part adhesive including an elastomer in either (A) an acrylic monomer, an organic peroxide, and a metal salt liquid solution and/or (B) an acrylic monomer and a curing accelerator liquid solution;
  • U.S. Pat. No. 5,264,525 which discloses a two-part adhesive composition containing (A) an acrylic monomer, chlorosulfonated polyethylene and a peroxide and (B) a condensation reaction product of an aldehyde and amine and an epoxy resin; and
  • U.S. Pat. No. 5,313,998 which relates to a two-part adhesive having (A) an acrylic and a peroxide and (B) a condensation reaction product of an aldehyde and amine and a copper salt and wherein an acid phosphate is added to either solution (A) or to both solutions (A) and (B).
  • U.S. Pat. No. 6,869,497 teaches a two part adhesive including (A) an acrylic monomer, a metal molybdate, and acrylic or methacrylic acid and (B) peroxide while U.S. Pat. Nos. 7,348,385 and 7,479,528 teach two part adhesives containing (A) acrylic monomer, chlorosulphonated polymer, and a peroxide and (B) a cycloheteroatom zirconate or titannate.
  • Known structural adhesives exhibit some shortcomings, for example, they exhibit inadequate heat stability, they contain hazardous peroxides, they exhibit slow cure, and/or have less than desired shear strengths. Therefore, there is a need for a structural adhesive that is environmentally friendly, storage-stable, and can be conveniently formulated and applied to provide strong bonds over a desired time range.
  • the present disclosure relates to a multipart structural adhesive system that is substantially free of peroxide.
  • the multipart adhesive system employs a part (A) containing a methacrylic component and a chlorosulfonated polymer and a part (B) containing an aldehyde-amine condensate and a metal quinolate.
  • the multipart structural adhesive system of the present disclosure may be used to bond a variety of substrates.
  • this disclosure provides a method for adhering a first surface to a second surface which includes: mixing a part (A) and a part (B) to form a curable composition, where the curable composition is substantially free of peroxide and where part (A) comprises a methacrylic component and a chlorosulfonated polymer and part (B) comprises an aldehyde-amine condensate and a metal quinolate; applying the curable composition to at least the first surface, pressing the second surface and the first surface together so that the curable composition is between the two surfaces for a time sufficient to effect curing of the curable composition.
  • the curing occurs at room temperature.
  • compositions claimed herein through use of the term “comprising” may include any additional additive, adjuvant, or compound, unless stated to the contrary.
  • the term, “consisting essentially of if appearing herein excludes from the scope of any succeeding recitation any other component, step or procedure, excepting those that are not essential to operability and the term “consisting of, if used, excludes any component, step or procedure not specifically delineated or listed.
  • alkyl refers to a group derived from an aliphatic hydrocarbon and includes linear, branched or a cyclic group, which may be substituted or unsubstituted.
  • alkenyl refers to a straight-chain or branched hydrocarbon residue containing at least one carbon-carbon double bond which may be substituted or unsubstituted.
  • alkylaryl refers to a group having both alkyl and aryl moieties.
  • alkoxy' refers to an alkyl group which is attached through an oxygen atom.
  • aryl refers to a group derived from an aromatic hydrocarbon which may be substituted or unsubstituted.
  • aryloxy refers to an aryl group which is attached through an oxygen atom.
  • cycloalkyl refers to refers to a monovalent carbocyclic radical of 3 to 10 carbon atoms, preferably 3 to 6 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl.
  • halogen refers to fluorine, chlorine, bromine, and iodine.
  • hetero indicates that one or more carbon atoms have been replaced with a different atom.
  • hydroxyl refers to an -OH group.
  • 8-hydroxyquinolate refers to a ligand derived from the compound 8- hydroxyquinoline, where the hydrogen on the hydroxy group is removed and the oxygen is coordinated to a metal.
  • the term “substantially free” means, when used with reference to the substantial absence of a material in an adhesive system or curable composition, that such a material is present, if at all, as an incidental impurity or by-product. In other words, the material does not affect the properties of the adhesive system or curable composition.
  • the multipart structural adhesive system is a two-part structural adhesive system that is substantially free of peroxide, employing a part (A) containing a methacrylic component and a chlorosulfonated polymer, and a part (B) containing an aldehyde-amine condensate and a metal quinolate.
  • A a methacrylic component and a chlorosulfonated polymer
  • B a part containing an aldehyde-amine condensate and a metal quinolate.
  • the multipart structural adhesive systems of the present disclosure exhibit cure properties similar to those observed in conventional two-part adhesive systems, yet are peroxide-free thus eliminating any environmental concerns.
  • the multipart structural adhesive systems of the present disclosure exhibit both improved storage stability, and upon curing, improved lap shear strength as compared to peroxide-containing adhesive systems.
  • part (A) of the two-part structural adhesive system includes a methacrylic component.
  • the methacrylic component may be any suitable material which contains at least one group having the general structural formula:
  • H 2 C CGC0 2 R
  • G is hydrogen, halogen, or a C 1 -C4 alkyl and R is a Ci-C 2 o alkyl, C 3 -C 10 cycloalkyl, C 2 -C 24 alkenyl, C7-C 30 alkylaryl or C 6 -C 20 aryl group, any of which may be optionally substituted by oxygen, halogen, carbonyl, hydroxyl, epoxy, ester, carboxylic acid, urea, urethane, carbonate, amine, amide, sulfur, or sulfone.
  • the methacrylic component contains a methacryloxy group.
  • the term "methacryloxy" or “methacrylate” refers to both acrylate and methacrylate, in which G is hydrogen or methyl, respectively.
  • the methacrylic component may be present in the form of a polymer, a monomer, or a combination thereof. If present in the form of a polymer, the methacrylic component may be a polymer chain to which is attached at least one of the above-identified groups. The groups may be located at a pendant or a terminal position of the backbone, or a combination thereof. Additionally, at least two such groups may be present, and may be located at terminal positions.
  • the methacrylic polymer chain may be polyvinyl, poly ether, polyester, polyurethane, polyamide, epoxy, vinyl, ester, phenolic, amino, oil- based, and the like, as is well known to those skilled in the art, or random or block combinations thereof.
  • the polymer chain of the methacrylic may be formed by polymerization of vinyl monomers.
  • vinyl monomers examples include: methyl methacrylate, methacrylic acid, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, 2- ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, phenyl methacrylate, tolyl methacrylate, benzyl methacrylate, 2-methoxyethyl methacrylate, 3-methoxy
  • the amount of the methacrylic component present in part (A) may range from about 20% by weight to about 90%> by weight, based on the total weight of part (A).
  • part (A) contains from about 50% by weight to about 70% by weight of the methacrylate component, based on the total weight of part (A).
  • Part (A) further contains a chlorosulfonated polymer.
  • the chlorosulfonated polymer includes those selected from among chlorosulfonated polyolefms, for example, chlorosulfonated polymers of ethylene, propylene, isobutylene and the like.
  • the chlorosulfonated polymer may be obtained according to techniques known in the art, such as by the chlorination and/or chlorosulfonation of a polyolefin.
  • Chlorosulfonated polyethylene is the preferred chlorosulfonated polymer, although chlorosulfonated copolymers of ethylene with small amounts of propylene or other olefins may be used as well.
  • the amount of the chlorosulfonated polymer present in part (A) may range from about 10%) by weight to about 45% by weight, and preferably ranges from about 25% to about 40%) by weight, based on the total weight of part (A).
  • part (A) may contain one or more organic acids to enhance adhesion.
  • the organic acid is a carboxylic acid.
  • suitable carboxylic acids include, but are not limited to, methacrylic acid, acrylic acid, maleic acid, crotonic acid, furmaric acid, malonic acid, acetylene dicarboxylic acid, dibromo maleic citranoic acid, mesaconic acid, and oxalic acid
  • the amount of the organic acid in part (A), when present, may range from about 0.01%) by weight to about 15% by weight, preferably from about 1% by weight to about 10%) by weight, based on the total weight of part (A).
  • Part (A) may also optionally contain a compound having at least one sulfonyl halide group having the structure I
  • X is selected from chlorine, bromine and iodine.
  • the sulfonyl halide-containing compounds may be mono- or polyfunctional.
  • the sulfonyl halide containing compound is an aliphatic sulfonyl halide having from 1 to 15 carbon atoms.
  • the sulfonyl halide- containing compound is an aromatic sulfonyl halide having from 1 to 3 aromatic nuclei and containing from 6 to 24 carbon atoms.
  • sulfonyl halide-containing compound include: methane sulfonyl chloride, biphenyl disulfonyl chloride, trichlorobenzene sulfonyl chloride, benzene sulfonyl chloride, p-toluene sulfonyl chloride, hexadecane sulfonyl chloride, and diphenyl ether-4,4'-sulfonly chloride.
  • the amount of the sulfonyl halide-containing compound in part (A) may range from about 0.1% to about 5% by weight, preferably from about 0.2% by weight to about 1% by weight, based on the total weight of part (A).
  • Part (A) may also include a free radical stabilizer such as a quinonone, hydroquinone, hydroxylamine, nitroxyl compound, phenol, amine, acrylamine, or phenothiazine.
  • a free radical stabilizer such as a quinonone, hydroquinone, hydroxylamine, nitroxyl compound, phenol, amine, acrylamine, or phenothiazine.
  • the free radical stabilizer may be present in an amount ranging from about 0.01%) by weight to about 5% by weight, preferably from about 0.2%> by weight to about 0.5%) by weight, based on the total weight of part (A).
  • part (B) of the two-part structural adhesive system contains an aldehyde-amine condensate.
  • the aldehyde-amine condensate includes conventional aldehyde-amine condensates of the type described, for example, in U.S. Pat. No. 3,591,438, columns 6-7, which is herein incorporated by reference. These condensates may be prepared by reacting from about 1 to 3.5 moles of aldehyde with 1 mole of amine at a temperature of from 40° C to 70° C.
  • aldehydes include, but are not limited to, acetaldehyde, propionaldehyde, butryaldehyde, crotonaldehyde, acrolein, hydrocinnamaldehyde and 2-phenylpropionaldehyde.
  • amines include, but are not limited to, secondary aliphatic amines or aromatic primary amines containing from 1 to 18 carbon atoms such as ethyleneamine, butylamine, pentylamine, cyclopentylamine, hexylamine, cyclohexylamine, dodecylamine, aniline, tolylamine and xylylamine.
  • a preferred aldehyde-amine condensate is the condensate of butryaldehyde and aniline, commercially available as VANAX® 808 HP condensate (R.T. Vanderbilt Company Inc.).
  • the amount of the aldehyde-amine condensate in part (B) may range from about 0.5% by weight to about 25% by weight, preferably from about 5% by weight to about 15%) by weight, based on the total weight of part (B).
  • the metal quinolate used in combination with the aldehyde-amine condensate in part (B) is a compound having the general formula
  • M is a metal in a +2, +3 or +4 oxidation state
  • n is 1, 2 or 3
  • Y is the same or different at each occurrence and is selected from the group consisting of 8-hyroxyquinolate and substituted 8-hydroxyquinolate having the formula
  • R 3 , R 4 and R 5 are, independently, a substituent selected from hydrogen, a Ci-C 2 o alkyl, an aryl having 6-20 carbon atoms, an alkylaryl having 7-30 carbon atoms, an alkoxy having 1-20 carbon atoms, an aryloxy having 6-20 carbon atoms, a heteroalkyl having 1-20 carbon atoms, a heteroaryl having 4-20 carbon atoms, a heteroalkylaryl having 4-20 carbon atoms, a heteroalkoxy having 1-20 carbon atoms, a heteroaryloxy having 4-20 carbon atoms, cyano, dialkylamino, diarylamine, and halogen.
  • M is a metal selected from the group consisting of aluminum, tin, beryllium, calcium, magnesium, lead, manganese, copper, nickel, iron, cadmium, silver, thallium, zinc, gallium, zirconium and indium.
  • the "n" can be 1 , 2 or 3, depending on the oxidation state of M, and is selected so that the overall complex is electrically neutral.
  • M is copper and n is 2.
  • the metal quinolate may be dissolved in an organic solvent.
  • Suitable solvents are those that will sufficiently dissolve, disperse or emulsify the metal quinolate and can be readily determined by one skilled in the art. Examples include Ci-C 2 o alcohols, ethers, such as glycol ethers, acid esters, C -Cn alkanes, aromatics, chlorinated hydrocarbons and any mixture thereof.
  • the amount of the metal quinolate in part (B) may range from about 0.00001% by weight to about 40%> by weight, preferably from about 0.0001% by weight to about 30%> by weight, based on the total weight of part (B).
  • part (B) may optionally contain a methacrylic component.
  • the specific methacrylic components used in part (B) are the same as those used in part (A) and are discussed above.
  • the methacrylic component may be used in amounts ranging from about 20% by weight to about 85% by weight, preferably from about 60% by weight to about 80%> by weight, based on the total weight of part (B).
  • part (B) may optionally contain an impact modifier.
  • impact modifier can be one impact modifier or two or more impact modifiers.
  • Various impact modifiers may be employed in the practice of the present disclosure and often include one or more elastomers.
  • the impact modifier includes at least one core/shell impact modifier and preferably the impact modifier includes a substantial portion of core/shell impact modifier.
  • the impact modifier is comprised of at least 60%, more typically at least 80% and even more typically at least 97% core/shell impact modifier.
  • the term core/shell impact modifier denotes an impact modifier wherein a substantial portion (e.g., greater than 30%>, 50%>, 70%> or more by weight) thereof is comprised of a first polymeric material (i.e., the first or core material) that is substantially encapsulated by a second polymeric material (i.e., the second or shell material).
  • the first and second polymeric materials can be comprised of one, two, or three or more polymers that are combined and/or reacted together (e.g., sequentially polymerized) or may be part of separate or same core/shell systems.
  • the first and second polymeric materials of the core/shell impact modifier can include elastomers, polymers, thermoplastics, copolymers, other components, and combinations thereof.
  • the first polymeric material, the second polymeric material or both of the core/shell impact modifier include or are substantially composed of (e.g., at least 70%>, 80%>, 90%> or more by weight) one or more thermoplastics.
  • Exemplary thermoplastics include, without limitation, styrenics, acrylonitriles, acrylates, acetates, polyamides, polyethylenes and the like.
  • the core/shell impact modifiers may be formed by emulsion polymerization followed by coagulation or spray drying. It is also preferred for the core/shell impact modifier to be formed of or at least include a core-shell graft co-polymer.
  • the first or core polymeric material of the graft copolymer preferably has a glass transition temperature substantially below (i.e., at least 10° C, 20° C, 40° C or more) the glass transition temperature of the second or shell polymeric material. Moreover, it may be desirable for the glass transition temperature of the first or core polymeric material to be below 23° C while the glass temperature of the second or shell polymeric material to be above 23° C, although not required
  • core-shell graft copolymers are those where hard containing compounds, such as styrene, acrylonitrile or methyl methacrylate, are grafted onto core made from polymers of soft or elastomeric containing compounds such as butadiene or butyl acrylate.
  • hard containing compounds such as styrene, acrylonitrile or methyl methacrylate
  • core-shell polymers the cores of which are made from butyl acrylate but can be based on ethyl isobutyl, 2-ethylhexel or other alkyl acrylates or mixtures thereof.
  • the core polymer may also include other copolymerizable containing compounds, such as styrene, vinyl acetate, methyl methacrylate, butadiene, isoprene, and the like.
  • the core polymer material may also include a cross linking monomer having two or more nonconjugated double bonds of approximately equal reactivity such as ethylene glycol diacrylate, butylene glycol dimethacrylate, and the like.
  • the core polymer material may also include a graft linking monomer having two or more nonconjugated double bonds of unequal reactivity such as, for example, diallyl maleate and allyl methacrylate.
  • the shell portion may be polymerized from methyl methacrylate and optionally other alkyl methacrylates, such as ethyl, butyl, or mixtures thereof. Up to 40% by weight or more of the shell monomers may be styrene, vinyl acetate, vinyl chloride, and the like. Additional core-shell graft copolymers useful in embodiments of the present invention are described in U.S. Pat. Nos. 3,984,497; 4,096,202; 4,034,013; 3,944,631; 4,306,040; 4,495,324; 4,304,709; and 4,536,436, the entireties of which are herein incorporated by reference.
  • core-shell graft copolymers examples include, but are not limited to, "MBS" (methacrylate -butadiene-styrene) polymers, which are made by polymerizing methyl methacrylate in the presence of polybutadiene or a polybutadiene copolymer rubber.
  • MBS methacrylate -butadiene-styrene
  • the MBS graft copolymer resin generally has a styrene butadiene rubber core and a shell of acrylic polymer or copolymer.
  • Examples of other useful core-shell graft copolymer resins include, ABS (acrylonitrile-butadiene-styrene), MABS (methacrylate- acrylonitrile-butadiene-styrene), ASA (acrylate-styrene-acrylonitrile), all acrylics, SA EPDM (styrene-acrylonitrile grafted onto elastomeric backbones of ethylene-propylene diene monomer), MAS (methacrylic-acrylic rubber styrene), and the like and mixtures thereof.
  • PARALOID The Dow Chemical Co.
  • Particularly preferred grades of PARALOID impact modifiers are polymethyl methacrylate shell and MBS core modifier and butyl- acrylate shell and acrylate core modifier sold under the designation EXL 2691 A and KM 330.
  • the amount of the core shell polymer in part (B), when present, may range from about 5% by weight to about 35% by weight, preferably from about 10% by weight to about 25% by weight, based on the total weight of part (B).
  • additives which may be included in part (B) include: plasticizers such as dioctyl phthalate, dibutyl phthalate, diisobutyl phthalate, diisodecyl phthalate; phthalate-free plasticizers, such as ricinoleate-based plasticizers, 2,2,4-trimethyl-l ,3- pentanediol diisobutyrate, dioctyl succinate, and diisodecyl adipate; fillers; pigments; and thixotropic agents.
  • plasticizers such as dioctyl phthalate, dibutyl phthalate, diisobutyl phthalate, diisodecyl phthalate
  • phthalate-free plasticizers such as ricinoleate-based plasticizers, 2,2,4-trimethyl-l ,3- pentanediol diisobutyrate, dioctyl succinate, and diisodec
  • the structural adhesive systems of the present disclosure may be prepared by first combining the respective ingredients in part (A) and part (B). Part (A) and part (B) can then be contacted or mixed using any conventional device just prior to use to form a curable composition.
  • the present disclosure provides a method of bonding at least two substrates together which includes:
  • part (A) and part (B) may be mixed in about a 5: 1 to 1 :5 ratio by volume, while in other embodiments part (A) and part (B) may be mixed in about a 10: 1 to 1 : 10 ratio by volume.
  • parts (A) and (B), after mixing, are applied to the surface of at least one substrate by brushing, rolling, spraying, dotting, or kniving to at least one substrate.
  • the surface may be untreated, oily, etc.
  • the substrates to be adhered may be clamped for firmness during cure in those installations where relative movement of the substrates might be expected.
  • an adherent quantity of the curable composition is applied to at least one surface, preferably to both surfaces, and the surfaces are contacted with the curable composition therebetween. The smoothness of the surfaces and their clearance will determine the required film thickness for optimum bonding.
  • the surfaces and the interposed curable composition are then maintained in engagement until the curable composition has cured sufficiently to bond the surfaces.
  • substrates which the curable composition may be applied to include, but are not limited to, steel, galvanized steel, aluminum, copper, brass, wood, glass, paper, composites, ceramics, plastics and polymeric materials such as polyester, polyamide, polyurethane, polyvinyl chloride, polycarbonates, ABS plastics, and plexiglass.
  • the two-part adhesive systems of the present disclosure provide very strong bond strengths which may range from about 3000-4500 psi in shear.
  • the setting time for the curable compositions may vary somewhat, but may range between about 5- 30 minutes but in some embodiments may range up to several hours in the case of large jobs where applying the curable composition to the substrate can take substantial time.
  • the cure time for the two-part adhesive system may range from about 10 minutes to about 120 minutes.
  • Example 1 The following components were combined to form parts (A) and (B) of a two-part structural adhesive system according to the present disclosure:
  • Parts (A) and (B) exhibited the following physical properties: Physical Property
  • Parts (A) and (B) were then mixed at a 1 : 1 ratio by volume to form a curable composition which exhibited the following properties in comparison to a commercially available two- part structural adhesive which contained peroxide:
  • Examples 2-7 The following components were combined to form parts (A) and (B) of a two-part structural adhesive system according to the present disclosure: Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7
  • Parts (A) and (B) were then mixed at a 1 : 1 ratio by volume to form a curable composition which exhibited the following properties: Phys. Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Property

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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)

Abstract

La présente invention concerne des systèmes d'adhésifs structuraux à plusieurs parties, qui sont sensiblement exempts de peroxyde. L'invention concerne également des procédés permettant de préparer les systèmes d'adhésifs structuraux à plusieurs parties et des procédés de collage de substrats les uns sur les autres avec ces systèmes d'adhésifs.
PCT/US2012/027865 2011-03-25 2012-03-06 Adhésifs structuraux à base de méthacrylate et exempts de peroxyde WO2012134735A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070155899A1 (en) * 2005-12-21 2007-07-05 Ips Corporation Elastic methacrylate compositions
US20070251640A1 (en) * 2006-04-27 2007-11-01 Freund David F Adhesive formulation for vacuum forming applications
US20080193640A1 (en) * 2007-02-09 2008-08-14 Jun Zhang Wood preserving composition for treatment of in-service poles, posts, piling, cross-ties and other wooded structures
US20080302479A1 (en) * 2005-12-15 2008-12-11 Huntsman International Llc Multiphase Acrylic Adhesives
US20090110835A1 (en) * 2007-10-31 2009-04-30 Pressley Mark W Additives for improved adhesion to oily substrates
US20100101724A1 (en) * 2007-07-06 2010-04-29 Henkel Corporation Acrylic adhesives

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080302479A1 (en) * 2005-12-15 2008-12-11 Huntsman International Llc Multiphase Acrylic Adhesives
US20070155899A1 (en) * 2005-12-21 2007-07-05 Ips Corporation Elastic methacrylate compositions
US20070251640A1 (en) * 2006-04-27 2007-11-01 Freund David F Adhesive formulation for vacuum forming applications
US20080193640A1 (en) * 2007-02-09 2008-08-14 Jun Zhang Wood preserving composition for treatment of in-service poles, posts, piling, cross-ties and other wooded structures
US20100101724A1 (en) * 2007-07-06 2010-04-29 Henkel Corporation Acrylic adhesives
US20090110835A1 (en) * 2007-10-31 2009-04-30 Pressley Mark W Additives for improved adhesion to oily substrates

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