WO1996015170A1 - Adhesif polyolefinique qui durcit par l'action de l'humidite - Google Patents

Adhesif polyolefinique qui durcit par l'action de l'humidite Download PDF

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Publication number
WO1996015170A1
WO1996015170A1 PCT/US1994/013267 US9413267W WO9615170A1 WO 1996015170 A1 WO1996015170 A1 WO 1996015170A1 US 9413267 W US9413267 W US 9413267W WO 9615170 A1 WO9615170 A1 WO 9615170A1
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Prior art keywords
adhesive composition
hydroxyl
carbon atoms
isocyanate
group
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PCT/US1994/013267
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English (en)
Inventor
Toshinori Wakabayashi
Gaddam N. Babu
Charles W. Stobbie, Iv
John C. Tangen
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Minnesota Mining And Manufacturing Company
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Publication date
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Priority to AU15499/95A priority Critical patent/AU1549995A/en
Publication of WO1996015170A1 publication Critical patent/WO1996015170A1/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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • 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
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/2815—Monohydroxy compounds
    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • 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
    • C08G18/2815—Monohydroxy compounds
    • C08G18/284—Compounds containing ester groups, e.g. oxyalkylated monocarboxylic acids
    • 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
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6204—Polymers of olefins
    • 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
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6204—Polymers of olefins
    • C08G18/6208—Hydrogenated polymers of conjugated dienes
    • 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
    • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
    • C08G18/633—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polymers of compounds having carbon-to-carbon double bonds
    • 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
    • C08G2170/00—Compositions for adhesives
    • C08G2170/20—Compositions for hot melt adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
    • C08L2666/06—Homopolymers or copolymers of unsaturated hydrocarbons; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/26—Natural polymers, natural resins or derivatives thereof according to C08L1/00 - C08L5/00, C08L89/00, C08L93/00, C08L97/00 or C08L99/00

Definitions

  • This invention relates to a moisture curable hot-melt adhesive having improved heat resistance as well as good adhesion to substrates having low surface energies and to a method of making this adhesive.
  • Moisture curable polyurethane compositions are widely known. They are generally used as adhesives, coatings, sealers, and casting materials. Moisture curable adhesives that adhere to unprimed substrates are described in U.S. Patent Nos. 4,539,345 and 4,661,542. These compositions comprise an isocyanate-functional prepolymer, a tackifier and, optionally, a plasticizer.
  • U.S. Patent No. 4,891,269 describes hot melt, pressure sensitive, moisture curable polyurethane compositions that have high green strength, extended pot life, high ultimate strength, and high elongation at break. These compositions comprise (a) a liquid urethane prepolymer made by reacting a polyisocyanate with a polyhydroxy compound having a molecular weight of less than about 20,000; (b) a tackifying resin; and (c) a polyethylene- vinyl monomer component.
  • Moisture curable hot-melt type adhesives comprising urethane prepolymers made from hydrocarbon-based polyols with hydroxyl end groups and diisocyanates are described in Kokai Nos. 2-272013 and 3-36015.
  • hot-melt adhesive compositions having improved heat resistance, reduced odor, and improved storage stability are disclosed.
  • These adhesives comprise a urethane prepolymer, obtained by reacting a diisocyanate with a polyolefin diol having a hydroxyl group at each end, and a tackifier.
  • the present invention provides a moisture curable hot-melt adhesive composition
  • a moisture curable hot-melt adhesive composition comprising the reaction product of a polyisocyanate compound and a maleated polyolefin.
  • the present invention provides an article of manufacture comprising at least one substrate coated with a layer of this moisture curable adhesive composition.
  • the present invention provides a method for preparing this moisture curable adhesive composition comprising the step of reacting a maleated polyolefin with at least one polyisocyanate, optionally in the presence of a catalyst and/or a tackifier.
  • the present invention provides a hot-melt adhesive composition comprising a pendent group comprising an isocyanate moiety. When exposed to moisture, the isocyanate forms a urethane-urea crosslinking moiety.
  • the isocyanate that reacts with moisture to form the urethane-urea linkage is incorporated into the polymer when a polyisocyanate compound reacts with a pendent group derived from maleic anhydride. This group can be either the anhydride or the diacid.
  • hydroxyl-containing material means a mono- or polyol
  • group or “ring system” or “monomer” or “compound” or “polymer” means a chemical species that allows for substitution by conventional substituents that do not interfere with the desired product
  • maleated polyolefin means a polyolefin that comprises mer unit(s) derived from maleic anhydride, with the proviso that the maleate functionality of the mer unit(s) can be in the form of the anhydride and/or the diacid.
  • the hot-melt adhesive produced when the composition is moisture cured has high shear strength at elevated temperatures and good adhesion to low surface energy substrates. Such an adhesive is useful in many glazing, manufacturing, and sealing applications.
  • the moisture curable hot-melt adhesive composition of the present invention comprises the reaction product of a maleated polyolefin and at least one polyisocyanate compound.
  • the polyisocyanate(s) can be in the form of an isocyanate-terminated urethane prepolymer.
  • a tackifying resin, and a catalyst can also be present.
  • Maleated polyolefins used in the preparation of the moisture curable composition of the invention have the general formula
  • R 1 is an alkyl group preferably having 4 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and most preferably 4 to 6 carbon atoms;
  • R 2 is hydrogen; an alkyl group having 1 to 18 carbon atoms, preferably 1 to 3 carbon atoms; or an aryl group having 6 to 12 carbon atoms;
  • R 3 is preferably hydrogen or, an organic group which together with R 2 and the carbon atoms to which they are attached, forms a saturated or unsaturated monocyclic or polycyclic ring system having 6 to 20 carbon atoms;
  • R 4 is R 1 or R 2 ;
  • R" is hydrogen when R 4 is R 1 and is R 3 when R 4 is R 2 ;
  • R is either
  • x, y, and z are numbers that define the relative molar amounts of the randomly spaced, two-carbon units making up the backbone chain of the polymer, with the following provisos:
  • x is at least 60 mole percent of the sum of x + y + z; 2) y is zero where R 1 and R 2 are the same and R 3 is hydrogen;
  • z is from about 3 to 15 mole percent of the sum of x + y + z;
  • the M w of the polymer will be in the general range of 15,000 to 250,000, preferably from 25,000 to 100,000.
  • Maleated polyolefins are commerically available from Eastman Chemical Company (Longview, TX). Most are available as part of Eastman's P 1284 series, in both high and low acid numbers, that includes selected amorphous homopolymers; propylene-ethylene, propylene-butene, and propylene-hexane copolymers; and propylene-ethylene-butene terpolymers.
  • Olefins that can be used in preparation of the maleated polyolefins of the invention can have from 2 to 20 carbon atoms.
  • Representative examples include, but are not limited to, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1- tetradecene, 1-octadecene, 1-eicosene, 2-butene, 2-pentene; branched olefins such as 3- methyl-1-butene, 3,3-dimethyl-l-butene, 4-methyl-l-pentene, 3-ethyl-l-pentene; cyclic olefins such as cyclopentene, cyclohexene, 3-methylcyclopentene, 4-w-butylcyclohexene, bicyclo[2.2.
  • the maleated polyolefins of the present invention can be prepared by reacting (a) a saturated homopolymer or copolymer made by polymerizing one or more C 6 to C
  • a free radical initiator preferably a peroxide catalyst together with an electron donor such as triphenyl phosphite or triethyl phosphate.
  • Preferred Ziegler-Natta catalysts include combinations of a complex of alkylaluminum and a halide of a transition metal from group 4 to group 10 of the Periodic Table (Chem. Abstracts Version).
  • Typical alkylaluminum complexes include triethylaluminum, tributylaluminum, diethylaluminum chloride, and dibutylaluminum chloride.
  • Transition metal halides include such compounds as titanium trichloride, titanium tetrachloride, vanadium trichloride, vanadium tetrachloride, and vanadium oxytrichloride.
  • a particularly preferred catalyst system commercially available from Stauffer Chemical Co. (Hartford, CT), is diethylaluminum chloride/aluminum-activated titanium trichloride.
  • Polyisocyanate and isocyanate compounds useful in the preparation of the moisture curable composition of the invention can be aliphatic or aromatic.
  • a list of useful polyisocyanates, which are commercially available from a variety of sources see Kirk-Othmer, Encyclopedia of Chemical Technology (3d ed.), vol. 13, p.
  • TDI 2,4- and 2,6-toluene diisocyanate
  • MDI diphenylmethane-2,4'- and 4,4'-diisocyanate
  • partially carbodiimidized MDI polymethylene polyphenyl isocyanate, 4,4'- dicyclohexylmethane diisocyanate, toluene diisocyanate, phenyl isocyanate, chlorophenyl isocyanate, 3,4-dichlorophenyl isocyanate, methyl isocyanate, ethyl isocyanate, n-butyl isocyanate, cyclohexyl isocyanate, octadecyl isocyanate, hexamethylene diisocyanate, biuret of hexamethylene diisocyante, and 3-isocyana
  • aromatic diisocyanates such as MDI and TDI, as well as mixtures thereof.
  • Other examples include naphthylene-l,5-diisocyanate, triphenylmethane-4,4',4"-triisocyanate, phenylene-l,3-diisocyanate, phenylene-1,4- diisocyanate, dimethyl-3,3'-biphenylene-4,4'-diisocyanate, diphenylisopropylidine-4,4'- diisocyanate, biphenylene diisocyanate, xylylene-l,3-diisocyanate, and xylylene-1,4- diisocyanate.
  • Oligomeric isocyanates derived from aromatic diisocyanates can also be used.
  • liquid mixtures of an isocyanate-functional derivative with melting point modifiers e.g., mixtures of MDI with carbodiimide adducts such as Isonate TM 143L (Dow Chemical Co.; Midland, MI) and Mondur TM CD (Miles Chemical Corp.; Pittsburgh, PA); up to 10% (by weight) of the total isocyanate component of polymeric MDI (e.g., PAPI " and the PAPI TM 20 through PAPI TM 901 series (Dow Chemical Co.); Mondur TM MR, Mondur TM MRS, and Mondur TM MRS- 10 (Miles Chemical Corp.); and Rubinate TM M (ICI Chemicals, Inc.; Wilmington, DE)); and blocked isocyanate compounds formed by reacting aromatic isocyanates or the above-described isocyanate-functional derivatives with blocking agents such as ketoxime. Such blocked isocyanate-functional derivatives will, for
  • Sufficient isocyanate should be present in the moisture curable composition to provide to the composition 0.5 to 4 equivalents, preferably 1.5 to 2.5 equivalents, of isocyanate groups to total acid equivalents of anhydride, carboxyl, and hydroxyl.
  • Hydroxyl-containing materials that can be (optionally) used in the moisture curable composition of the invention have molecular weights of about 150 to about 10,000, preferably from about 200 to 2000.
  • Useful materials include hydroxyl-substituted polyolefins, polyesters, polyethers, polyamides, polyimides, and the like.
  • Preferred mono- or polyols are liquid to waxy materials at room temperature and have from 0.5 to 4 hydroxyl equivalents. Particularly preferred are the aliphatic mono- and polyols. Of these, polyolefinic, polyester, and polyether mono- and polyols are the most preferred.
  • Hydroxyl-substituted polyolefins can be prepared in many ways.
  • One well known method is to effect polymerization of one or more of ⁇ -olefins and dienes using anion or Ziegler-Natta catalysis. Hydrogenation of the polymerization product reduces unsaturation to preferably less than about 5% to yield a suitable hydroxyl-containing polyolefin.
  • hydroxyl-containing polyolefins examples include alcohols such as NOVA Guerbet Alcohol 20i' " (NOVA Molecular Technologies, Inc.; Janesville, WI); polybutadienes such as Polytaif-H and HA (Mitsubishi Kasei America, Inc.; White Plains, NY); Epof hydrogenated polyisoprenes (Idemitsu Petrochemical Co., Ltd.; Southfield, MI); low- viscosity ethylene-butylene copolymers having terminal primary hydroxyl groups such as HPVM TM -2500 (available on an experimental basis from Shell Chemical Co.; Houston, TX); polyalkylene oxides such as Voranol TM (Dow Chemical Co.); and saturated, linear, long-chain alcohols such as Unilin' " 350, 425, 550, or 700 (Petrolite Corp.; Tulsa, OK). ,
  • Preferred mono- and polyols have the general formula
  • R 5 is hydrogen or an aliphatic group having 1 to 12 carbon atoms and a valence of a;
  • R 6 is hydrogen or an alkyl group with 1 to 4 (inclusive) carbon atoms;
  • X is an element or a divalent radical, preferably oxygen;
  • a is an integer from 1 to 4 (inclusive);
  • b is a number that designates the average number of units in the hydroxyl-containing material such that the material has a M consult of 150 to 10,000, preferably from 200 to 2000;
  • c is O or 1; and d is 1 or 2.
  • Polyether mono- and polyols are well known and are prepared by well known reactions of compounds containing hydroxyl groups with ethylene oxide and/or propylene oxide in the presence of a base catalyst.
  • a myriad of hydroxyl-group containing compounds can be used to initiate the reaction including, for example, methanol, ethanol, propanol, butanol, ethylene glycol, butylene glycol, glycerine, 2,2-dimethylolpropane, and pentaerythritol.
  • hydroxyl-functional polyethers examples include ArcolTM polyether polyols such as PPGTM 425, PPGTM 725, LHTTM 112, LHTTM 28, and LG TM 168 (Arco Chemical Co.; Newtown Square, PA); polyethylene glycols such as the CarbowaxTM series (Union Carbide Corp.; Danbury, CT), having a molecular weight from 350 to 5000; PluracolTM E 1450 polyethylene glycol (BASF Corp.; Parsippany, NJ); and TERATHANE TM poly(tetramethylene oxide) polyols (E.I. DuPont de Nemours; Wilmington, DE).
  • ArcolTM polyether polyols such as PPGTM 425, PPGTM 725, LHTTM 112, LHTTM 28, and LG TM 168 (Arco Chemical Co.; Newtown Square, PA)
  • polyethylene glycols such as the CarbowaxTM series (Union Carbide Corp.; Danbury, CT), having a mole
  • Polyester mono- and polyols are also well known and are prepared by condensation reactions of a polyol and a dicarboxylic acid in the presence of a catalyst.
  • Preferred polyester alcohols have the general formula
  • R 5 , a, and b are defined as above, and
  • R 7 and R 8 are independently selected from the group consisting of
  • composition of the present invention can contain an effective amount of at least one of catalysts and reaction accelerators such as tertiary amines and organometallic compounds, and co-curatives such as oxazolidine, as is well known in the art.
  • Dibutyltin dilaurate is a preferred organometallic catalyst, although others such as dibutyltin diacetate, dibutyltin disulfide, tin octanoate, and tetrabutyl titanate also can be used.
  • Organometallic catalyst preferably can be present from about 0.01 to 2% (by weight), more preferably about 0.05 to about 1% (by weight), of the prepolymer.
  • the moisture curable composition of the present invention comprises up to 100 parts by weight (pbw), preferably 10 to 60 pbw, and more preferably 20 to 50 pbw, of tackifying resin per 100 pbw of maleated polyolefin.
  • Tackifying resin can be used to lower the viscosity of the reaction mixture. Adhesive mixtures with lower viscosities can be more readily hot-melt coated; thus, the resultant coating will have better tackiness and peel adhesion than a coating of the untackified polymer alone.
  • Tackifying resins also enhance internal strength and thermal stability.
  • Useful tackifying resins include those derived from polymerization of unsaturated
  • Hydrocarbon tackifying resins can be prepared by polymerization of monomers consisting primarily of olefins and diolefins and include, for example, residual byproduct monomers of the isoprene manufacturing process. These hydrocarbon tackifying resins typically exhibit ball and ring softening points (see ASTM E28-67, "Softening Point by Ring and Ball Apparatus") from about 80° to about 145°C, acid numbers from about 0 to 2, and saponification values of less than one.
  • tackifying resins examples include Wingtack TM 95 and Wingtack TM 115 (Goodyear Tire and Rubber Co.; Akron, OH).
  • Other hydrocarbon resins include Regalrez TM 1078 and 1126 (Hercules Chemical Co., Inc.; Wilmington, DE), Escorez TM resins (Exxon Chemical Co.; Newark, NJ), and the Arkon TM series of resins (Arakawa Chemical Co.; Chicago, IL).
  • Particularly preferred tackifiers are the Arkon TM P and E series of highly hydrogenated hydrocarbon tackifying resins, such as Arkon TM E-90.
  • the tackifying resin may contain ethylenic unsaturation. However, saturated tackifying resins are preferred for those applications where oxidation resistance is important.
  • compositions of the invention can contain other components.
  • chain extension agents e.g., short chain polyols such as ethylene glycol or butanediol
  • fillers such as carbon black, metal oxides (e.g., zinc oxide), talc, clay, silica, silicates, glass or polymeric microbubbles, and conductive particles; thermoplastic resins; plasticizers; antioxidants; pigments; UV absorbers; and adhesion promoters (e.g., silanes) may be included to impart to the composition characteristics which are desirable for a particular purpose.
  • Such components should be added in amounts that do not interfere with the composition's adhesion to surfaces having low surface energies and with its shear strength at elevated temperatures.
  • These components can comprise up to 50% (by weight) of the composition.
  • a preferred embodiment of the adhesive composition of the present invention comprises a) the reaction product of
  • a hydroxyl- containing material is present, it is preferably reacted with the polyisocyanate compound(s) so as to form an isocyanate-terminated urethane prepolymer, which is then allowed to react with the maleated polyolefin.
  • the moisture curable composition of the invention can be prepared by mixing the components in a conventional mixing apparatus. Elevated temperatures can be used where necessary.
  • the components other than isocyanate and catalyst will be separately dried by heating (50° to 250°C) under vacuum for a period of time (e.g., 2 to 24 hours) before being mixed and will be maintained at 50° to 150°C under an inert gas (e.g., nitrogen) during mixing until the reaction is complete.
  • an inert gas e.g., nitrogen
  • the hydroxyl-containing material of the reaction mixture is a monool
  • approximately equimolar amounts of the monool and the isocyanate component are mixed (and heated at a temperature of 50° to 150°C, if necessary), optionally in the presence of a catalyst, examples of which are given above, to form an isocyanate- terminated urethane.
  • This material is then reacted with a maleated polyolefin, adding catalyst if desired.
  • the reaction can be driven to completion by heating (50° to 150°C) for a period of time (generally from about 5 minutes to 5 hours).
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R, R', X, b, c, d, x, y, and z are defined as above;
  • R 9 is an organic group having a valence of g+1 and is selected from the group consisting of
  • reaction mixture up to 100, preferably 10 to 60, and more preferably 20 to 50, parts by weight of a tackifying resin and up to 3 equivalents of additional polyisocyanate is added to the reaction mixture (based on the total molar equivalent weights of the maleated polyolefin and the monool).
  • hydroxyl-containing material of the reaction mixture is a poiyol
  • addition of the poiyol to the polyisocyanate will preferably be accomplished in separate operations, each being performed so that 0.5 to 4 equivalents of isocyanate per hydroxyl equivalent in the poiyol and per acid equivalent in the maleated polyolefin are present.
  • Scheme II shows a series of reactions that might take place.
  • the product of Reaction A can also randomly react with the maleated polyolefin from Reaction B to provide isocyanate-terminated polymers which, upon exposure to moisture, form urea linkages.
  • the product of Reaction A or B can hydrolyze to produce an amine-terminated product which can react with the product of the other reaction to produce urea linkages.
  • R ⁇ R 2 , R 3 , R 4 , R 5 , R 6 , R 9 , R, R', R", X, b, c, d, x, y, and z are defined as above; e is 1 to 3; and f is an integer from 2 to 4 (inclusive).
  • the products of reaction schemes A and B are then combined and mixed with up to 100, preferably 10 to 60, and more preferably 20 to 50, pbw tackifying resin. Generally, the preparation is made without the use of solvents.
  • the molten product is packaged in containers that are sealed so as to exclude moisture.
  • the composition of the invention can be packaged according to techniques known to those skilled in the art. Suitable packages include, for example, caulking tubes (made, for example, of metal or plastic), screw-capped squeezable tubes, cans, drums, and the like.
  • the composition of the present invention is cured by exposure to moisture (e.g., water vapor). Curing occurs when water molecules react with remaining isocyanate units (i.e., those not involved in the reaction with maleated polyolefin). Ambient humidity usually is adequate to promote curing. Heat and/or high humidity produce faster cure rates whereas low temperatures (e.g., 5°C or less) and low humidity (e.g., a relative humidity of 15% or less) produce slower cure rates.
  • moisture e.g., water vapor
  • Curing occurs when water molecules react with remaining isocyanate units (i.e., those not involved in the reaction with maleated polyolefin).
  • Ambient humidity usually is adequate to promote curing. Heat and/or high humidity produce faster cure rates whereas low temperatures (e.g., 5°C or less) and low humidity (e.g., a relative humidity of 15% or less) produce slower cure rates.
  • compositions of the invention can be employed in applications where a high- performance adhesive, coating, sealant, or casting resin is desired.
  • One such use includes the bonding of original or replacement glazing materials (e.g., windshields and back-lights of laminated safety glass) to transportation vehicles such as automobiles, trucks, aircraft, trains, and the like.
  • original or replacement glazing materials e.g., windshields and back-lights of laminated safety glass
  • transportation vehicles such as automobiles, trucks, aircraft, trains, and the like.
  • the compositions of the invention provide rapid drive- away times following glazing material installation.
  • compositions can also be used in building construction (e.g., as a panel adhesive, moisture barrier, or glazing sealant), assembly line manufacturing (e.g., assembly of parts such as windows by adhesive bonding), lamination of products such as skis, coatings for outdoor surfaces (e.g., concrete deck coatings or roof membranes), and sealants (e.g., marine sealants or sealants for use in cable splice housings).
  • the compositions of the invention can be applied to substrates such as glass, metal (whether bare or painted), ceramics, thermoplastics, thermosetting materials, foam materials, canvas, wood, paper, leather, rubber, and textiles (both woven and nonwoven).
  • the compositions are particularly useful on low surface energy materials such as polyolefins.
  • the use of a diluent is desirable.
  • inert diluents which may be employed are vegetable oils; mineral oils such as napthenic and paraffinic distillates; and esters such as dibutyl phthalate, dioctyl phthalate, and dioctyl adipate.
  • esters such as dibutyl phthalate, dioctyl phthalate, and dioctyl adipate.
  • Heat resistance of the moisture-curable composition of the invention was determined by subjecting overlap shear bonds to incremental temperature increases and determining the temperature at which bond failure occurred.
  • Overlap shear bonds were prepared from 2.5 cm x 10 cm x 8 mm Douglas fir coupons (W.B. Martin Lumber; St. Paul, MN) with at least one smooth face, using spacers with diameters of 0.33 mm.
  • the composition was extruded at 120°C onto one end of one of the smooth faces of a coupon and immediately spacers were put in place, a thermocouple was embedded in the composition, and a second coupon placed thereon to overlap 2.5 cm of the first coupon.
  • the assembly was pressed at 0.7 MPa for 15 to 20 seconds, which forced the composition to cover the 2.5 cm x 2.5 cm area of the overlap and to ooze out from the edges of the bonded area.
  • the bonded constructions were conditioned at 25°C and 50% relative humidity for 10 days. A 0.9 kg (2 pounds) weight was hung from one end of the bonded construction and the bonded construction suspended from the other end in an oven at 48.9°C (120°F). Once the embedded thermocouple showed a temperature of 48.9°C, the samples were allowed to stand at that temperature for 15 minutes. Cycles of raising the temperature of the oven in 5.55°C (10°F) increments and holding that temperature for 15 minutes were repeated until bond failure occurred.
  • a composition's heat resistance is defined as the last temperature at which bond failure did not occur within the 15-minute holding time.
  • Peel adhesion was determined using a modified version of ASTM D-903 in which the flexible substrate was canvas and the rigid substrate was either abraded aluminum, cold rolled steel, polypropylene, polyethylene, polycarbonate, polystyrene or poly(methyl methacrylate).
  • the adhesive was extruded at 120° C onto the center portions of: (1) 2.5 cm x 10 cm x 0.15 cm pieces of 2024-grade aluminum (Vincent Metals; Minneapolis, MN) which had been wiped with methyl ethyl ketone (MEK), (2) 2.5 cm x 10 cm x 0.079 cm (20 gauge) pieces of cold rolled steel (Vincent Metals; Minneapolis, MN) which had been wiped with MEK, (3) 2.5 cm x 10 cm x 0.3 cm pieces of rigid polystyrene (Huntsman grade 730) (Precision Punch & Plastics Co.; Minnetonka, MN) which had been wiped with isopropanol, and (4) 2.5 cm x 10 cm x 0.3 cm pieces of rigid polypropylene (National Tool & Manufacturing Co.; Kenil worth, NJ) which had been wiped with MEK.
  • Peel adhesion was measured as the average of the high and low readings of the three coupons and is reported in pounds per inch width (piw) and Newtons per centimeter width (N/cm).
  • parts means pbw). These components are identified as follows: MAPO (Maleated polyolefin) P 1824-011 (Eastman Chemical Co.) is a maleated amorphous poly(propylene- hexene) (APH) having an acid number of 42. It was dried by heating in a vacuum oven at 121°C (250°F) for 16 hours.
  • P 1824-012 (Eastman Chemical Co.) is an APH having an acid number of 40. It was dried by heating in a vacuum oven at 121 °C (250°F) for 16 hours.
  • P I 824-013 (Eastman Chemical Co.) is an APH having an acid number of 20.
  • NOVA Guerbet Alcohol 20iTM hydroxyl-functional polyolefin (NOVA Molecular Technologies, Inc.), molecular weight 298, has a hydroxyl group attached near the center of a fully saturated backbone. It was dried by heating in a vacuum oven at 121 °C (250°F) for 2 hours.
  • UnilinTM 700 (Petrolite Corp.) is a linear hydrocarbon alcohol having 50 carbon atoms. It was dried by heating in a vacuum oven at 121°C (250°F) for 2 hours.
  • Polyols PolytailTM-H and PolytailTM-HA (Mitsubishi Kasei Corp.) are hydrogenated polybutadiene diols having hydroxyl numbers of 37-53 and 41-55, respectively. They were dried by heating in a vacuum oven at 121°C (250°F) for 2 hours.
  • EpolTM polyisoprene (Idemitsu Petrochemical Co. Ltd.) is a hydrogenated polyisoprene diol. It was dried by heating in a vacuum oven at 121°C (250°F) for 2 hours.
  • HPVM TM -2500 (Shell Chemical Co.; Houston, TX) is a hydrogenated polybutadiene diol having terminal hydroxyl groups. It was dried in a vacuum oven at 121°C (250°F) for 2 hours.
  • MDI is diphenylmethane-4,4'-diisocyanate available as Mondur TM M (Miles Chemical Co .).
  • Silan TM A-1310 (Union Carbide Co ⁇ .; Danbury, CT) is 3-isocyanatopro- pyltriethoxysilane. Tackifier
  • Arkon TM E-90 (Arakawa Chemical Co.; Chicago, EL) is a deeply hydrogenated hydrocarbon tackifying resin.
  • Catalysts DBTDL is dibutyltin dilaurate.
  • DMDEE is dimorpholine diethyl ether.
  • Examples 1-7 Monools Relative amounts of components used in the preparation of moisture curable hot- melt compositions in which the hydroxyl group-containing component is a monool are given in Table I. The table also sets forth viscosities (in cP) of the resulting uncured compositions at 121°C (250°F), their dead load heat resistances, and the 180° peel obtained for each moisture cured composition. These compositions were prepared according to the following procedure: A stainless steel reactor was preheated to about 107°C (225°F) and purged with nitrogen. Polyisocyanate was added so as to provide two equivalents of isocyanate per hydroxyl equivalent. Monool was added to the reactor, and the mixture was stirred for 10 to 20 minutes.
  • Table I shows the amounts of reagents used in the preparation of and the performance characteristics of moisture-curable hot-melt compositions in which the hydroxyl group-containing component is a monool.
  • Polypropylene 61.2 Polystyrene 49.0 Glass 56.0 Aluminum 56.0 Cold rolled steel 64.7
  • a stainless steel reactor was preheated to about 107°C (225°F) and purged with nitrogen before polyisocyanate was added. Poiyol was added to the reactor, and the mixture was stirred for 10 to 20 minutes. A mixture of MAPO and tackifier was added to the reactor. Mixing was continued for about 10 minutes at 107°C (225°F) before catalyst was added. The nitrogen purge was discontinued, a vacuum of 20-30 in Hg was applied, and mixing was continued for 30 minutes. The product was discharged and stored in aluminum cartridges sealed against moisture. TABLE III
  • compositions 17-21 were prepared according to the following procedure:
  • a stainless steel reactor was preheated to 107°C (225°F) and purged with nitrogen before polyisocyanate was added. When it had melted, MAPO and tackifier were added. After approximately 20 to 30 minutes of mixing at 107°C (225°F) under nitrogen purge, catalyst was added. The nitrogen purge was discontinued and a vacuum of 20-30 in Hg was applied. Mixing was continued for an additional 30 minutes. The product was discharged into aluminum cartridges and sealed against moisture.
  • Examples 16 and 22 are comparative examples containing no polyisocyanate. They were prepared by adding MAPO and tackifier to a stainless steel reactor and mixing, under vacuum, for 20 to 30 minutes at 107°C (225°F). The product was discharged into aluminum cartridges and sealed against moisture.

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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)
  • Polyurethanes Or Polyureas (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

On décrit des compositions de colles auto-adhésives qui durcissent sous l'effet de l'humidité, laquelle transforme des groupes isocyanate en liaisons uréthane-urée. Les adhésifs formés à partir de ces compositions ont une résistance élevée au cisaillement aux températures élevées, une adhésion améliorée aux substrats à faible énergie de surface, une résistance améliorée à la chaleur et une durée de conservation avant l'utilisation plus longue. Les compositions contiennent le produit de réaction d'un polyisocyanate et d'une polyoléfine maléique, avec en plus, à titre facultatif, une composé hydroxylé ayant réagi avec le polyisocyanate et une résine pour améliorer l'adhésivité.
PCT/US1994/013267 1994-11-16 1994-12-30 Adhesif polyolefinique qui durcit par l'action de l'humidite WO1996015170A1 (fr)

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US08/340,521 1994-11-16

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998028379A1 (fr) * 1996-12-21 1998-07-02 Ppg Industries Ohio, Inc. Compose de scellage et son utilisation en vue de produire des recipients etanches
WO2001094426A2 (fr) * 2000-06-05 2001-12-13 Bridgestone Corporation Polymeres greffes proches de leur point de gelification presentant des proprietes d'amortissement elevees
EP1036103B2 (fr) † 1997-12-01 2008-07-16 Henkel AG & Co. KGaA Adhesif thermofusible de polyurethane modifie
WO2023161761A1 (fr) 2022-02-23 2023-08-31 Sasol South Africa Limited Composition adhésive thermofusible

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51114438A (en) * 1975-04-02 1976-10-08 Mitsubishi Petrochem Co Ltd Reactive hot-melt adhesives
EP0420246A1 (fr) * 1989-09-27 1991-04-03 Sekisui Chemical Co., Ltd. Composition d'un adhésif thermofusible réactif
EP0632077A2 (fr) * 1993-07-01 1995-01-04 Minnesota Mining And Manufacturing Company Adhésif de polyuréthane durcissable par l'humidité

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51114438A (en) * 1975-04-02 1976-10-08 Mitsubishi Petrochem Co Ltd Reactive hot-melt adhesives
EP0420246A1 (fr) * 1989-09-27 1991-04-03 Sekisui Chemical Co., Ltd. Composition d'un adhésif thermofusible réactif
EP0632077A2 (fr) * 1993-07-01 1995-01-04 Minnesota Mining And Manufacturing Company Adhésif de polyuréthane durcissable par l'humidité

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 86, no. 4, 24 January 1977, Columbus, Ohio, US; abstract no. 17960m, INOUE ET AL: "REACTIVE HOT-MELT ADHESIVES" page 69; column 2; *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998028379A1 (fr) * 1996-12-21 1998-07-02 Ppg Industries Ohio, Inc. Compose de scellage et son utilisation en vue de produire des recipients etanches
EP1036103B2 (fr) † 1997-12-01 2008-07-16 Henkel AG & Co. KGaA Adhesif thermofusible de polyurethane modifie
WO2001094426A2 (fr) * 2000-06-05 2001-12-13 Bridgestone Corporation Polymeres greffes proches de leur point de gelification presentant des proprietes d'amortissement elevees
WO2001094426A3 (fr) * 2000-06-05 2002-05-23 Bridgestone Corp Polymeres greffes proches de leur point de gelification presentant des proprietes d'amortissement elevees
WO2023161761A1 (fr) 2022-02-23 2023-08-31 Sasol South Africa Limited Composition adhésive thermofusible

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