WO1998018843A1 - Produits d'etancheite a base de poly(ether-urethane) fonctionnel aloxy-silane durcissables a l'humidite - Google Patents
Produits d'etancheite a base de poly(ether-urethane) fonctionnel aloxy-silane durcissables a l'humidite Download PDFInfo
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- WO1998018843A1 WO1998018843A1 PCT/US1997/019367 US9719367W WO9818843A1 WO 1998018843 A1 WO1998018843 A1 WO 1998018843A1 US 9719367 W US9719367 W US 9719367W WO 9818843 A1 WO9818843 A1 WO 9818843A1
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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
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
- C09J171/02—Polyalkylene oxides
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
- C08G18/4841—Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
Definitions
- the present invention pertains to moisture curable sealant compositions based on alkoxysilane functional poly(ether-urethane)s which provide improved paint adhesion even in the absence of polar solvents or polar plasticizers.
- the present invention also provides coated substrates and laminates formed from such compositions.
- Sealants are often used in automotive, marine, aerospace, and construction markets to fill gaps, to prevent corrosion, and to create aesthetically pleasing surfaces. Commercially viable sealants strike an acceptable balance among end use performance properties such as cure speed, shelf life, rheological characteristics, adhesion to various substrates, and thermal and ultraviolet light stability. Consequently, such sealants typically contain rheology modifiers, adhesion promoters, oxidative stabilizers, plasticizers, and cure catalysts. A variety of technologies have been found useful in the manufacture of these sealants, including acrylic latexes, moisture curing silicones, and moisture curing isocyanate functional polymers. Moisture curing isocyanate functional polymers generally cure rapidly and, after cure, provide good adhesion to paint overcoats.
- sealants based on moisture curing isocyanate functional polymer technology are particularly preferred. Even so, several problems attend the use of sealants based on moisture curing isocyanate functional polymers; under very hot, humid conditions these sealants are prone to foaming and the alcoholic co-solvents which are present in many paints react with the isocyanate termini of the moisture curing isocyanate functional polymers thereby rendering them non-reactive and permanently preventing cure.
- sealants based on moisture curing alkoxysilane functional polymers have been proposed as alternative to those based on moisture curing isocyanate functional polymers.
- the alkoxysilane functional polymers are preferred over isocyanate functional polymers especially because they do not foam under hot, humid conditions and they cure properly even in the presence of alcoholic paint co- solvents. It is possible, therefore, to paint sealants based on alkoxysilane functional polymers before they are fully cured (i.e., wet-on-wet) thereby eliminating the non- productive cure time required before painting sealants based on moisture curing isocyanate functional polymers.
- Alkoxysilane functional polymers known in the art have been prepared by numerous methods including: condensation of isocyanate functional polymers with amine, mercaptan, or hydroxyl functional silanes; condensation of amine, mercaptan, or hydroxyl functional polymers with isocyanate functional silanes; coupling of mercaptan or hydrosilane functional polymers with alkene functional silanes; and coupling of alkene functional polymers with mercaptan functional silanes or alkoxyhydrosilanes.
- Alkoxysilane functional polymers may be compounded to form materials useful as moisture curable sealants. While a large number of alkoxysilane functional polymers has been disclosed in the art, none provide moisture curing sealants exhibiting acceptable paint adhesion when the paint is applied during the latter stages of cure.
- U.S. Patent No. 3,627,722 (Waterr), U.S. Patent No. 4,067,844 (Barron et al.), U.S. Patent No. 4,857,623 (Emmerling et al.), and U.S. Patent No. 5,364,955 (Zwiener et al.) each disclose alkoxysilane functional poly(ether urethanes). None of these teaches a moisture curable sealant exhibiting acceptable paint adhesion when the paint is applied during the latter stages of cure.
- U.S. Patent Nos. 5,476,889 and 5,464,888 (Owen) describe alkoxysilane functional polymer based sealant compositions in which the alkoxysilane endgroups are attached to a polypropylene oxide backbone through alkylene linking groups.
- sealants based on alkoxysilane functional polymers we have observed an unacceptable, time dependent decrease in the adhesion of paint to the previously known moisture curable sealants based on alkoxysilane functional polymers.
- previously known alkoxysilane functional polymers provide only minimal paint adhesion when the sealants are allowed to cure completely prior to paint application. This exactly opposes what is observed with sealants based on moisture curing isocyanate functional polymers.
- the present invention pertains to moisture curable sealant compositions based on alkoxysilane functional poly(ether-urethane)s which provide improved paint adhesion even in the absence of polar solvents or polar plasticizers.
- the present invention also provides coated substrates and laminates formed from such composition.
- the moisture curable sealant composition of the present invention comprises an alkoxysilane functional poly(ether-urethane) having formula (I): co
- W 1 and W 2 are independently selected from the group consisting of -CO 2 R 9 , -CONR 9 2 , -CN, and -COR 9 ; or W 1 and W 2 taken together form a divalent linking group selected from the group consisting of -CO 2 -R 8 -O 2 C-, -CONR 9 -R 8 -NR 9 CO-, -CONR 9 -R 8 -O 2 C-, and -CONR 9 CO- such that W 1 ,
- x is selected from the group consisting of integers greater than or equal to
- each L is independently selected from the group consisting of (i) a polyether segment comprising an internal polypropylene oxide block and terminal polyethylene oxide blocks, the segment comprising 20 to 30 mol % EO and the segment having a number average molecular weight of about 3000 to about 6000.
- each L is independently selected from the group consisting of (i) a polyether segment comprising an internal polypropylene oxide block and terminal polyethylene oxide blocks, the segment comprising 20 to 30 mol % EO and the segment having a number average molecular weight of about 3000 to about 6000; each R 4 is independently selected from the group consisting of 1,6-hexylene and isophorone-diyl. each z is independently selected from integers 0 to 4; each R 5 is independently selected from the group consisting of Ci to C alkyl; each n is the integer 3; each x is independently selected from integers 2 to 4.
- the moisture curable sealant composition of the present invention comprises a homogenous blend comprising: (a) 100 parts by weight of an alkoxysilane functional poly(ether-urethane) of formula I;
- the present invention further comprises a laminate article, wherein the laminate comprises: (a) a substrate;
- the present invention even further comprises a cured laminate article, wherein the laminate comprises:
- a preferred embodiment of the present invention comprises a laminate article, wherein the laminate comprises: (a) a substrate;
- a preferred embodiment of the present invention comprises a cured laminate article, wherein the laminate comprises: (a) a substrate; (b) a cured layer of the moisture curable sealant composition of the invention bonded to at least a portion of the substrate;
- the laminate articles described above may include, for example, portions of land vehicles (such as automobiles, buses, trucks, vans, trains, etc.), aircraft, and watercraft (such as boats).
- the present invention provides a moisture curable sealant composition
- a moisture curable sealant composition comprising an alkoxysilane functional poly(ether-urethane) of formula (I) as previously defined: (I)
- the alkoxysilane functional poly(ether-urethane) is the reaction product of an isocyanate functional poly(ether-urethane) of formula (IV): (IV)
- R 6 , X, R 5 , Y and n are as previously defined.
- a preferred endgroup precursor compound has the structure:
- m is selected from the group consisting of integers 2 to 6 and R 5 , R , W 1 , W , and n have the definitions provided above and which may be formed, for example, by the Michael addition of a primary amine functional alkoxysilane compound of formula (VI) with a Michael receptor of formula (VII) as taught in U.S. Patent No. 5,364,955 incorporated by reference herein.
- Preferred Michael receptors (VII) are maleic and/or fumaric acid diesters.
- Formulas (VI) and (V ⁇ ) are as follows:
- R 5 , R 6 , W 1 , W 2 , m, and n have the definitions provided above.
- preferred end group precursor compounds (V) include HS(CH 2 ) 3 ,(OCH 3 ) 3 ; H 2 N(CH 2 ) 3 Si(OCH 3 ) 3 ; H 2 N(CH 2 ) 3 Si(OCH 2 CH 3 ) 3 ,
- the isocyanate functional poly(ether-urethane) of formula (IV) may be prepared by the condensation reaction of one or more isocyanate reactive materials with an excess of one or more polyisocyanates, preferably diisocyanates, and preferably in the presence of a catalyst.
- Isocyanate reactive materials useful according to the invention include polyethers which have molecular weights of about 2000 to about 8000, EO contents greater than about 15 mol % and less than about 40 mol %, and one or more hydroxyl, mercaptan, primary or secondary amine groups.
- Isocyanate reactive materials useful according to the invention also include diols and diamines having a number average molecular weights of less than about 200 (known in the art as "chain extenders").
- Blends of two or more isocyanate reactive materials may be used to make the isocyanate functional poly(ether- urethane)s.
- isocyanate functional poly(ether- urethane)s A summary of basic polyurethane chemistry can be found in Polyurethanes: Chemistry and Technology, Saunders and Frisch, Interscience
- Preferred isocyanate reactive materials are block and random copolymers of ethylene oxide and propylene oxide having number average molecular weights in the range of from about 2000 to about 8000, more preferably from about 3000 to about 6000 and containing greater than about 15 mol% and less than about 40 mol% ethylene oxide (EO) units, more preferably about 20 mol% to about 30 mol%. Diols are especially preferred. When the EO content is less than or equal to about 15 mol%, little improvement in paint adhesion is observed. When the EO content is above about 40 mol %, the viscosity of the sealant often rises, moisture sensitivity increases, and compatibility with additives may be reduced.
- EO ethylene oxide
- Polyether diols are commercially available from a large number of sources and may be prepared by ring-opening polymerization reactions that are well known in the polymer art. The chemistry and mechanism of ring-opening polymerizations, for example, are discussed in detail in Ring-Opening Polymerization (Volumes 1, 2, and 3) edited by K.J. Ivin and T. Saegusa, 1984. Polyether diols useful as synthons in the present invention comprises ethylene oxide and higher alkylene oxide randomly or in blocks.
- Sequential polymerization of ethylene oxide (EO) and higher alkylene oxide, preferably propylene oxide (PO), will produce block copolymers, for example those having an internal polypropylene oxide block and terminal polyethylene oxide blocks, hereinafter denoted EO(PO)EO, and those having an internal polyethylene oxide block and terminal polypropylene oxide blocks, hereinafter denoted PO(EO)PO.
- EO(PO)EO an internal polypropylene oxide block and terminal polyethylene oxide blocks
- PO(EO)PO internal polyethylene oxide block and terminal polypropylene oxide blocks
- Simultaneous polymerization of ethylene oxide and higher alkylene oxide, preferably propylene oxide will produce random copolymers, hereinafter denoted EO/PO.
- Numerous polyether diols are commercially available, for example from
- a particularly preferred polyether diol is Pluronic L92 from ARCO, an EO(PO)EO block copolymer having 20 mol% EO units and number average molecular weight of about 3650.
- Suitable polyisocyanates useful in preparation of isocyanate functional poly(ether-urethane)s of formula (IV) include aliphatic and cycloaliphatic polyisocyanates.
- Representative examples of useful polyisocyanates include the diisocyanates isophorone diisocyanate (hereinafter denoted IPDI) and 1,6-hexanediisocyanate. Dimers and trimers of the above mentioned diisocyanates, for example those containing uretadione, biuret, and isocyanurate linkages, are also contemplated.
- a preferred polyisocyanate is IPDI.
- the condensation reaction to form an isocyanate functional poly(ether- urethane) is typically conducted in the presence of up to 5 % by weight (wt%) catalyst based on the isocyanate reactive material weight, preferably 0.02 to 0.4 wt%.
- wt% catalyst examples include but are not limited to those listed in Polyurethanes: Chemistry and Technology. Part I, Table 30, Chapter 4, Saunders and Frisch, Interscience Publishers, New York, 1963.
- Preferred catalysts are the tin IV compounds, for example dibutyltin dilaurate.
- reaction time required to convert the reactants to the desired isocyanate functional poly(ether-urethane)s will vary widely. Reaction times will depend upon several factors, including the nature of the reactants, the concentration of reactants, and the temperature of the reaction. Progress of the reaction is readily monitored by infrared (LR) spectroscopy by following the reduction of the isocyanate stretching frequency near 2270 cm '1 . Suitable reaction temperatures are usually between 0°C and 120°C, preferably between 25°C and 90°C, more preferably between 50°C and 90°C.
- the alkoxysilane functional poly(ether-urethane) of formula (I) useful in the present invention is prepared by reacting an isocyanate functional poly(ether- urethane) of formula (IV) with the endgroup precursor of formula (V) described above.
- the isocyanate functional poly(ether-urethane) has a number average molecular weight in the range of about 6000 to about 10,000, more preferably about 7000 to about 9000.
- the ratio of equivalents of NCO to equivalents of endgroup precursor is 1 : 1.
- a stepwise procedure is followed whereby the isocyanate functional poly(ether-urethane) is separately formed and then combined with the endgroup precursor to form the alkoxysilane functional poly(ether-urethane).
- reaction time required to convert the reactants to the desired alkoxysilane functional poly(ether-urethane)s of formula (I) will vary widely.
- Reaction times will depend upon several factors, including the nature of the reactants, the concentration of reactants, and the temperature of the reaction. Progress of the reaction is readily monitored by infrared (LR) spectroscopy by following the disappearance of the isocyanate stretching frequency near 2270 cm “1 . Suitable reaction temperatures are usually between 0°C and 120°C, preferably between 25°C and 90°C, more preferably between 50°C and 90°C.
- the moisture curable sealant compositions of the present invention comprise at least one alkoxysilane functional poly(ether-urethane) of formula (I), at least one plasticizer, at least one antioxidant, at least one catalyst, and at least one adhesion promoter.
- the moisture curable sealant compositions of the present invention may further comprise one or more of the following optional ingredients: rheology modifiers, biocides, corrosion inhibitors, dehydrators, organic solvents, fillers, colorants, photostabilizers, and perfumes.
- the components may be combined before or during the formation of the alkoxysilane functional poly(ether-urethane), provided that the components are not reactive with isocyanate.
- the components are combined with the alkoxysilane functional poly(ether-urethane) after its formation.
- Each component is introduced to perform a specific function and should be present at a level sufficient to perform that function.
- Catalysts present in the moisture curable sealant compositions of the present invention enable the sealants to cure at rapid, controllable rates.
- Useful catalysts include, for example, metal salts and complexes, amines, and organic and inorganic acids. Specific examples of useful catalysts include dibutyltin diacetylacetonate, tetraisopropyl titanate, calcium oxide, N,N,N',N'-tetramethylguanidine, tetrabutylammonium hydroxide, trifluoroacetic acid, and dibutyl phosphate.
- Plasticizers present in the moisture curable sealant compositions of the present invention lower the viscosities of the sealants before cure and lower their moduli after cure.
- Useful plasticizers include, for example, benzoates, phthalates, adipates, and sulfonamides. It is generally preferred that the amount of plasticizer not exceed about 20% of the total weight of the composition.
- Specific examples of useful plasticizers include butyl benzyl phthalate, dipropylene glycol dibenzoate, dioctyl adipate, N-ethyl- -toluenesulfonamide, diisodecyl phthalate, and dibutyl phthalate.
- Adhesion promoters present in the moisture curable sealant compositions of the present invention provide good bonding between the sealants and the various substrates to which they are applied.
- Useful adhesion promoters include silanes, for example, 3 -(2-aminoethyl)aminopropyltrimethoxysilane, 3 -glycidoxypropyl- trimethoxysilane, and 3-mercaptopropyltrimethoxysilane.
- Antioxidants present in the moisture curable sealant compositions of the present invention retard the oxidative degradation of its organic components.
- the presence of an antioxidant is especially important when the sealant is to be used in extreme temperature environments.
- useful antioxidants include but are not limited to those selected from the group consisting of hindered phenols and hindered amines. Specific example of useful antioxidants include 2,6-di-tert-butyl-
- the antioxidant comprises a mixture of about 20 wt% hindered amine and 80 wt% hindered phenol.
- Rheology modifiers which may be present in the moisture curable sealant compositions of the present invention cause the sealants to resist flow under static conditions, yet allow desirable flow while under shear.
- Useful rheology modifiers include, for example, castor waxes, fumed silicas, treated clays, and polyamides.
- the rheology modifier is non-reactive with the alkoxysilane functional poly(ether-urethane) .
- one or more organic solvents may be present in the moisture curable sealant compositions of the present invention.
- Organic solvents reduce sealant viscosities.
- preferred solvents are those which are unreactive with isocyanates and alkoxysilanes and include, for example, ketones, ethers, esters, amides, and hydrocarbons.
- preferred solvents include acetone, butanone, ethyl acetate, toluene, naphtha, N-methylpyrrolidinone, N,N-dimethylformamide, acetonitrile, tetrahydrofuran, l-methoxy-2-propyl acetate, and Isopar H (an aliphatic hydrocarbon solvent available from Exxon).
- Especially preferred solvents are polar solvents.
- a specific example of an especially preferred solvent is
- Dehydrators which may be present in the moisture curable sealant compositions of the present invention react with any moisture which may enter the sealant during processing or during storage and thus prevent premature gelation.
- useful dehydrators include vinyltrimethoxysilane, trimethyl orthoformate, tetra(butanone oximino)silane, and vinyltri(butanone oximino)silane.
- Fillers which may be present in the moisture curable sealant compositions of the present invention may be added to alter the color, rheology, and ultimate mechanical properties of the moisture curable sealant composition.
- useful fillers include carbon black, calcium carbonate, titanium dioxide, iron oxide, talc, ceramic microspheres, and clay. The fillers are preferably free of groups which react with the alkoxysilane functional poly(ether-urethane)s. Stearic acid surface treated, precipitated calcium carbonates are preferred fillers in applications where low cost and opacity are desirable.
- Ultraviolet light stabilizers which may be present in the moisture curable sealant compositions of the present invention absorb ultraviolet radiation, thereby shielding the other organic components from this harmful energy.
- Useful ultraviolet light stabilizers include substituted hydroxyphenylbenzotriazoles.
- a specific example of a useful ultraviolet light stabilizer is 2-(3.5-di-tert-butyl-2- hydroxyphenyl)-5-chlorobenzotriazole.
- the moisture curable sealant compositions of the invention may be formulated such that, they provide good adhesion to a variety of substrates, they provide good adhesion to a variety of paints, primers, and paint sealers, and they are sprayable, caulkable, or paste-like.
- the physical properties of the moisture curable sealant compositions before and after cure will depend strongly on the amounts and identities of the components comprising the moisture curable sealant compositions. Viscosities of the moisture curable sealant compositions before cure will generally decrease, for example, with increasing levels of solvent or plasticizer, decreasing alkoxysilane silane functional poly(ether-urethane) molecular weight, decreasing filler concentration, and increasing filler particle size.
- a desirable viscosity for a sprayable moisture curable sealant composition for example, would be between about 400 and about 700 Pa sec (Brookfield spindle #7 at 2 rpm, 22 °C).
- Useful substrates for the articles of the invention include but are not limited to those selected from the group consisting of glass, metal, wood, and polymers.
- Useful metal substrates include, for example, cold rolled steel, primed steel, galvanized steel, and aluminum.
- Useful polymeric substrates include, for example, thermoplastics, paint coated surfaces, and fiberglass reinforced plastics.
- Useful primers, paints, and paint sealers include for example those which utilize epoxy, acrylic, urethane, lacquer and enamel chemistries in commercially available formulations. Other paints, primers and paint sealers are also considered as useful and the above examples shall not be considered as limiting in any way.
- Viscosities were determined at 22°C using a Brookfield DV-1+ viscometer and are reported in Pascal seconds (Pa sec).
- IR spectra were obtained using a Nicolet 510 FT-IR spectrometer. NMR spectra were obtained using a Varion Unity 500 NMR Spectrometer. The NMR Spectrometer was operated at 500 megahertz to obtain ⁇ -NMR spectra. All NMR runs were carried out using CDC1 3 solvent at 22°C using standard acquisition parameters.
- Tack free time was the time required to produce a surface on the moisture curable sealant composition bead which could be lightly touched by an applicator stick without transfer to the applicator stick.
- This test was performed in a controlled environment having a temperature of 21°C and a relative humidity of 50%.
- a 0.64 cm bead of moisture curable sealant composition was applied to the test surface.
- the hardness of the bead was measured after 24 hours (initial reading) and after seven days (final reading), using a Shore Durometer Type A.
- a 0.64 cm diameter, 22.9 cm long bead of moisture curable sealant composition was applied to a cold rolled steel panel (30.5 cm x 10.16 cm) that had been cleaned by wiping first with methyl ethyl ketone, then with toluene, and then again with methyl ethyl ketone.
- the bead was allowed to cure for one week in a controlled environment having a temperature of 21°C and a relative humidity of 50%.
- One end of the bead was cut away from the steel panel to form a free end. The free end was pulled, and the failure mode of the sealer was noted. Cohesive failure occurred when the sealer split, leaving sealer residue on the panel. Adhesive failure occurred when the sealer lifted off the panel, leaving no residue. Of these two modes of failure, cohesive failure is preferred.
- a panel bearing a bead of cured, moisture curable sealant composition was prepared as described according to the adhesion test method above. The panel was cooled and held at -20°C for one hour. The panel was then quickly bent 180 degrees over a 2.54 cm diameter rod with the sealer on the outside radius. The sealer failed this test if it pulled away from the panel without leaving any residue (i.e., adhesive failure) or if it showed any cracks at the point of bending.
- a 0.64 cm diameter, 22.9 cm long bead of moisture curable sealant composition was applied to a cold rolled steel panel (30.5 cm x 10.16 cm) that had been previously cleaned by wiping first with methyl ethyl ketone, then with toluene, and then again with methyl ethyl ketone. The bead was then smoothed to form a
- Proper paint cure was indicated by a dry paint surface. Proper moisture curable sealant composition cure was determined by cutting the sealer and examining whether it was dry throughout. If no defects were seen using these inspection procedures, the sealer was considered to have wet-on- wet paintability.
- a 0.64 cm diameter, 22.9 cm long bead of moisture curable sealant composition was applied to a cold rolled steel panel (30.5 cm x 10.16 cm) that had been previously cleaned by wiping first with methyl ethyl ketone, then with toluene, and then again with methyl ethyl ketone. The bead was then smoothed to form a
- Paint PPG Deltron base clear available from Pittsburgh Paint & Glass, Inc. located in Strongsville, OH was applied to separate films of the moisture curable sealant compositions immediately and after the films of moisture curable sealant composition had aged for one hour, 24 hours, and 72 hours.
- the painting sequence was per the manufacturer instructions: One part base coat (DBU 9700) was mixed with 1.5 parts reducer (DRR 1170). Two applications of base coat were applied fifteen minutes apart using a spray pressure of 310 kilopascals.
- a moisture curable sealant composition which has been painted one hour after its application to a substrate will have a paint adhesion value of at least 4B, more preferably 5B.
- a moisture curable sealant composition which has been painted 24 hours after its application to a substrate will also have a paint adhesion value of at least 4B, more preferably 5B.
- a moisture curable sealant composition which has been painted 72 hours after its application to a substrate will have a paint adhesion value of at least 3B, more preferably at least 4B, and most preferably 5B.
- a cartridge containing the moisture curable sealant composition was tested for viscosity, tack free time, hardness, adhesion, and cold flexibility, and then stored at 50°C. After four weeks, the moisture curable sealant composition was re- submitted to the above tests. If the moisture curable sealant composition remained homogeneous and again passed these tests, then the moisture curable sealant composition was considered to have good shelf life. Cartridges used for aging were high density polyethylene.
- Dabco T-12 dibutyltin dilaurate Air Products, Allentown, PA
- Pluronic L92 EO(PO)EO polyether diol 20 mol% EO, 3650 MW (BASF)
- Pluronic 17R2 PO(EO)PO polyether diol 20 mol% EO, 2150 MW (BASF)
- Pluronic 31R1 PO(EO)PO polyether diol 10 mol% EO, 3250 MW (BASF)
- Desmodur I isophorone dusocyanate (Bayer, Inc., Pittsburgh, PA) Mondur TD-80 Blend of 2,4- and 2,6-tolylene diisocyanates (80:20) (Bayer, Inc.)
- Irganox 1010 pentaerythritol tetrakis[3 -(3 , 5-di-tert-butyl-4- hydroxyphenyl)propionate] (Ciba-Geigy)
- Dislon 6500 polyamide thickener (King Industries, Norwalk, CT) (currently named Disparlon 6500)
- Pfinyl 402 5.5 micron, ground, stearated calcium carbonate (Specialty Minerals, Adams, MA)
- Neostann U220 dibutyltin diacetylacetonate (Kaneka America, New York, NY) The invention is further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this invention.
- the polyether polyol was mixed with phosphoric acid (85 wt% solution in water, 0.14 mmol acid per kilogram polyol) and then dried over a four hour period at 105°C under pump vacuum (about 0.5 torr).
- the polyether polyol was allowed to cool to about 50°C in the absence of moisture and then mixed under a nitrogen blanket with a dusocyanate and Dabco T-12.
- the mixture was agitated without external temperature control for one half hour, then heated to and held at 70°C for three hours.
- the isocyanate functional poly(ether-urethane) thus obtained was allowed to cool to about 50°C, a secondary amine functional alkoxysilane prepared as in Examples 1-3 was added and mixed under a nitrogen blanket, and the mixture was again heated to and held at 70°C. An IR spectrum taken after the mixture had been held at 70°C for six hours exhibited no isocyanate band (2270 cm "1 ).
- the identities and quantities of polyether polyols, diisocyanates, and secondary amine functional alkoxysilanes used and the quantities of Dabco T-12 used are shown in Table 2.
- the viscosities and theoretical molecular weights of the resulting alkoxysilane functional poly(ether-urethane)s are shown in Table 3. Note that Examples C10-C15 are comparative.
- Moisture curable sealant compositions were prepared from each of the alkoxysilane terminated poly(ether-urethanes) prepared in Examples 4-9 and
- a vacuum reactor fitted with a high shear mixer was flushed with nitrogen and filled with the following components:
- the components were mixed at low shear for 5 minutes while under a nitrogen blanket. Dislon 6500 (see Table 4) was added and mixing occurred at high sheer for 10 minutes.
- the particulate fillers selected from Ultrapflex, Pfinyl 402, and Zeeospheres 600 as specified in Table 4, previously dried overnight at 105°C) were added and mixed at high speed under full vacuum for 30 minutes while heating the mixture to 90°C. The mixture was then cooled to 50°C, and the reactor purged with nitrogen to break the vacuum.
- a solution containing Isopar H, Dabco T-12, and Silquest A171 in the amounts specified in Table 4 was added and mixed at high shear for 1 hour under nitrogen at 50°C.
- Dabco T- 12 wt. 0.1 g 0.1 g o.i g 0.1 g 0.2 g 0.2 g
- Dislon 6500 wt. 10 g 10 g 10 g 10 g 8 g 12 g
- Pfinyl 402 wt. 550 g 550 g 550 g 550 g 400 g 400 g
- Dabco T-12 wt. 0.1 g 0.1 g 0.1 g 0.2 g 0.2 g 0.2 g
- Neostann U220 wt. 2 g 2 g 2 g 3 g 2 g H
Abstract
Cette invention a trait à des compositions d'étanchéité à base de poly(éther-uréthane) fonctionnel aloxy-silane, durcissables à l'humidité et assurant une meilleure adhérence à la peinture et ce, même en l'absence de solvants ou de plastifiants polaires. Elle concerne également des substrats revêtus et des stratifiés préparés à l'aide de ces produits.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU49999/97A AU4999997A (en) | 1996-10-31 | 1997-10-28 | Moisture curable alkoxysilane functional poly(ether-urethane) based sealants |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US74159496A | 1996-10-31 | 1996-10-31 | |
US08/741,594 | 1996-10-31 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998018843A1 true WO1998018843A1 (fr) | 1998-05-07 |
Family
ID=24981361
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1997/019367 WO1998018843A1 (fr) | 1996-10-31 | 1997-10-28 | Produits d'etancheite a base de poly(ether-urethane) fonctionnel aloxy-silane durcissables a l'humidite |
Country Status (2)
Country | Link |
---|---|
AU (1) | AU4999997A (fr) |
WO (1) | WO1998018843A1 (fr) |
Cited By (25)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0994138A1 (fr) * | 1998-10-14 | 2000-04-19 | Bayer Aktiengesellschaft | Composés durcissables à l'humidité contenant des groupements isocyanate et alcoxysilane |
EP0994139A1 (fr) * | 1998-10-14 | 2000-04-19 | Bayer Aktiengesellschaft | Composées durcissables à l'humidité contenant des groupements ioscyanate et alcoxysilane |
EP0999225A1 (fr) * | 1998-10-14 | 2000-05-10 | Bayer Corporation | Composés durcissables à l'humidité contenant des groupements isocyanate et alcoxysilane |
WO2001016201A1 (fr) * | 1999-08-20 | 2001-03-08 | Crompton Corporation | Compositions durcissables a l'humidite a extremites protegees au silane |
US6265517B1 (en) | 1999-09-07 | 2001-07-24 | Bostik, Inc. | Silylated polyether sealant |
US6649016B2 (en) | 2002-03-04 | 2003-11-18 | Dow Global Technologies Inc. | Silane functional adhesive composition and method of bonding a window to a substrate without a primer |
WO2004060952A1 (fr) | 2002-12-20 | 2004-07-22 | Bayer Materialscience Llc | Procede de preparation d'urethane de polyether durcissable a l'humidite avec des groupes terminaux uree cycliques /silane reactifs |
WO2004060953A1 (fr) | 2002-12-20 | 2004-07-22 | Bayer Materialscience Llc | Urethanes de polyether durcissables a l'humidite a groupes terminaux uree cycliques / silane reactifs et leur utilisation en tant qu'agent d'etancheite, adhesifs et revetement |
US6809170B2 (en) | 2002-05-31 | 2004-10-26 | Bayer Materialscience Llc | Moisture-curable, polyether urethanes with reactive silane groups and their use as sealants, adhesive and coatings |
US6833423B2 (en) | 2002-06-18 | 2004-12-21 | Bayer Polymers Llc | Moisture-curable, polyether urethanes with reactive silane groups and their use as sealants, adhesives and coatings |
US6844413B2 (en) | 2002-06-18 | 2005-01-18 | Bayer Materialscience Llc | Moisture-curable, polyether urethanes with reactive silane groups and their use as sealants, adhesives and coatings |
US6887964B2 (en) | 2002-05-31 | 2005-05-03 | Bayer Materialscience Llc | Moisture-curable, polyether urethanes with reactive silane groups and their use as sealants, adhesives and coatings |
US6919414B2 (en) | 1999-05-05 | 2005-07-19 | Bp Chemicals Limited | Copolymers and films thereof |
EP1605008A2 (fr) * | 2004-05-28 | 2005-12-14 | Bostik Sa | Composition adhésive à base de polymère à terminaison bloquée avec des groupes silyle |
WO2005118679A2 (fr) * | 2004-05-28 | 2005-12-15 | Bostik Sa | Nouvelle composition d'adhesif |
US6998459B2 (en) | 2002-06-18 | 2006-02-14 | Bayer Materialscience Llc | Polyether urethanes containing one reactive silane group and their use in moisture-curable polyether urethanes |
US7060750B2 (en) | 2004-04-28 | 2006-06-13 | Bayer Materialscience Llc | Moisture-curable, polyether urethanes and their use in sealant, adhesive and coating compositions |
US7115696B2 (en) | 2002-05-31 | 2006-10-03 | Bayer Materialscience Llc | Moisture-curable, polyether urethanes with reactive silane groups and their use as sealants, adhesives and coatings |
US7345130B2 (en) | 2005-10-25 | 2008-03-18 | Dow Global Technologies Inc. | Silane functional prepolymer and isocyanate functional prepolymer blend based adhesive composition |
US7368487B2 (en) | 2001-11-15 | 2008-05-06 | 3M Innovative Properties Company | Aqueous ink jet printable compositions |
US7465778B2 (en) | 2003-12-19 | 2008-12-16 | Bayer Materialscience Llc | Silante terminated polyurethane |
US7482420B2 (en) | 2004-03-24 | 2009-01-27 | Construction Research & Technology Gmbh | Silane-terminated polyurethanes with high strength and high elongation |
EP2183332A2 (fr) * | 2007-07-26 | 2010-05-12 | Bayer MaterialScience LLC | Adhésifs hydrophiles |
WO2010105814A1 (fr) * | 2009-03-19 | 2010-09-23 | Bostik S.A. | Composition adhésive présentant une résistance améliorée en vert |
WO2023160197A1 (fr) * | 2022-02-23 | 2023-08-31 | 广州市白云化工实业有限公司 | Agent d'étanchéité monocomposant modifié par du silicium organique susceptible de subir rapidement un durcissement en couche profonde à basse température et procédé de préparation associé |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0164520A1 (fr) * | 1984-04-19 | 1985-12-18 | Henkel Kommanditgesellschaft auf Aktien | Compositions de polyuréthane ayant incorporé un agent d'accrochage |
EP0210444A1 (fr) * | 1985-06-28 | 1987-02-04 | Union Carbide Corporation | Polymères de polyuréthanes vulcanisables terminés par des silanes |
EP0269819A2 (fr) * | 1986-10-30 | 1988-06-08 | Bayer Ag | Utilisation de produits de polyaddition de polyéther-uréthane-urée comme masse d'empreinte dentaire |
EP0410199A2 (fr) * | 1989-07-22 | 1991-01-30 | Bayer Ag | Matériau en plastique durcissable en plusieurs étapes |
EP0459304A2 (fr) * | 1990-05-30 | 1991-12-04 | Adco Products, Inc. | Composition de scellement à une composante |
US5364955A (en) * | 1992-11-06 | 1994-11-15 | Bayer Aktiengesellschaft | Compounds containing alkoxysilane and amino groups |
-
1997
- 1997-10-28 AU AU49999/97A patent/AU4999997A/en not_active Abandoned
- 1997-10-28 WO PCT/US1997/019367 patent/WO1998018843A1/fr active Application Filing
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0164520A1 (fr) * | 1984-04-19 | 1985-12-18 | Henkel Kommanditgesellschaft auf Aktien | Compositions de polyuréthane ayant incorporé un agent d'accrochage |
EP0210444A1 (fr) * | 1985-06-28 | 1987-02-04 | Union Carbide Corporation | Polymères de polyuréthanes vulcanisables terminés par des silanes |
EP0269819A2 (fr) * | 1986-10-30 | 1988-06-08 | Bayer Ag | Utilisation de produits de polyaddition de polyéther-uréthane-urée comme masse d'empreinte dentaire |
EP0410199A2 (fr) * | 1989-07-22 | 1991-01-30 | Bayer Ag | Matériau en plastique durcissable en plusieurs étapes |
EP0459304A2 (fr) * | 1990-05-30 | 1991-12-04 | Adco Products, Inc. | Composition de scellement à une composante |
US5364955A (en) * | 1992-11-06 | 1994-11-15 | Bayer Aktiengesellschaft | Compounds containing alkoxysilane and amino groups |
Cited By (35)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0994138A1 (fr) * | 1998-10-14 | 2000-04-19 | Bayer Aktiengesellschaft | Composés durcissables à l'humidité contenant des groupements isocyanate et alcoxysilane |
EP0994139A1 (fr) * | 1998-10-14 | 2000-04-19 | Bayer Aktiengesellschaft | Composées durcissables à l'humidité contenant des groupements ioscyanate et alcoxysilane |
EP0999225A1 (fr) * | 1998-10-14 | 2000-05-10 | Bayer Corporation | Composés durcissables à l'humidité contenant des groupements isocyanate et alcoxysilane |
US6919414B2 (en) | 1999-05-05 | 2005-07-19 | Bp Chemicals Limited | Copolymers and films thereof |
WO2001016201A1 (fr) * | 1999-08-20 | 2001-03-08 | Crompton Corporation | Compositions durcissables a l'humidite a extremites protegees au silane |
KR100727217B1 (ko) * | 1999-08-20 | 2007-06-13 | 제너럴 일렉트릭 캄파니 | 실란 말단-캡씌어진 습윤 경화성 조성물 |
AU762409B2 (en) * | 1999-08-20 | 2003-06-26 | General Electric Company | Silane endcapped moisture curable compositions |
KR100753732B1 (ko) * | 1999-08-20 | 2007-08-31 | 제너럴 일렉트릭 캄파니 | 실란의 제조방법 |
US6265517B1 (en) | 1999-09-07 | 2001-07-24 | Bostik, Inc. | Silylated polyether sealant |
US7368487B2 (en) | 2001-11-15 | 2008-05-06 | 3M Innovative Properties Company | Aqueous ink jet printable compositions |
US6649016B2 (en) | 2002-03-04 | 2003-11-18 | Dow Global Technologies Inc. | Silane functional adhesive composition and method of bonding a window to a substrate without a primer |
US6809170B2 (en) | 2002-05-31 | 2004-10-26 | Bayer Materialscience Llc | Moisture-curable, polyether urethanes with reactive silane groups and their use as sealants, adhesive and coatings |
US6887964B2 (en) | 2002-05-31 | 2005-05-03 | Bayer Materialscience Llc | Moisture-curable, polyether urethanes with reactive silane groups and their use as sealants, adhesives and coatings |
US7115696B2 (en) | 2002-05-31 | 2006-10-03 | Bayer Materialscience Llc | Moisture-curable, polyether urethanes with reactive silane groups and their use as sealants, adhesives and coatings |
US6833423B2 (en) | 2002-06-18 | 2004-12-21 | Bayer Polymers Llc | Moisture-curable, polyether urethanes with reactive silane groups and their use as sealants, adhesives and coatings |
US6844413B2 (en) | 2002-06-18 | 2005-01-18 | Bayer Materialscience Llc | Moisture-curable, polyether urethanes with reactive silane groups and their use as sealants, adhesives and coatings |
US6998459B2 (en) | 2002-06-18 | 2006-02-14 | Bayer Materialscience Llc | Polyether urethanes containing one reactive silane group and their use in moisture-curable polyether urethanes |
WO2004060953A1 (fr) | 2002-12-20 | 2004-07-22 | Bayer Materialscience Llc | Urethanes de polyether durcissables a l'humidite a groupes terminaux uree cycliques / silane reactifs et leur utilisation en tant qu'agent d'etancheite, adhesifs et revetement |
WO2004060952A1 (fr) | 2002-12-20 | 2004-07-22 | Bayer Materialscience Llc | Procede de preparation d'urethane de polyether durcissable a l'humidite avec des groupes terminaux uree cycliques /silane reactifs |
US7309753B2 (en) | 2002-12-20 | 2007-12-18 | Bayer Materialscience Llc | Process for the preparation of moisture-curable, polyether urethanes with terminal cyclic urea reactive silane groups |
US7465778B2 (en) | 2003-12-19 | 2008-12-16 | Bayer Materialscience Llc | Silante terminated polyurethane |
US8394909B2 (en) | 2004-03-24 | 2013-03-12 | Construction Research & Technology Gmbh | Silane-terminated polyurethanes with high strength and high elongation |
US7482420B2 (en) | 2004-03-24 | 2009-01-27 | Construction Research & Technology Gmbh | Silane-terminated polyurethanes with high strength and high elongation |
US7060750B2 (en) | 2004-04-28 | 2006-06-13 | Bayer Materialscience Llc | Moisture-curable, polyether urethanes and their use in sealant, adhesive and coating compositions |
EP1605008A2 (fr) * | 2004-05-28 | 2005-12-14 | Bostik Sa | Composition adhésive à base de polymère à terminaison bloquée avec des groupes silyle |
EP1605008A3 (fr) * | 2004-05-28 | 2006-06-14 | Bostik Sa | Composition adhésive à base de polymère à terminaison bloquée avec des groupes silyle |
WO2005118679A2 (fr) * | 2004-05-28 | 2005-12-15 | Bostik Sa | Nouvelle composition d'adhesif |
WO2005118679A3 (fr) * | 2004-05-28 | 2006-06-15 | Bostik Sa | Nouvelle composition d'adhesif |
US7345130B2 (en) | 2005-10-25 | 2008-03-18 | Dow Global Technologies Inc. | Silane functional prepolymer and isocyanate functional prepolymer blend based adhesive composition |
EP2183332A2 (fr) * | 2007-07-26 | 2010-05-12 | Bayer MaterialScience LLC | Adhésifs hydrophiles |
EP2183332A4 (fr) * | 2007-07-26 | 2012-08-22 | Bayer Materialscience Llc | Adhésifs hydrophiles |
WO2010105814A1 (fr) * | 2009-03-19 | 2010-09-23 | Bostik S.A. | Composition adhésive présentant une résistance améliorée en vert |
CN102388082A (zh) * | 2009-03-19 | 2012-03-21 | 博斯蒂克股份公司 | 具有改进的生强度的粘合剂组合物 |
US9109146B2 (en) | 2009-03-19 | 2015-08-18 | Bostik S.A. | Adhesive composition with improved green strength |
WO2023160197A1 (fr) * | 2022-02-23 | 2023-08-31 | 广州市白云化工实业有限公司 | Agent d'étanchéité monocomposant modifié par du silicium organique susceptible de subir rapidement un durcissement en couche profonde à basse température et procédé de préparation associé |
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