EP0764179A1 - Polymere mit oximinosilanendgruppen, sowie daraus hergestellte elastomere - Google Patents

Polymere mit oximinosilanendgruppen, sowie daraus hergestellte elastomere

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Publication number
EP0764179A1
EP0764179A1 EP95917800A EP95917800A EP0764179A1 EP 0764179 A1 EP0764179 A1 EP 0764179A1 EP 95917800 A EP95917800 A EP 95917800A EP 95917800 A EP95917800 A EP 95917800A EP 0764179 A1 EP0764179 A1 EP 0764179A1
Authority
EP
European Patent Office
Prior art keywords
silane
polymer
polyols
carbon atoms
terminated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP95917800A
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English (en)
French (fr)
Inventor
Dale Russell Flackett
Edward Thanaraj Asirvatham
Chempolil Thomas Mathew
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Honeywell International Inc
Original Assignee
AlliedSignal Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by AlliedSignal Inc filed Critical AlliedSignal Inc
Publication of EP0764179A1 publication Critical patent/EP0764179A1/de
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C08G18/83—Chemically modified polymers
    • C08G18/837—Chemically modified polymers by silicon containing 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
    • C08G18/83—Chemically modified 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/6715—Unsaturated monofunctional alcohols or amines
    • 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
    • C08G18/83—Chemically modified polymers
    • C08G18/834—Chemically modified polymers by compounds containing a thiol group
    • C08G18/835—Unsaturated polymers modified by compounds containing a thiol group

Definitions

  • the invention relates to oximinosilane terminated polymers which are cured at room temperature to become stable elastomers. They have improved physical properties such as elongation, moisture resistance, variable cure rate, tensile and tear strength in various formulations. Such polymers have use as adhesives, coatings and sealants.
  • polysiloxane having hydrolyzable silicon-end groups are often used in single-component sealant formulations. Upon exposure to the atmosphere, the polymer undergoes rapid vulcanization with atmospheric moisture. Due to the high cost of polysiloxane polymers, it is desirable to use low-cost organic polymers such as polyethers, polyesters and polysulfides as the polymer backbone.
  • organic polymers such as polyethers, polyesters and polysulfides
  • silane terminated polymers are the most desirable due to the ease of curing with atmospheric moisture and their low odor and toxicity. However, these silane terminated polymers are in limited use because of their poor physical properties such as low tensile and tear strengths.
  • U.S. Patent 3,317,461 discloses oximesilane terminated polysulfides made by reacting a mercaptan terminated polysulfide with a silane having hydrolyzable groups and at least one olefinic double bond. These polymers, when cured, do not have high tensile and tear strength due to the lack of urethane groups.
  • U.S. Patent 4,960,844 discloses silane endcapped polymers with urethane groups in the polymer chain. Hydrolyzable groups attached to the silicon atom are alkoxy groups with lower alkyl groups.
  • the silane terminated polymers of this invention are easily cured at room temperature in the presence of normal humidity to a hydrolytically stable solid elastomer having high tensile and tear strength and low compression set. No catalyst is required for this cure to take place although a wide variety of catalysts known to the art can be used to decrease cure times.
  • An object of the invention is to provide an organic liquid polymer endblocked with silanes containing ketoximes as the hydrolyzable groups that can be cured at room temperature into a rubber-like elastomer or leathery adhesive when exposed to moisture.
  • R is an organic polymer containing a backbone of polyether, polythioether or polyester
  • R 1 is a divalent organic radical
  • R 2 is an alkylene group having at least
  • X is 0 or N ⁇ where R 6 is either hydrogen or a monovalent lower alkyl group, Y is sulfur or S-R 7 -S where R 7 is an alkylene thioether having 4-12 carbon atoms, alkylene having 2 to 10 carbon atoms, or a substituted cyclohexyl ring group having the formula:
  • R 3 is an alkyl radical of 1 to 7 carbon atoms or an alkoxy radical of 1 to 6 carbon atoms and R 4 and R 5 are independently a saturated straight chain or branched alkyl radical of 1 to 7 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl and amyl, or R 4 and R 5 taken together form a cyclized group, p is 2 to 3, m is 0 to 2, n is 1 to 3 and the sum of m and n is 3.
  • the invention further provides a method for the production of the above oximinosilane terminated polymers.
  • a prepolymer is formed by reacting a hydroxyl- terminated polymer with an organic diisocyanate to produce an isocyanate terminated polymer.
  • the isocyanate terminated polyol is reacted with an olefinic alcohol or amine in which the olefinic group is separated by at least one carbon atom to give olefin terminated polyether polyol.
  • the invention still further provides a method for the production of the above oximinosilane terminated polymers by reacting the isocyanate terminated polyol with a mercapto alcohol to produce a mercaptan terminated polymer; and then reacting with a vinyloxime silane.
  • the invention also provides a formulated sealant, coating, foam or adhesive composition which comprises the above oximinosilane terminated polymer in admixture with a plasticizer, filler, .and moisture scavenger as well as an optional adhesion promoter, catalyst, rheology modifier and/or crosslinker.
  • the invention encompasses organic polymers, having hydrolyzable ketoximino silyl group at each end of each molecule as is shown by the formula described above.
  • the polymeric backbone, noted as R in the general formula can be such as hydroxyl terminated polypropylene oxide polyols, polybutyleneoxide glycol polyols, polytetramethylene glycol polyols, polyester polyols, polythioether polyols, polyalkylene glycol co-polymer polyols, and polyalkylene glycol-polyester copolymer polyols.
  • R organic diisocyante
  • organic diisocyanates are toluene diisocyanate, diphenylmethane 4,4'-diisocyanate, 1,6- hexamethylene diisocyanate and isophorone diisocyanate.
  • the prepolymers can be converted to mercaptan- erminated polymers by either 1) reacting with a mercapto alcohol in which the mercaptan and the hydroxyl groups are separated by at least two methylene groups or 2) or reacting with a olefinic alkylene alcohol or amine of at least three carbon atoms wherein the olefin group is separated from the hydroxyl or amine by at least 1 carbon atom.
  • the resulting olefin-terminated polymer is then reacted with a dimercaptan, in which the mercaptan functionality is separated by alkylenes, alkylene ethers, alkylene thioethers, alkylene esters and substituted cyclohexyl rings to .give mercaptan-terminated polymers. Hydrogen sulfide can also be used to obtain the mercaptan terminated polymer by using at least 1 mole for each equivalent of olefinic polymer to ensure all olefin functionality is terminated with the mercaptan groups.
  • the preferred dimercaptans are 1,2-ethane dithiol, 1,6-hexane dithiol, 1,10-decane dithiol, 2-mercaptoethylether, 2- mercaptoethylsulfide, glycol dimercapto acetate, glycol dimercapto propionate, p-menthane-2,9-dithiol and ethylcyclohexane dithiol.
  • Preferred mercapto alcohols are 2-mercaptoethanol, 3-mercapto-1-propanol.
  • the above straight forward reaction is catalyzed by 0.1 to 1.0 weight % of radical initiators such as organic peroxides or azobis alkyl nitriles.
  • the reaction temperature is maintained between 55°C and 120°C with the preferred range between 55°C and 85°C.
  • a silane terminated polymer which is preferably a liquid and preferably has a molecular weight of from about 1200 to about 100,000. This is also a radical initiated addition reaction between the mercaptan group of the polymer and the olefin group of the vinyloximesilane.
  • the preferred silane has the formula, R4
  • ketoximino silane terminated liquid polymers of the present invention are different from the prior art by having urethane groups and the sulfur atoms separated by just 2 or more carbon atoms in the polymer backbone and also because of at least one fast hydrolyzable neutral ketoximino group attached to the silicon atom.
  • the oximinosilane terminated polymers may be used alone, but more preferably are blended with additives known in the art for the preparation of such adhesives, sealants and coating compositions.
  • additives known in the art for the preparation of such adhesives, sealants and coating compositions.
  • non-exclusively include plasticizers, fillers, reinforcing agents, moisture scavengers, rheology modifiers, colorants, uv stabilizers, fungicides, mildewcides, antimicrobial agents, antioxidants, polymers, crosslinkers, coupling agents, adhesion promoters, and catalysts, thixotropic agents, flame retardants, thermal and electrically conductive fillers, blowing agents, surfactants, heat stabilizers, and solvents etc. to tailor the composition to a specifically desired application. These usually may be added at any stage of the mixing operation but care should be taken to add them under anhydrous conditions to avoid introducing additional moisture.
  • the amount of polymer to be used in this invention ranges from above 5 to about 90 percent by weight of the total composition but preferably ranges from about 15 to about 60 percent by weight of the total composition.
  • the polymer may be used to create a foam by those skilled in the art through the use of a low boiling point liquid or other suitable blowing agent, an example of which is 1,1-dichloro-l-fluoro ethane in combination with a surfactant as a foam stabilizer.
  • a low boiling point liquid or other suitable blowing agent an example of which is 1,1-dichloro-l-fluoro ethane in combination with a surfactant as a foam stabilizer.
  • the composition can contain a filler which may be a reinforcing silica filler, a semireinforcing filler, a non-reinforcing filler or mixtures thereof.
  • a filler which may be a reinforcing silica filler, a semireinforcing filler, a non-reinforcing filler or mixtures thereof.
  • reinforced silica fillers are fumed silica and precipitated silica.
  • useful silica fillers •are described in U.S. Patents 3,837,878; 2,938,009; 3,004,859, and 3,635,743 which are incorporated by reference.
  • the amounts of reinforcing filler ranges from 0 to about 50 percent by weight of the total composition, preferably from about 0 to about 14 percent by weight and most preferably 2 to 8 percent by weight.
  • a non-reinforcing or semi-reinforcing filler can also be used at levels up to 75%. These include fillers such as calcium carbonate and ground quartz. Other semi-reinforcing fillers or extending fillers which are known in the art may be used. These include, but are not limited to silica aerogel, diatomaceous earth, iron oxide, titanium oxide, aluminum oxide, zirconium silicate, calcined clay, magnesium oxide, talc, wollastonite, hydrated alumina, and carbon black. The total amount of all fillers in the composition ranges from 0% to about 60% and preferably from about 6% to about 55% by weight of the overall composition.
  • Methyl tris- (methyl ethyl ketoximino) silane, vinyl tris- (methyl ethyl ketoximino) silane and tetrakis- (methyl ethyl ketoximino) silane are the predominant oxime silanes used commercially as crosslinkers in oxime RTV compounds and are used to speed the cure. Also useful as crosslinklers and herein are those silanes described in U.S. patent 3,189,576 and is hereby incorporated by reference.
  • Crosslinker can be present in an amount of from about 0 to about 10 percent by weight of the total composition, however from about 3 to about 7 percent by weight is preferred and from about 3 to about 6 percent by weight is most preferred.
  • Tetrafunctional alkoxy- ketoxime silanes as disclosed in U.S. Patents 4,657,967 and 4,973,623 can also be used as crosslinkers and are incorporated herein by reference.
  • U.S. Patent 4,705,877 describes aminohydrocarbyl substituted ketoximinosilanes as coupling agents and is incorporated herein by reference.
  • adhesion promoters non-exclusively including gamma-aminopropyltriethoxy silane and gamma- aminopropyltrimethoxy silane as described in U.S. Patent 4,720,530.
  • Other adhesion promoters may include 3- glycidoxypropyl trimethoxy silane or gamma-mercaptopropyl trimethoxy silane.
  • the amount of adhesion promoter may range from about 0 to about 5.0 percent by weight of the total composition. Preferably 0.5 to 1.5 percent by weight of the total composition is used.
  • the composition may further contain an optional catalyst which accelerates the reaction of the polymer.
  • catalysts non-exclusively include organotin carboxylates such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctoate, dibutyltin maleate, dialkyl tin hexoates, dioctyltin dilaurate, iron octanoate, zinc octanoate, lead octanoate, cobalt naphthenate, amines such as diamine, and titanantes.
  • Dibutyltindilaurate is the preferred catalyst.
  • Use levels of catalyst can range from 0 to about 2.0 percent by weight of the total composition, preferably about 0.05 to about 1 percent and most preferably from about 0.2 to about 0.5 weight percent.
  • the composition may also contain an optional plasticizer to improve the extrusion properties of the composition and to modify the modulus of the cured composition.
  • an optional plasticizer to improve the extrusion properties of the composition and to modify the modulus of the cured composition.
  • Such include phthalates, adipates, and aromatic hydrocarbons.
  • Suitable plasticizers include dibutylphthalate, dioctylphthalate, triarylphosphate and substituted analogs thereof.
  • the plasticizer is added in an amount ranging from 0 to 50 weight percent based on the overall composition, preferably from about 10 to about 30 weight percent.
  • Preferred viscosity of the plasticizer ranges from about 100 to about 1000 cps. at 25°C.
  • Common uv stabilizers include benzophenones and hydroxyphenyl benzotriazoles families, including hydroxyphenyl benzotriazole monomers and dimers. Hydroxyphenyl benzotriazole monomers are disclosed in U.S. Patents 3,204,896; 5,097,041; 4,943,637 and 5,104,992. 2-hydroxy-4-alkoxybenzophenones are useful uv absorbers and light stabilizers.
  • U.S. Patents 3,399,237 and 3,310,525 show compounds having benzophenone functional groups. The uv stability of such materials is improved by mixing the polymer with from about 0.1% to about 5 % based on the weight of the polymer composition of the asymmetrical dimer of this invention.
  • Moisture scavengers are preferably present in an amount of from 0 to about 5% by weight of the composition.
  • Suitable moisture scavengers non-exclusively include trifunctional or greater oximinosilanes, molecular sieves and other moisture reactive materials.
  • Rheology modifiers are preferably present in an amount of from 0 to about 5% by weight of the composition.
  • Suitable rheology modifiers non-exclusively include smectic clay, fumed silica, castor oil, castor wax and fibers.
  • Preferred colorants for this invention are pigments and dyes.
  • colorants are titanium dioxide, carbon black, silica, zinc oxide, and clay. It is preferably present in an amount ranging from about 5% to about 10% based on the weight of the solids in the layer.
  • the composition also may contain an optional bacteriostat/fungistat.
  • the most preferred compound is acetoxy-dimethoxydioxane. Such are preferably present in an amount of from about 0.001% to about 1.0% by weight of the composition.
  • Solvents useful for forming coating compositions include essentially any inert organic solvent that is a solvent for the other composition components. Solvents may be ethers, ketones, hydrocarbons and halocarbons, among others. The amount of solvent can be determined by the skilled artisan depending on the end use. The other optional components may be present in an amount ranging from about 0 to about 10 weight percent based on the entire composition.
  • composition of the present invention can be used in the form of a one component room temperature curing composition which is produced by mixing the above described components and various additives in the absence of moisture and storing in a closed vessel which is impervious to moisture.
  • the composition is cured to an elastomer by exposure to atmospheric moisture at the time of use when the package is broken.
  • olefinic terminated polymer To the above obtained olefinic terminated polymer is added 94.2 g (1.0 moles) of 1,2-ethane dithiol and 4.65 g azobisisobutyronitrile and heated to 80-95°C for two hours with slow stirring to prevent vortex formation. The mercaptan content of the polymer is confirmed by iodometric titration and the mercaptan equivalent weight is calculated. To the mercaptan polymer thus obtained is added 267.5 g methyl vinyl bis(2-butanone oxime) silane (1.05 moles, 95% assay) and 5.18 g azobisisobutyronitrile initiator and the mixture is heated at 80-95°C for 2 hours with continuous stirring. The nitrogen blanket is kept throughout the reaction.
  • the M.W. of the polymer at different steps is determined by GPC.
  • the final polymer is moisture sensitive therefore is stored in a nitrogen flushed closed container.
  • the viscosity of the polymer ranges between 900-1100 poise at 23°C (90,000-110,000 cps) .
  • EXAMPLE 2 An olefin terminated polymer is prepared following the procedure described in Example 1.
  • the pre-polymer is prepared from 1,100 grams of polypropylene glycol polyol with hydroxyl number of 28.8, 96 grams of toluene diisocyanate and 0.30 grams of DABCO.
  • the olefin terminated polymer is prepared by reacting the prepolymer with 33.6 grams of allyl alcohol and 1.20 grams of DABCO.
  • EXAMPLE 3 An olefin terminated polymer is prepared according to the procedure described in Example 1. 1300 Grams of polypropylene glycol polyol with a hydroxyl number of 28.8, 130.5 grams of toluene diisocyanate and 0.36 gram of DABCO catalyst are heated at 80°C for 1 1/2 hours to give isocyanate terminated polymer which is converted to olefin terminated polymer by reacting with 43.6 grams of allyl alcohol and 1.26 grams of DABCO catalyst at 80°C for 4 hours.
  • TDI 80/20 and 0.33 gm 24% solution of DABCO are added to polybutyleneoxide having a molecular weight 4878 (300 g, 0.0615 moles) under nitrogen atmosphere. The mixture is heated to 80°C for 1-2 hours. Allyl alcohol (7.15 gm, 0.123 moles, 99%) and 1.31 gm DABCO solution are added to the above mixture and heated to 80°C for 1-2 hours with continuous stirring. To the polymer thus obtained is added (146 gm 0.123 moles, 99%) 1,2-ethane dithiol and 0.51 gm azobisisobutyronitrile and heated for 2 hours at 80-90°C.
  • methylvinyl bis(2- butanone oxime) silane and 0.56 gm AIBN are added to the mercaptan polymer and heated for 2 hours at 80-90°C.
  • the polymer at different steps is characterized by IR, GPC and volumetric titration.
  • the viscosity of the silyl terminated polymer is 100,000 cps at 24°C.
  • polyester polyol To 300 gm (0.14465 moles) propyleneoxide pentanediol and polyester polyol is added 50. 4 gm (0.2893 moles) toluene diisocyanate and 0.37 gm DABCO catalyst solution.
  • the polyester polyol used has a molecular weight of 2074 and hydroxyl number 54.1. The mixture is heated to 80°C for 1-2 hours in a nitrogen atmosphere. Allyl alcohol 16.8 gm (0.2893 moles, 99%) and 1.5 gm DABCO solution is added and heated for 1-2 hours at 80°C with continuous stirring.
  • the allyl terminated polymer thus obtained is reacted with 19.2 g (0.2040 moles) 1,2-ethane dimercaptan and 0.55 g AIBN initiator. The temperature of the reaction is kept between 80-90°C for 2 hours. Finally 54.5 g (0.2142 moles) 95% assay methyl vinyl bis(2-butanone oxime) silane and 0.62 g AIBN is added and reacted at 80-90°C for 2 hours.
  • the silyl terminated polymer thus obtained is highly viscous (1 million cps at 24.5°C).
  • EXAMPLE 7 A polythioether polyol, 300 g (0.15 mole), having hydroxyl number 56 and molecular weight 2000 is reacted with 52.4 g (0.30 mole) of toluene diisocyanate in the presence of 0.37 g DABCO solution at 80°C for 1-2 hours. The prepolymer thus obtained is reacted with 17.4 g (0.30 moles) of allyl alcohol in the presence of 1.5 g DABCO catalyst solution for 1-2 hours. 28.3 g (0.30 moles) of 1,2 ethane dithiol and 0.15 weight% of AIBN are added and stirred slowly for 2 hours at 80-90°C.
  • Cure rate is compared for identical polymers with varying types of silane end capping.
  • the mercaptan terminated polymer prepared as in Example 1 is divided into three reactors designated A, B and C.
  • the polymer in reactor A is capped with methylvinyl bis(methoxy) silane
  • the polymer in B is capped with methylvinyl bis(ethoxy) silane
  • the polymer in reactor C capped with methyl vinyl bis(2-butanone oxime) silane as described in Example 1 for ketoximino silane.
  • the capped polymers are prepared as sealants to compare physical properties such as curing rates and strength by the following formu ⁇ lations and methods.
  • Sealant is produced from each polymer using the formulas and methods in Table 1. Cure times, cure though rates and mechanical properties are measured and listed in Table 1. Sealant prepared by formulation 1 or 2 with ethoxy silane capped polymer fails to cure.
  • Example 6 To 50 parts by weight of the polymer of Example 6 is added 50 parts by weight of a modified cumene-indole resin (softening point, Ring and Ball by ASTM E-28 100°C) at a temperature of between 150 and 200°C. The mixture is prepared as a sheet on polypropylene and allowed to cool. The sheet is allowed to cure for 15 days at room temperature after which it is exposed to 100°C for 6 hours followed by an additional 9 days at room temperature. Tensile properties are as follows: tensile strength - 15 N/mm2; elongation - 790%, hardness (Shore A) -17. Formulation 6
  • Adhesion is ranked on a scale of 1 to 6 with 1 being no adhesion and 6 being cohesive failure at both tensile force angles.
  • the samples are then exposed to boiling water for 15 days and re-tested using the same method. The sample consistently exhibits partial cohesive failure at 45° tensile pull and 100% cohesive failure at 90° pull.
  • Di-octyl phthalate 24.50 CaC03 43.00 Methyl tri(2-butanone oxime) silane 2.00
  • Moisture scavenger Oxzolidine (Angus Chemical) 3.00 3-ethyl-2-methyl-2- (3-methyl butyl) -1,3-oxazolidine
  • Example 2 Example 3 Example 1 Skin Over Time 100-150 80-100 300 (Minutes)
  • EXAMPLE 8 A 1 liter three neck reactor flask fitted with an overhead stirrer, thermometer and addition funnel is charged with 17.5 grams of toluene diisocyanate (0.10M) and heated to 80° to 90°C. Polypropylene oxide diol with average molecular weight of 4000, (200 gm, 0.05M) is added slowly. The reaction mixture is refluxed at 80° to 90°C for 2-4 hours and the progress of the condensation is monitored by infrared spectroscopy. 2-mercaptoethanol (7.8 gm. , 0.10M) is added slowly to the reaction mixture and refluxed at 90° to 100°C until the infrared spectrum of the pot sample shows no isocyanate absorption at 2265 cm "1 .
  • Methylvinyl bis(methylethylketoximino)silane (31.3 gm. , 0.10M) and AIBN (460 mg) are added to the mercapto terminated polyol and refluxed at 85-90°C for 3 hours to give an oximesilane terminated liquid polyol polymer.
  • EXAMPLE 9 Example 8 is repeated except 3-mercaptopropanol (92 g, 0.10M) is used. Similar results are noted.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Sealing Material Composition (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Silicon Polymers (AREA)
EP95917800A 1994-06-07 1995-05-03 Polymere mit oximinosilanendgruppen, sowie daraus hergestellte elastomere Withdrawn EP0764179A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US25520494A 1994-06-07 1994-06-07
US255204 1994-06-07
PCT/US1995/005473 WO1995033784A1 (en) 1994-06-07 1995-05-03 Oximino silane terminated polymers and elastomers formed therefrom

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EP0764179A1 true EP0764179A1 (de) 1997-03-26

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EP (1) EP0764179A1 (de)
JP (1) JPH10502392A (de)
KR (1) KR970703377A (de)
CN (1) CN1149880A (de)
AU (1) AU2372995A (de)
BR (1) BR9507837A (de)
CA (1) CA2190751A1 (de)
CZ (1) CZ358896A3 (de)
HU (1) HUT75496A (de)
NZ (1) NZ285011A (de)
WO (1) WO1995033784A1 (de)

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US8314183B2 (en) 2007-12-22 2012-11-20 Bridgestone Corporation Silane coupled polymers
US8816044B2 (en) * 2011-09-21 2014-08-26 PRC DeSoto International, Inc Flexible polyamines, flexible amine-terminated adducts, compositions thereof and methods of use
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CA2190751A1 (en) 1995-12-14
HU9603384D0 (en) 1997-02-28
HUT75496A (en) 1997-05-28
JPH10502392A (ja) 1998-03-03
BR9507837A (pt) 1997-09-02
MX9605594A (es) 1998-05-31
WO1995033784A1 (en) 1995-12-14
NZ285011A (en) 1998-05-27
CZ358896A3 (en) 1997-06-11
KR970703377A (ko) 1997-07-03
CN1149880A (zh) 1997-05-14
AU2372995A (en) 1996-01-04

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