WO1990008168A1 - Metallic oxide-oxirane polymers and prepolymers - Google Patents
Metallic oxide-oxirane polymers and prepolymers Download PDFInfo
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- WO1990008168A1 WO1990008168A1 PCT/US1990/000370 US9000370W WO9008168A1 WO 1990008168 A1 WO1990008168 A1 WO 1990008168A1 US 9000370 W US9000370 W US 9000370W WO 9008168 A1 WO9008168 A1 WO 9008168A1
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- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
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- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
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- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
Definitions
- This invention relates to novel polymers and more particularly to high performance polymers provided by cross-reaction of an inorganic with an organic oligomer.
- Oxirane oligomers are known to be very useful for meeting high performance needs in fabricating structural composites, protective coatings, adhesives, castings, laminating, electrical potting compounds and the like.
- the performance and utility of oxirane polymers are also known to be dependent upon their chemical structure, the curing agent used and conditions of cure.
- One important factor in achieving a high performance polymer is often the chemical structure of the polymer.
- polymer systems can be produced having enhanced properties in areas such as chemical and corrosion resistance, high adhesive strength, high heat deflection temperatures and toughness. These properties are often based on the crosslink density capabilities of the particular oligomer or prepolymer used. Usually, the higher the crosslink density, the higher the chemical and corrosion resistance, the higher the adhesive strength, the higher the mechanical strength, the higher the heat deflection temperature and the better the toughness.
- DGER diglycidyl ether of resorcinol
- Diglycidyl ether of resorcinol has an epoxide equivalent of bebween 120 and 135 and a viscosity at 25oC. of between 300 and 500 CPS.
- the small molecular size leads to the low epoxide equivalent and indicates that the molecule can achieve a high final crosslink density.
- Another oxirane oligomer is a low molecular weiglit diglycidyl ether of bisphenol A, having an epoxide equivalent between 172 and 176 and a viscosity at 25oC. between 4000 and 6000 CPS.
- This compound has the following structure:
- U.S. Patent 4,383,060 to Dearlove teaches an epoxy adhesive comprising an epoxy novolac resin, an epoxy flexibilizer, natural and colloidal silica and an imidazole curing agent.
- U.S. Patent 4,499,217 to Yoshimura et al. is directed to a thermosetting resinous liquid compositions comprising a composite formed from a dispersion of silica colloid in alcohol and a thermosetting resin such as an epoxy-phenol.
- U.S. Patent 4,383,060 to Dearlove teaches an epoxy adhesive comprising an epoxy novolac resin, an epoxy flexibilizer, natural and colloidal silica and an imidazole curing agent.
- U.S. Patent 4,499,217 to Yoshimura et al. is directed to a thermosetting resinous liquid compositions comprising a composite formed from a dispersion of silica colloid in alcohol and a thermosetting resin such as an epoxy-phenol.
- Patent 4,486,558 to Guilbert discloses an electrically insulating powder comprising a blend of (1) a derivative of a polyglycidyl ether of bisphenol A and (2) finely divided silica, while U.S. Patent 4,574,132 to Sayles describes an adhesive comprising (1) diglycidyl ether of bisphenol A, (2) diglycidyl ether of 1,4 butanediol, and (3) silica.
- U.S. Patent 4,748,300 to Lalancette is directed to a polyhydroxysilicate-polymer reaction product.
- the product is prepared by reacting a finely divided polyhydroxysilicate and a hydroxy-containing polymer.
- the Lalancette product is obtained by reacting the polyhydroxysilicate and the hydroxy-containing polymer without the use of a coupling agent and the teaching stresses the elimination of the coupling agent.
- the resultant material is, in any case, a completely polymerized mass.
- the present invention relates to a novel oxirane prepolymer comprising the catalyzed reaction product of an inorganic oxide having at least one hydrolyzable oxygen with a difunctional oxirane oligomer having at least one aromatic moiety and at least one oxirane containing aliphatic moiety, characterized in that substantially all of the hydrolyzable oxygen atoms in said oxide are bonded to said oligomer and there is substantially no bonding between oligomer moieties.
- the present invention relates to a novel inorganic oxide containing polymer, said polymer comprising at least three crosslinked prepolymer moieties, each said prepolymer moiety being the reaction product of an inorganic oxide having at least one hydrolyzable oxygen with a difunctional oxirane oligomer having at least one aromatic moiety and at least one oxirane containing aliphatic moiety.
- the present invention relates to a process for preparing metallic oxide-oligomer prepolymers which comprise reacting a metallic oxide containing at least one hydrolyzable oxygen, with an oxirane oligomer having at least one aromatic moiety and at least one oxirane containing aliphatic moiety, in the presence of a quantity of catalyst sufficient to effect reaction of substantially all of the hydrolyzable oxygen atoms in the metallic oxide with the oligomer while effecting substantially no crosslinking of metallic oxide-oligomer moieties.
- novel polymers of the present invention are prepared by chemically bonding an inorganic oxide having a hydrolyzable oxygen, such as aluminum oxide, silica, magnesium oxide, or the like with a difunctional oxirane oligomer, such as the diglycidyl ether of resorcinol (DGER) or the diglycidyl ether of bisphenol A (DGEBA); causing only partial reaction of the oligomer with hydroxyl groups of the inorganic oxide, to form an organic-inorganic backbone, with the inorganic oxide grafted to the aromatic oxirane oligomer.
- a difunctional oxirane oligomer such as the diglycidyl ether of resorcinol (DGER) or the diglycidyl ether of bisphenol A (DGEBA)
- prepolymers can be further reacted and polymerized with tertiary, secondary or primary amines, anhydrides, Lewis acids, Lewis bases, amides, ureas, melamines, triazines and other commonly used hardeners and catalysts.
- the prepolymers By forming the prepolymers, and reacting all the inorganic oxide functional groups with a portion of the oxirane groups, prior to final polymerization, it is possible to obtain enhanced properties in the final polymer such as heat deflection temperature, chemical resistance, toughness, tensile-flexural strengths, as compared to polymers formed by mere physical blending and direct polymerizing of the same oligomers, oxide filler, catalyst, hardener or initiator.
- the prepolymer is a liquid at or slightly above room temperature, with all hydrolyzable sites reacted irreversibly, eliminating further hydrolysis and chemical reaction.
- a further advantage when using DGER is that after cross linking with the inorganic oxide, the problem of dermatitis in handling is reduced or eliminated.
- the surface area of oxide becomes extremely important.
- silica has 3 to 6 silanol (SiOH hydroxyl) groups per 100 square angstroms. Therefore, 1 micron of surface area of silica has 300-600 hydroxyl groups.
- the inorganic oxides also have a critical particle size. Since they must have enough surface area, with exposed hydroxyl functional groups available for reaction, simply having a larger particle size, results in only a small portion of functional groups being available for reaction, the balance being in only a physical mixture. Because of its weight and gravitational force, when a mere physical mixture is heated up and the viscosity lowered, the large and heavy particles will separate and contribute to sedimentation.
- the low viscosity of the prepolymers allows for sprayable coatings without having to use solvents, prepregging fibers, such as carbon, graphite, ceramic, glass, silicon carbide, etc., encapsulation of electronic equipment, reaction injection molding, filament winding and many other functions requiring or facilitated by low viscosity.
- These organic-inorganic prepolymers can be cured immediately, or at a future date, using any suitable oxirane (epoxy) catalyst or hardener.
- suitable epoxy catalyst and hardeners include primary and secondary amines, tertiary amines, anhydrides, imidazoles, amides, and the like.
- Each prepolymer using a different metallic oxide delivers properties that are uniquely distinct from one another, e.g., fused silica gives low coefficient of thermal expansion, aluminum oxide gives abrasion resistance and flame retardancy, magnesium oxide gives high coefficient of thermal conductivity.
- the polymer prepared from the prepolymer of the present invention had a heat distortion temperature of 304oC. While heat distortion temperatures for the equivalent polymers from the diglycidyl ether of bisphenol A (DGEBA) was approximately 178oC and for diglycidyl ether of resorcinol was approximately 148°C.
- DGEBA diglycidyl ether of bisphenol A
- prepolymers rather than admixtures are involved, it is appropriate to refer to the prepolymers as siloxirane prepolymers when silica is the inorganic oxide, aloxirane when alumina is the inorganic oxide, magoxirane when a magnesium oxide is the inorganic oxide.
- inorganic oxides By incorporating inorganic oxides in a medium such as, diglycidyl ether of resorcinol, there are far more reactive groups in the polymer (DGER) than are available in the inorganic constituent. Once reaction is initiated, all the available reactive groups on the oxides are reacted, but by minimizing the amount of the catalyst, full polymerization of the prepolymer is prevented. The catalyst only initiates the reaction between the hydroxyl or reactive sites of the inorganic oxide, and a portion of the oxirane groups, leaving other oxirane groups available for further polymerization. This gives a chemically bonded inorganic backbone or moiety to the polymer.
- DGER diglycidyl ether of resorcinol
- the preferred oxirane oligomers of the present invention are dimers, trimers or tetramers, composed of or at least one aromatic moiety and at least one aliphatic moiety having an oxirane group, and having an expoxide equivalent in the range of from about 120 to about 200.
- Suitable oligomers on the other hand may have an epoxide equivalent in the range of from about 100 to about 3000.
- the preferred catalysts are those of the imidazole and imidazoline series, and especially imidazole, 1-methlyimidazole, 2-methlyimidazole, 2-ethyl-4-methylimidazole, 2,4-dimethylimidazole, 2-phenylimidazole, 1-vinyl-2-methylimidazole, 2-ethyl-4-methylimidazoline and imidazole lactate.
- suitable inorganic oxides As examples of suitable inorganic oxides, the following specific material are suggested, again, by way of illustration and not by way of limitation.
- a list of representative oxides are as follows:
- Silicon Oxide (Silica)
- the catalysts employed are imidazoles, benzimidazoles, dihydropyromidines, tetra hydropyrimidines, dihydroquinazolines and imidazolines which contain from 0-2 substitutents and especially from 0-1 substitutents.
- the preferred substitutents being lower alkyl, lower alkyl aryl, lower alkenyl, lower alkoxy and especially methyl, ethyl, phenyl and vinyl.
- the partial polymerization is carried out using one of the preferred catalyst in an amount less than about one (1) part of catalyst per one hundred (100) parts of the oxirane oligomer.
- the inorganic oxide can range from thirty (30) parts per one hundred (100) parts of oligomer to four hundred (400) parts per one hundred (100) parts of oligomer depending on the physical properties desired, such as viscosity, heat distortion temperature, flow, and the like.
- the catalyst is most preferably used in an amount of between 0.01 and 0.50 parts per hundred (100) parts of oligomer. This is a small amount of catalyst compared to the 2 to 10 parts of catalyst per hundred (100) parts of oligomer normally used for complete polymerization.
- silica fused silicon oxide
- aluminum oxide aluminum oxide, magnesium oxide or titanium dioxide
- titanium dioxide are the inorganic oxides, and are used in the following preferred ranges per hundred
- Titanium Dioxide 30 to 100 parts.
- Reaction and partial polymerization with bonding of the reactive sites of the inorganic oxide to a portion of the oxirane group is accomplished by heating the oligomer in a reactor containing a high sheer mixer, until the oligomer reaches a predetermined temperature, generally between 60oC. and 90oC.
- the catalyst is added and mixed into the oligomer for a predetermined period of time, generally between about 5 to about 10 minutes.
- the inorganic oxide is added and sheered into the oligomer causing all surface areas of the oxide particle to be coated with the partially catalyzed oligomer. This mixing takes place for a predetermined period of time, generally between about one half (1/2) hour to about two (2) hours, at a temperature in the range from about 100oC. and 135oC. Heating of the reaction solution, at this temperature, causes all the excess water to be evaporated from the inorganic oxide prior to cross-linking of the reactive sites of the inorganic oxide with a portion of the oxirane groups.
- the temperature of the reaction solution is subsequently increased to a predetermined temperature, generally from about 140oC. to about 220oC., for a predetermined period of time, generally from about one (1) hour to about four (4) hours.
- a predetermined temperature generally from about 140oC. to about 220oC.
- This heating of the reaction solution is believed to cause the hydroxyl groups of the inorganic oxide to react with a portion of the oxirane groups, giving a partially polymerized prepolymer.
- the reaction ceases when all the available sites have reacted and heating is then discontinued.
- Increasing the catalyst, temperature or time above the preferred levels, may cause the polymer to polymerize to an unusable degree or state.
- 2-ethyl-4-methylimidazole were charged to a reactor equipped with an exhaust system and a high shear mixer.
- the reactants were mixed while raising the temperature to 80°C.
- 80oC 3405 grams of silica, having an average particle size of 4 microns were added to the reactor.
- the reactants were then heated to 150oC, while mixing at 3000 RPM.
- the solution changed color after about thirty (30) minutes, and exotherm continued to increase solution temperature to 235oC., at which time the mixer was removed, and the solution was removed from reactor and cooled externally.
- 2-ethyl-4-methylimidazole were charged to a reactor equipped with an exhaust system and a high shear mixer.
- the reactants were mixed while raising the temperature to 80°C.
- 80oC 3405 grams of silica, having an average particle size of 4 microns were added to the reactor.
- the temperature of reactants was then increased to 150oC., for three (3) hours after which the solution still had very little color change.
- the temperature was then increased to 205oC. for one (1) hour with no measurable change in color.
- the temperature was increased to 250° C. still with no apparent change in color. Heating was then discontinued, and the solution was allowed to cool down.
- Example 2 provides a fully polymerized mass
- Example 3 yields a product in which much of the inorganic oxide is merely admixed with the other reactants and separates out prior to the final polymerization.
- the fully polymerized product of Example 2 had substantially inferior physical properties, in comparison to the product of Example 1, as described in the earlier Table.
Abstract
The present invention relates to a novel oxirane prepolymer comprising the catalyzed reaction product of an inorganic oxide having at least one hydrolyzable oxygen with a difunctional oxirane oligomer having at least one aromatic moiety and at least one oxirane containing aliphatic moiety, characterized in that substantially all of the hydrolyzable oxygen atoms in said oxide are bonded to said oligomer and there is substantially no bonding between oligomer moieties. The present invention also relates to a novel inorganic oxide containing polymer, said polymer comprising at least three crosslinked prepolymer moieties, each said prepolymer moiety being the reaction product of an inorganic oxide having at least one hydrolyzable oxygen with a difunctional oxirane oligomer having at least one aromatic moiety and at least one oxirane containing aliphatic moiety.
Description
METALLIC OXIDE-OXIRANE POLYMERS AND PREPOLYMERS
BACKGROUND OF THE INVENTION
This invention relates to novel polymers and more particularly to high performance polymers provided by cross-reaction of an inorganic with an organic oligomer.
Oxirane oligomers are known to be very useful for meeting high performance needs in fabricating structural composites, protective coatings, adhesives, castings, laminating, electrical potting compounds and the like. The performance and utility of oxirane polymers are also known to be dependent upon their chemical structure, the curing agent used and conditions of cure. One important factor in achieving a high performance polymer is often the chemical structure of the polymer.
With proper formulation, polymer systems can be produced having enhanced properties in areas such as chemical and corrosion resistance, high adhesive strength, high heat deflection temperatures and toughness. These properties are often based on the crosslink density capabilities of the particular oligomer or prepolymer used. Usually, the higher the crosslink density, the higher the chemical and corrosion resistance, the higher the adhesive strength, the higher the mechanical strength, the higher the heat deflection temperature and the better the toughness.
One oxirane oligomer having a very low molecular weight and compact structure is diglycidyl ether of resorcinol (DGER), i.e.,; 1,3-BIS-(2-3 epoxy propoxy) benzene, which has the following structure:
Diglycidyl ether of resorcinol has an epoxide equivalent of bebween 120 and 135 and a viscosity at 25ºC. of between 300 and 500 CPS. The small molecular size leads to the low epoxide equivalent and indicates that the molecule can achieve a high final crosslink density.
Another oxirane oligomer is a low molecular weiglit diglycidyl ether of bisphenol A, having an epoxide equivalent between 172 and 176 and a viscosity at 25ºC. between 4000 and 6000 CPS. This compound has the following structure:
As already noted, both of these oxirane oligomers are known to be useful in preparing higher molecular weight crosslinked polymers. For example, U.S. Patent 4,383,060 to Dearlove teaches an epoxy adhesive comprising an epoxy novolac resin, an epoxy flexibilizer, natural and colloidal silica and an imidazole curing agent. U.S. Patent 4,499,217 to Yoshimura et al. is directed to a thermosetting resinous liquid compositions comprising a composite formed from a dispersion of silica colloid in alcohol
and a thermosetting resin such as an epoxy-phenol. U.S. Patent 4,486,558 to Guilbert discloses an electrically insulating powder comprising a blend of (1) a derivative of a polyglycidyl ether of bisphenol A and (2) finely divided silica, while U.S. Patent 4,574,132 to Sayles describes an adhesive comprising (1) diglycidyl ether of bisphenol A, (2) diglycidyl ether of 1,4 butanediol, and (3) silica.
U.S. Patent 4,748,300 to Lalancette is directed to a polyhydroxysilicate-polymer reaction product. The product is prepared by reacting a finely divided polyhydroxysilicate and a hydroxy-containing polymer. The Lalancette product, however, is obtained by reacting the polyhydroxysilicate and the hydroxy-containing polymer without the use of a coupling agent and the teaching stresses the elimination of the coupling agent. The resultant material is, in any case, a completely polymerized mass.
A great deal of work has been conducted with respect to the use of oxirane polymers, but little or no work has been done directed to chemically bonding an inorganic oxide to an organic oxirane polymer and, insofar as is known, none on the use of partial polymerization of the hydroxyl group of the inorganic and the oxirane group. This cross-linking of the inorganic oxide, with the organic oligomer, through partial polymerization can eliminate undesirable characteristics which result with mere physical blending and adds the beneficial properties of chemical bonding, while maintaining a prepolymer capable of being fully polymerized at a later date.
SUMMARY OF INVENTION
In one aspect, the present invention relates to a novel oxirane prepolymer comprising the catalyzed reaction product of an inorganic oxide having at least one hydrolyzable oxygen with a difunctional oxirane oligomer having at least one aromatic moiety and at least one oxirane containing aliphatic moiety, characterized in that substantially all of the hydrolyzable oxygen atoms in said oxide are bonded to said oligomer and there is substantially no bonding between oligomer moieties.
In another aspect, the present invention relates to a novel inorganic oxide containing polymer, said polymer comprising at least three crosslinked prepolymer moieties, each said prepolymer moiety being the reaction product of an inorganic oxide having at least one hydrolyzable oxygen with a difunctional oxirane oligomer having at least one aromatic moiety and at least one oxirane containing aliphatic moiety.
In still another aspect, the present invention relates to a process for preparing metallic oxide-oligomer prepolymers which comprise reacting a metallic oxide containing at least one hydrolyzable oxygen, with an oxirane oligomer having at least one aromatic moiety and at least one oxirane containing aliphatic moiety, in the presence of a quantity of catalyst sufficient to effect reaction of substantially all of the hydrolyzable oxygen atoms in the metallic oxide with the oligomer while effecting substantially no crosslinking of metallic oxide-oligomer moieties.
The novel polymers of the present invention are prepared by chemically bonding an inorganic oxide
having a hydrolyzable oxygen, such as aluminum oxide, silica, magnesium oxide, or the like with a difunctional oxirane oligomer, such as the diglycidyl ether of resorcinol (DGER) or the diglycidyl ether of bisphenol A (DGEBA); causing only partial reaction of the oligomer with hydroxyl groups of the inorganic oxide, to form an organic-inorganic backbone, with the inorganic oxide grafted to the aromatic oxirane oligomer. These prepolymers can be further reacted and polymerized with tertiary, secondary or primary amines, anhydrides, Lewis acids, Lewis bases, amides, ureas, melamines, triazines and other commonly used hardeners and catalysts.
By forming the prepolymers, and reacting all the inorganic oxide functional groups with a portion of the oxirane groups, prior to final polymerization, it is possible to obtain enhanced properties in the final polymer such as heat deflection temperature, chemical resistance, toughness, tensile-flexural strengths, as compared to polymers formed by mere physical blending and direct polymerizing of the same oligomers, oxide filler, catalyst, hardener or initiator. The prepolymer is a liquid at or slightly above room temperature, with all hydrolyzable sites reacted irreversibly, eliminating further hydrolysis and chemical reaction. A further advantage when using DGER is that after cross linking with the inorganic oxide, the problem of dermatitis in handling is reduced or eliminated.
In order to react enough hydroxyl groups on the inorganic oxide to chemically bond them, and have the bound filler remain in solution when lowering the
viscosity by heating or solvent addition, the surface area of oxide becomes extremely important. For example, silica has 3 to 6 silanol (SiOH hydroxyl) groups per 100 square angstroms. Therefore, 1 micron of surface area of silica has 300-600 hydroxyl groups. The inorganic oxides also have a critical particle size. Since they must have enough surface area, with exposed hydroxyl functional groups available for reaction, simply having a larger particle size, results in only a small portion of functional groups being available for reaction, the balance being in only a physical mixture. Because of its weight and gravitational force, when a mere physical mixture is heated up and the viscosity lowered, the large and heavy particles will separate and contribute to sedimentation.
The low viscosity of the prepolymers allows for sprayable coatings without having to use solvents, prepregging fibers, such as carbon, graphite, ceramic, glass, silicon carbide, etc., encapsulation of electronic equipment, reaction injection molding, filament winding and many other functions requiring or facilitated by low viscosity. These organic-inorganic prepolymers can be cured immediately, or at a future date, using any suitable oxirane (epoxy) catalyst or hardener. Such suitable epoxy catalyst and hardeners include primary and secondary amines, tertiary amines, anhydrides, imidazoles, amides, and the like.
Each prepolymer using a different metallic oxide delivers properties that are uniquely distinct from one another, e.g., fused silica gives low coefficient of thermal expansion, aluminum oxide gives
abrasion resistance and flame retardancy, magnesium oxide gives high coefficient of thermal conductivity.
Physical evidence of formation of the organic-inorganic prepolymer is quite convincing. The product appears smooth and uniform and when dissolved in a solvent such as MEK or acetone, little or no separation or sedimentation takes place. Also, when the oligomer is heated to 93ºC, its viscosity drops to 190 CPS, but little or no separation or sedimentation takes place even when spun in a centrifuge at 3300 RPM.
Chemical evidence of formation of the organic-inorganic prepolymer is seen in the improvement of its heat and chemical resistance of the subsequent polymer. 1000 grams of the prepolymer of Example 1 hereinafter were mixed with 144 grams of diaminodiphenyl sulfone (DADS) and cured 4 hrs. at 175ºC plus 24 hrs. at 120ºC. 1000 grams of diglycidyl ether of resorcinol (DGER) and 1000 grams of the diglycidyl ether of bisphenol A were seperately mixed with 360 grams of diaminodiphenyl sulfone (DADS) and cured 4 hrs. at 175ºC plus 24 hrs. at 120ºC. W h e n cured with the diaminodiphenyl sulfone (DADS), the polymer prepared from the prepolymer of the present invention had a heat distortion temperature of 304ºC. While heat distortion temperatures for the equivalent polymers from the diglycidyl ether of bisphenol A (DGEBA) was approximately 178ºC and for diglycidyl ether of resorcinol was approximately 148°C.
Since true prepolymers rather than admixtures are involved, it is appropriate to refer to the prepolymers as siloxirane prepolymers when silica is the inorganic oxide, aloxirane when alumina is the
inorganic oxide, magoxirane when a magnesium oxide is the inorganic oxide.
In every test case when DGEBA or DGER were cured with primary and secondary amines, tertiary amines, anhydrides or other epoxy hardeners or catalysts, their chemical resistance was considerably lower than for equivalent polymers prepared from the prepolymer of the present invention using the same hardener or catalyst and cure temperature.
1000 grams of the prepolymer (DGEBA/Silica) were mixed with 190 grams of meta-phenylene diamine (MPDA) and cured 2 hrs. at 125ºC plus 2 hrs. at 175ºC. 1000 grams of diglycidyl ether of bisphenol A (DGEBA) were also mixed with 190 grams of meta-phenylene diamine (MPDA) and cured 2 hrs. at 125° C plus 2 hrs. at 175ºC. Testing of these equivalent polymers prepared from admixture vs. a prepolymer produced the data set forth in the following Table.
T A B L E
ADMIXTURE
CHEMICAL DATA: TEST DATA STATUS:
DISS. ATTACK. UNAFF. AFTER
CHEMICAL % TEMP. (*) (**) ( ***) DAYS
H2SO4 96% 90ºC * 14
Glacial Acetic
Acid 90ºC * 05
Chromic Acid 50% 70ºC * 14
HNO3 70% 25ºC * 02
Methanol 25ºC *** 28
Methylene
Chloride 25ºC ** 14
Hydrofluoric
Acid 52% 25°C * 03 = Weight gain - +9.5%
PRE POLYMER
DISS. ATTACK. UNAFF. AFTER
CHEMICAL % TEMP. (*) (**) (***) DAYS
H2SO4 96% 90°C *** 180
Glacial Acetic
Acid 90ºC *** 180
Chromic Acid 50% 70 º C *** 180 HNO3 70% 25 º C *** 60
Methanol 25ºC *** 180
Methylene
Chloride 25ºC *** 180
Hydrofluoric
Acid 52% 25ºC *** 60
*...... DISSOLVED/DISINTEGRATED INTO TEST SOLUTION
**..... ATTACKED BY TEST SOLUTION
***.... NO LOSS OF INTEGRITY, NO WEIGHT LOSS/GAIN, NO
CHEMICAL ATTACK
...... ADDITIONAL FACTS
While not willing to be bound by any specific theory or theories which might explain the unexpected improvement achieved using the techniques and materials of the present invention, the following discussion relates to some possible explanations.
By incorporating inorganic oxides in a medium such as, diglycidyl ether of resorcinol, there are far more reactive groups in the polymer (DGER) than are available in the inorganic constituent. Once reaction
is initiated, all the available reactive groups on the oxides are reacted, but by minimizing the amount of the catalyst, full polymerization of the prepolymer is prevented. The catalyst only initiates the reaction between the hydroxyl or reactive sites of the inorganic oxide, and a portion of the oxirane groups, leaving other oxirane groups available for further polymerization. This gives a chemically bonded inorganic backbone or moiety to the polymer.
Another advantage of the present invention would appear to be with regard to water. Ordinarily, moisture is present on fillers, and is either physisorbed or chemisorbed, physisorbed meaning capable of being boiled off; chemisorbed meaning in some way chemically bonded and therefore not easily debonded or boiled off.
By heating the organic/inorganic mixture, to initiate the reaction between the hydroxyl and oxirane groups, excess physisorbed water is driven off after completion of the reaction. This excess water normally remains in conventional epoxy-filler mixtures, and can be very detrimental particularly to coatings and composite structures since it causes bubbles, cavities, and the like during or after final polymerization. Since all the hydroxyl groups are now chemically bonded, there are essentially no groups available to be hydrolyzed and cause problems at final polymerization.
It would further appear that reactivity is satisfied by minimum catalyst reacting all available hydroxyl groups, with a limited amount of oxirane groups. The resultant steric hindrance prevents any further polymerization of the prepolymer, until
additional catalyst or hardener is added to effect three dimensional cross linking and full polymerization.
The following equation sets forth, by way of illustration and not by way of limitation, the sequence of the principal reactions which are thought to be involved.
In general, the preferred oxirane oligomers of the present invention are dimers, trimers or tetramers, composed of or at least one aromatic moiety and at least one aliphatic moiety having an oxirane group, and having an expoxide equivalent in the range of from about 120 to about 200. Suitable oligomers on the other hand may have an epoxide equivalent in the range of from about 100 to about 3000.
As examples of suitable catalysts, the following specific materials are suggested by way of illustration and not by way of limitation. imidazole
4-acetaminoimidazole
5-acetaminoimidazole
1-acetylimidazole
4-aminoimidazole
5-aminoimidazole
2-(2-aminoethyl)-imidazole
5-amino-1-methylimidazole
1-benzoylimidazole
2-benzylthiσimidazole
4, 5-bis(p-bromophenyl)-imidazole
2-chloroimidazole
4-benzylthio-5-nitroimidazole
5-benzylthio-4-nitroimidazole
4-bromoimidazole
5-bromoimidazole
2-bromo-4,5-diphenyl-imidazole
2-butylthio-2-cyclohexyl-4,5-diethylimidazole
1,5-dimethylimidazole
1-methylimidazoli
2-methylimidazole
2-ethyl-4-methylimidazole
4-methylimidazole
1-methyl-4-phenylimidazole 1-methyl-4-nitroimidazole
5-nitroimidazole
1-phenylimidazole
2-phenylimidazole
1-methylimidazole imidazole-4-acetic acid
1-vinyl-2-methylimidazole imidazole-1-acetic acid imidazole-1-aniline
5-butyramidoimidazole 4-carboxamidoimidazole
1-carbboxyimidazole
2-carboxyl-1-benzylimidazole
4,5-dicarboxamidoimidazole
4,5-dicarboxyimidazole imidazole-1-ethanol
2-thioimidazole
2-acetamino-1-benzylbenzimidazole
1-acetylbenzimidazole
2-aminiobenzimidazole 2-(1-aminobutyl)4-amino-6-ethoxybenzimidazole
2-amino-1-ethylbenzimidazole 2-amino-1-methylbenzimidazole 1-benzylbenzimidazole 2-benzylaminobenzimidazole 1-benzyl-2-chlorobenzimidazole
2-benzyl-5-nitrobenzimidazole 2-p-bromobenzylbenzimidazole
2-butylthiobenzimidazole
5-chlorobenzimidazole
6-chlorobenzimidazole
6-chloro-1,2-dimethylbenzimidazole 5,6-dichlorobenzimidazole
5,6-dimeththylbenzimidazole
5,6-dinitrobenzimidazole 2-ethyl-5-nitrobenzimidazole
1-methylbenzimidazole 6-methyl-2-phenylbenzimidazole
6-phenylbenzimidazole
2-acetamino-N-methylbenzimidazole benzimidazole-2-acetic acid
2-carboxamidobenzimidazole 2-carboxy-benzimidazole
2-carboyl-5-bromobenzimidazole
2,4-dimethylimidazoline 2-methylimidazoline 1-vinyl-2-methylimidazoline
2-ethyl-4-methylimidazoline
2-chloromethyl-2-imidazoline
2-methylimidazoline phenate imidazole lactate imidazoleacetate 3,4-dihydro-4-phenylpyrimidine
4-methyl-1,4,5,6-tetrahydropyrimidine
3,4-dihydroquinazoline 2-benzyl-2-imidazoline-4-carboxylic acid
2-(1-naphthylmethyl)-2-imidazoline and 2-chloromethyl-2-imidazoline
The preferred catalysts are those of the imidazole and imidazoline series, and especially imidazole, 1-methlyimidazole, 2-methlyimidazole, 2-ethyl-4-methylimidazole, 2,4-dimethylimidazole, 2-phenylimidazole, 1-vinyl-2-methylimidazole, 2-ethyl-4-methylimidazoline and imidazole lactate.
As examples of suitable inorganic oxides, the following specific material are suggested, again, by way of illustration and not by way of limitation. A list of representative oxides are as follows:
Silicon Oxide (Silica)
Aluminum Oxide
Titanium Oxide
Magnesium Oxide
Antimony Oxide
Zinc Oxide
Ferric Oxide
Molybdenum Oxide
PREFERRED EMBODIMENT
In the preferred aspect of this invention, the catalysts employed are imidazoles, benzimidazoles, dihydropyromidines, tetra hydropyrimidines, dihydroquinazolines and imidazolines which contain from 0-2 substitutents and especially from 0-1 substitutents. The preferred substitutents being lower alkyl, lower alkyl aryl, lower alkenyl, lower alkoxy and especially methyl, ethyl, phenyl and vinyl.
The partial polymerization is carried out using one of the preferred catalyst in an amount less than about one (1) part of catalyst per one hundred (100) parts of the oxirane oligomer. The inorganic
oxide can range from thirty (30) parts per one hundred (100) parts of oligomer to four hundred (400) parts per one hundred (100) parts of oligomer depending on the physical properties desired, such as viscosity, heat distortion temperature, flow, and the like. The catalyst is most preferably used in an amount of between 0.01 and 0.50 parts per hundred (100) parts of oligomer. This is a small amount of catalyst compared to the 2 to 10 parts of catalyst per hundred (100) parts of oligomer normally used for complete polymerization.
In preferred prepolymers silica (fused silicon oxide), aluminum oxide, magnesium oxide or titanium dioxide, are the inorganic oxides, and are used in the following preferred ranges per hundred
(100) parts of oligomer:
Silica - 30 to 200 parts.
Aluminum Oxide - 40 to 400 parts.
Magnesium Oxide - 30 to 200 parts.
Titanium Dioxide - 30 to 100 parts.
Particle Size - 10 micron or less
Average 4 micron or less
Reaction and partial polymerization with bonding of the reactive sites of the inorganic oxide to a portion of the oxirane group, is accomplished by heating the oligomer in a reactor containing a high sheer mixer, until the oligomer reaches a predetermined temperature, generally between 60ºC. and 90ºC. The catalyst is added and mixed into the oligomer for a predetermined period of time, generally between about 5 to about 10 minutes. The inorganic oxide is added and
sheered into the oligomer causing all surface areas of the oxide particle to be coated with the partially catalyzed oligomer. This mixing takes place for a predetermined period of time, generally between about one half (1/2) hour to about two (2) hours, at a temperature in the range from about 100ºC. and 135ºC. Heating of the reaction solution, at this temperature, causes all the excess water to be evaporated from the inorganic oxide prior to cross-linking of the reactive sites of the inorganic oxide with a portion of the oxirane groups.
The temperature of the reaction solution is subsequently increased to a predetermined temperature, generally from about 140ºC. to about 220ºC., for a predetermined period of time, generally from about one (1) hour to about four (4) hours. This heating of the reaction solution is believed to cause the hydroxyl groups of the inorganic oxide to react with a portion of the oxirane groups, giving a partially polymerized prepolymer. The reaction ceases when all the available sites have reacted and heating is then discontinued.
Increasing the catalyst, temperature or time above the preferred levels, may cause the polymer to polymerize to an unusable degree or state.
The invention will be better understood by reference to the following examples, which are presented for purpose of illustration only and are not intended to be construed in a limiting sense.
EXAMPLE 1:
2724 grams of liquid resin, diglycidyl ether of resorcinol, and 4.09 grams of catalyst, 2-ethyl-4-
methylimidazole were charged to a reactor equipped with an exhaust system and a high shear mixer. The reactants were mixed while raising the temperature to
80°C. Upon reaching 80ºC., 3405 grams of silica, having an average particle size of 4 microns were added to the reactor. The reactants were heated to 150ºC, while mixing at 3000 RPM for a period of three (3) hours. When the solution changed color, the reactor was removed from the heat, but mixing was continued for one (1) hour, after which the product was discharged from the reactor and recovered.
Results
Color Dark Tan Opaque
Viscosity @ 77ºC. 3500 CPS
(Broodfield RV7, 20 RPM)
Non-Volatile Content 99.99%
Specific Gravity 1.29 - 1.32
Epoxy Equivalent Weight, G 165 - 180
% Sedimentation <0.1 EXAMPLE 2:
2724 grams of liquid resin, the diglycidyl ether of resorcinol, and 17.70 grams of catalyst,
2-ethyl-4-methylimidazole were charged to a reactor equipped with an exhaust system and a high shear mixer. The reactants were mixed while raising the temperature to 80°C. Upon reaching 80ºC, 3405 grams of silica, having an average particle size of 4 microns were added to the reactor. The reactants were then heated to 150ºC, while mixing at 3000 RPM. The solution changed
color after about thirty (30) minutes, and exotherm continued to increase solution temperature to 235ºC., at which time the mixer was removed, and the solution was removed from reactor and cooled externally.
Results
Exothermic reaction caused the solution to continue to polymerize, until it was an irreversible solid.
EXAMPLE 3:
2724 grams of liquid resin, the diglycidyl ether of resorcinol, and 2.45 grams of catalyst,
2-ethyl-4-methylimidazole were charged to a reactor equipped with an exhaust system and a high shear mixer. The reactants were mixed while raising the temperature to 80°C. Upon reaching 80ºC, 3405 grams of silica, having an average particle size of 4 microns were added to the reactor. The temperature of reactants was then increased to 150ºC., for three (3) hours after which the solution still had very little color change. The temperature was then increased to 205ºC. for one (1) hour with no measurable change in color. The temperature was increased to 250° C. still with no apparent change in color. Heating was then discontinued, and the solution was allowed to cool down.
Results
After the solution had cooled, observation showed liquid-solid separation. Over 60% of the Silica had sedimentated to the bottom.
Example 4 ( DGEBA) :
2724 Grams of liquid resin, diglycidyl ether of bisphenol A (DGERA), and 4.09 grams of catalyst, 2-ethyl-4 methylimidazole were charged to a reactor equipped with an exhaust system and high shear mixer.
The reaction was then carried out in the manner set forth in Example 1 above.
Results
Color Dark Tan Opaque
Viscosity 18,000 CPS
(Brookfield RV7, 20 RPM)
Non-Volatile Content 99.99%
Epoxy Equivalent Weight 201 - 213
% Sedimentation 0 Example 5 (Tri-Functional Epoxy):
In a manner similar to that set forth in Example 1 above, 2724 grams of tris- (hydroxyphenyl) methane triglycidyl ether and 5.40 grams of catalyst, 2-ethyl-4-metylimidazol were charged to a reactor equipped with an exhaust system and high shear mixer. The reactants wee mixed at a temperature of 80ºC and 3405 grams of silica, having an average particle size of 4 microns were added to the reactors. The reactants were heated to 150ºC, while mixing at 3500 RPM for a period four (4) hrs. The product was discharged from the reactor and recovered.
Results
Color Cream Opaque
Viscosity at 150ºF 9000
(Brookfield RV7, 20 RPM) Non Volatile Content 99.99%
Specific Gravity 1.3-1.32
Epoxy Equivalent Weight 180-198
% Sedimentation 0
From the foregoing examples it will be clear that an excess of catalyst (Example 2) provides a fully polymerized mass, while a deficiency of catalyst (Example 3) yields a product in which much of the inorganic oxide is merely admixed with the other reactants and separates out prior to the final polymerization. The fully polymerized product of Example 2 had substantially inferior physical properties, in comparison to the product of Example 1, as described in the earlier Table.
The patents, and any patent publications set forth in this specification are intended to be incorporated by reference herein.
It is apparent that there has been provided in accordance with this invention novel polymers and prepolymers, as well as a process for producing such polymers and prepolymers. While the invention has been described in combination with the specific materials and embodiments thereof, it is evident that many substitutions, alternatives, modifications, and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, it is intended to embrace all such substitutions,
alternatives, modifications and variations as fall within the spirit and scope of the appended claims.
Claims
1. An oxirane prepolymer comprising the catalyzed reaction product of an inorganic oxide having at least one hydrolyzable oxygen with a difunctional oxirane oligomer having at least one aromatic moiety and at least one oxirane containing aliphatic moiety, characterized in that substantially all of the hydrolyzable oxygen atoms in said oxide are bonded to said oligomer and there is substantially no bonding between oligomer moieties.
2. The prepolymer according to claim 1 wherein said oligomer is the diglycidyl ether of resorcinol.
3. The prepolymer of claim 1 wherein said oligomer is the diglycidyl ether of bisphenol A.
4. The prepolymer of claim 2 wherein said metallic oxide is silica.
5. The prepolymer of claim 3 wherein said metallic oxide is silica.
6. The prepolymer of claim 4 wherein said silica is present in the range of from about 20 to about 200 parts by weight per 100 parts by weight of oligomer, and wherein said oligomer and said silica have been reacted in the presence of a catalyst comprising from about 0.01 to about 0.5 parts by weight of an imidazole compound per 100 parts by weight of oligomer.
7. The prepolymer of claim 5 wherein said silica is present in the range of from about 20 to about 200 parts by weight per 100 parts by weight of oligomer, and wherein said oligomer and said silica have been reacted in the presence of a catalyst comprising from about 0.01 to about 0.5 parts by weight of an imidazole compound per 100 parts by weight of oligomer.
8. The prepolymer of claim 2 wherein said metallic oxide is aluminum oxide.
9. The prepolymer of claim 3 wherein said metallic oxide is aluminum oxide.
10. The prepolymer of claim 2 wherein said metallic oxide is magnesium oxide.
11. The prepolymer of claim 3 wherein said metallic oxide is magnesium oxide.
12. The prepolymer of claim 2 wherein said metallic oxide is a member selected from the group consisting of titanium oxide, antimony oxide, zinc oxide, iron oxide and molybdenum oxide.
13. The prepolymer of claim 3 wherein said metallic oxide is a member selected from the group consisting of titanium oxide, antimony oxide, zinc oxide, iron oxide and molybdenum oxide.
14. A novel inorganic oxide containing polymer, said polymer comprising at least three crosslinked prepolymer moieties, each said prepolymer moiety being the reaction product of an inorganic oxide having at least one hydrolyzable oxygen with a difunctional oxirane oligomer having at least one aromatic moiety and at least one oxirane containing aliphatic moiety.
15. The prepolymer according to claim 14 wherein said oligomer is the diglycidyl ether of resorcinol.
16. The prepolymer of claim 14 wherein said oligomer is the diglycidyl ether of bisphenol A.
17. The prepolymer of claim 15 wherein said metallic oxide is silica.
18. The prepolymer of claim 16 wherein said metallic oxide is silica.
19. The prepolymer of claim 17 wherein said silica is present in the range of from about 20 to about 200 parts by weight per 100 parts by weight of oligomer, and wherein said oligomer and said silica have been reacted in the presence of a catalyst comprising from about 0.01 to about 0.5 parts by weight of an imidazole compound per 100 parts by weight of oligomer.
20. The prepolymer of claim 18 wherein said silica is present in the range of from about 20 to about 200 parts by weight per 100 parts by weight of oligomer, and wherein said oligomer and said silica have been reacted in the presence of a catalyst comprising from about 0.01 to about 0.5 parts by weight of an imidazole compound per 100 parts by weight of oligomer.
21. The prepolymer of claim 15 wherein said metallic oxide is aluminum oxide.
22. The prepolymer of claim 16 wherein said metallic oxide is aluminum oxide.
23. The prepolymer of claim 15 wherein said metallic oxide is magnesium oxide.
24. The prepolymer of claim 16 wherein said metallic oxide is magnesium oxide.
25. The prepolymer of claim 15 wherein said metallic oxide is a member selected from the group consisting of titanium oxide, antimony oxide, zinc oxide, iron oxide and molybdenum oxide.
26. The prepolymer of claim 16 wherein said metallic oxide is a member selected from the group consisting of titansium oxide, antimony oxide, zinc oxide, iron oxide and molybdenum oxide.
27. A process for preparing metallic oxide-oligomer prepolymers which comprise reacting a metallic oxide containing at least one hydrolyzable oxygen, with an oxirane oligomer having at least one aromatic moiety and at least one oxirane containing aliphatic moiety, in the presence of a quantity of catalyst sufficient to effect reaction of substantially all of the hydrolyzable oxygen atoms in the metallic oxide with the oligomer while effecting substantially no crosslinking of metallic-oxide oligomer moieties.
28. The process of claim 27 wherein said oligomer and said catalyst are heated to a temperature of from about 60ºC to about 90ºC, then adding the inorganic oxide to the mixture of catalyst and oligomer under high shear mixing, said mixing being continued for a period of about 1/2 to about 2 hours at a temperature in the range of from about 100ºC to about 135ºC, then increasing the temperature of the reaction solution to a temperature of from about 177ºC to about 220°C for a period of from about 1 to about 4 hours, then recovering the prepolymer product.
29. The process according to claim 28 wherein said oligomer is the diglycidyl ether of resorcinol.
30. The process according to claim 28 wherein said oligomer is the diglycidyl ether of bisphenol A.
31. The process according to claim 28 wherein said metallic oxide is a member selected from the group consisting of silica, aluminum oxide, magnesium oxide and titanium oxide.
32. The process according to claim 29 wherein said metallic oxide is a member selected from the group consisting of silica, aluminum oxide, magnesium oxide and titanium oxide.
33. The process according to claim 30 wherein said metallic oxide is a member selected from the group consisting of silica, aluminum oxide, magnesium oxide and titanium oxide.
34. The process according to claim 28 wherein said catalyst is an imidazole compound.
35. The process according to claim 29 wherein said catalyst is an imidazole compound.
36. The process according to claim 30 wherein said catalyst is an imidazole compound.
37. The process according to claim 31 wherein said catalyst is an imidazole compound.
38. The process according to claim 32 wherein said catalyst is an imidazole compound.
39. The process according to claim 33 wherein said catalyst is an imidazole compound.
40. The process according to claim 29 wherein said metallic oxide is silica, present in the range of from about 20 to about 200 parts by weight per 100 parts by weight of oligomer and wherein said catalyst is an imidazole compound.
41. The process according to claim 30 wherein said metallic oxide is silica, present in the range of from about 20 to about 200 parts by weight per 100 parts by weight of oligomer and wherein said catalyst is an imidazole compound.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP90902483A EP0407554B1 (en) | 1989-01-19 | 1990-01-18 | Metallic oxide-oxirane polymers and prepolymers |
DE69031445T DE69031445T2 (en) | 1989-01-19 | 1990-01-18 | METAL OXIDE-OXIRANE POLYMERS AND PREPOLYMERS |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/299,887 US5026816A (en) | 1989-01-19 | 1989-01-19 | Metallic oxide-oxirane polymers and prepolymers |
US299,887 | 1989-01-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1990008168A1 true WO1990008168A1 (en) | 1990-07-26 |
Family
ID=23156726
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1990/000370 WO1990008168A1 (en) | 1989-01-19 | 1990-01-18 | Metallic oxide-oxirane polymers and prepolymers |
Country Status (8)
Country | Link |
---|---|
US (1) | US5026816A (en) |
EP (1) | EP0407554B1 (en) |
AT (1) | ATE158323T1 (en) |
CA (1) | CA2025667C (en) |
DE (1) | DE69031445T2 (en) |
DK (1) | DK0407554T3 (en) |
ES (1) | ES2106731T3 (en) |
WO (1) | WO1990008168A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012119968A1 (en) | 2011-03-07 | 2012-09-13 | Akzo Nobel Coatings International B.V. | Cargo tank coating |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5658996A (en) * | 1996-02-20 | 1997-08-19 | Keehan; Donald J. | Multi-functional oxirane polymers |
JP2001200023A (en) * | 2000-01-17 | 2001-07-24 | Jsr Corp | Curable composition, its cured product and laminate |
US6794761B2 (en) * | 2001-04-26 | 2004-09-21 | Intel Corporation | No-flow underfill material |
US20040204515A1 (en) * | 2003-01-17 | 2004-10-14 | Edita Rojasova | Chemical resistant epoxy composition |
US7157549B2 (en) * | 2003-05-30 | 2007-01-02 | The University Of Akron | Polymerization of oxiranes with a lithium-containing initiator |
FR2889537B1 (en) * | 2005-08-08 | 2007-09-28 | Nexans Sa | FIRE-RESISTANT COMPOSITION, IN PARTICULAR FOR CABLE MATERIAL OF ENERGY AND / OR TELECOMMUNICATION |
US8505364B2 (en) | 2011-11-04 | 2013-08-13 | General Electric Company | Systems and methods for use in monitoring operation of a rotating component |
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US3055858A (en) * | 1957-05-23 | 1962-09-25 | Dow Corning | Method of preparing silicone-epoxide resins |
FR1462141A (en) * | 1965-01-05 | 1966-12-09 | Lockheed Aircraft Corp | Moldable ceramic-ceramic compositions resistant to high temperatures |
JPS5029957B2 (en) * | 1972-06-05 | 1975-09-27 | ||
JPS57128760A (en) * | 1981-02-02 | 1982-08-10 | Shokubai Kasei Kogyo Kk | Liquid thermosetting resin composition |
US4383060A (en) * | 1982-06-01 | 1983-05-10 | General Motors Corporation | Epoxy adhesive for structurally bonding molded SMC |
US4486558A (en) * | 1984-02-09 | 1984-12-04 | Minnesota Mining And Manufacturing Company | Electrical insulating powder for providing wire coating |
-
1989
- 1989-01-19 US US07/299,887 patent/US5026816A/en not_active Expired - Fee Related
-
1990
- 1990-01-18 DK DK90902483.8T patent/DK0407554T3/en active
- 1990-01-18 WO PCT/US1990/000370 patent/WO1990008168A1/en active IP Right Grant
- 1990-01-18 DE DE69031445T patent/DE69031445T2/en not_active Expired - Fee Related
- 1990-01-18 EP EP90902483A patent/EP0407554B1/en not_active Expired - Lifetime
- 1990-01-18 AT AT90902483T patent/ATE158323T1/en not_active IP Right Cessation
- 1990-01-18 ES ES90902483T patent/ES2106731T3/en not_active Expired - Lifetime
- 1990-01-18 CA CA002025667A patent/CA2025667C/en not_active Expired - Fee Related
Patent Citations (6)
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US3264235A (en) * | 1961-06-01 | 1966-08-02 | Hustinx Edmond | Process for preparing soluble reaction products of epoxy resins and varnishes and paint made therefrom |
US3394105A (en) * | 1963-05-02 | 1968-07-23 | Shell Oil Co | Process for curing polyepoxides and resulting products |
US3329652A (en) * | 1965-02-15 | 1967-07-04 | Shell Oil Co | Process for curing polyepoxides with anhydrides and activators therefor |
US3748300A (en) * | 1971-07-02 | 1973-07-24 | Univ Sherbrooke | Polyhydroxysilicate-polymer reaction product |
US4089840A (en) * | 1976-04-19 | 1978-05-16 | Blount David H | Process for the production of epoxy silicate resinous products |
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WO2012119968A1 (en) | 2011-03-07 | 2012-09-13 | Akzo Nobel Coatings International B.V. | Cargo tank coating |
US8986799B2 (en) | 2011-03-07 | 2015-03-24 | Akzo Nobel Coatings International B.V. | Cargo tank coating |
Also Published As
Publication number | Publication date |
---|---|
DE69031445T2 (en) | 1998-02-12 |
EP0407554A1 (en) | 1991-01-16 |
ATE158323T1 (en) | 1997-10-15 |
DE69031445D1 (en) | 1997-10-23 |
CA2025667A1 (en) | 1990-07-20 |
EP0407554A4 (en) | 1992-10-21 |
EP0407554B1 (en) | 1997-09-17 |
DK0407554T3 (en) | 1997-10-06 |
US5026816A (en) | 1991-06-25 |
ES2106731T3 (en) | 1997-11-16 |
CA2025667C (en) | 1998-04-14 |
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