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
  • 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
  • C08G59/02—Polycondensates containing more than one epoxy group per molecule
  • C08G59/027—Polycondensates containing more than one epoxy group per molecule obtained by epoxidation of unsaturated precursor, e.g. polymer or monomer
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L53/005—Modified block copolymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
  • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

• This invention relates to compatible blends of epoxy resins and epoxidized polydiene polymers. More specifically, the invention relates to blends of epoxy resins and epoxidized polydienes which are compatibilized and cured with anhydride curing agents.
• Epoxy resins such as glycidyl ethers prepared by the reaction of epichlorohydrin with a compound containing at least one hydroxyl group carried out under alkaline reaction conditions are known to be useful in adhesives, and particularly in structural adhesives. Such epoxy resins are described in U.S. Patent 5,169,910.
• Structural adhesives are bonding agents used to form permanent load bearing joints between adherands and generally should have the characteristics of high strength, good adhesion, and environmental resistance. Structural adhesives containing such epoxy resins have the disadvantage that they tend to be inflexible and have low impact resistance.
• Low viscosity epoxidized polydiene polymers are also known to be useful in adhesives. Such polymers are described in U.S. patent 5,229,464. These polymers have a relatively high degree of flexibility and also a relatively high impact resistance.
• the present invention relates to a polymer blend having sufficient compatibility to form a homogeneous mixture comprising a curable aromatic epoxy resin, an epoxidized polydiene polymer, and an anhydride or polycarboxylic acid curing agent.
• an accelerator is added to the blend and the blend is cured.
• the blend may be cured by baking in an oven at 93 to 178 "C.
• the preferred epoxy resins are glycidyl ethers prepared by the reaction of epichlorohydrin with an aromatic compound containing at least one hydroxy group carried out under alkaline reaction conditions.
• the preferred epoxidized polydiene polymers are low molecular weight low viscosity polymers which have a relatively small amount of epoxidation.
• Suitable anhydride curing agents include those selected from the group consisting of phthalic anydride, substituted phthalic anhydrides, and hydrophthalic anhydrides.
• the preferred anhydride curing agents are dodecenylsuccinic anhydride and hexahydrophthalic anhydride.
• the composition in accordance with the present invention includes an epoxy resin.
• the epoxy resin component of the composition can be any curable resin having, on the average, more than one vicinal epoxide group per molecule and which has at least one aromatic group, and may bear substituents which do not materially interfere with the curing reaction.
• Suitable epoxy resins include glycidyl ethers prepared by the reaction of epichlorohydrin with an aromatic compound containing at least one hydroxyl group carried out under alkaline reaction conditions.
• the epoxy resin products obtained when the hydroxyl group-containing compound is bisphenol-A are represented below by the structure below wherein n is zero or a number greater than 0, commonly in the range of 0 to 10, preferably in the range of 0 to 2, and R is H or an alkyl group, preferably methyl or ethyl.
• epoxy resins can be prepared by the reaction of epichlorohydrin with mononuclear di- and trihydroxy phenolic compounds such as resorcinol and phloroglucinol, selected polynuclear polyhydroxy phenolic compounds such as bis(p-hydroxyphenyl)methane and 4,4-dihydroxybiphenyl, or aliphatic polyols such as 1,4-butanediol and glycerol.
• mononuclear di- and trihydroxy phenolic compounds such as resorcinol and phloroglucinol
• selected polynuclear polyhydroxy phenolic compounds such as bis(p-hydroxyphenyl)methane and 4,4-dihydroxybiphenyl
• aliphatic polyols such as 1,4-butanediol and glycerol.
• Epoxy resins suitable for the invention compositions have molecular weights generally within the range of 86 to 10,000, preferably 200 to 1500.
• Resin 828 a reaction product of epichlorohydrin and 2,2-bis(4-hydroxyphenylpropane) (bisphenol-A) having a molecular weight of 400, an epoxide equivalent (ASTM D-1652) of 185-192, and an n value (from the formula above) of 0.2, is presently the preferred epoxy resin because of its low viscosity and commercial availability.
• Polymers containing ethylenic unsaturation can be prepared by copolymerizing one or more olefins, particularly dienes, by themselves or with one or more alkenyl aromatic hydrocarbon monomers.
• the copolymers may, of course, be random, tapered, block or a combination of these, as well as linear, star or radial.
• the polymers containing ethylenic unsaturation or both aromatic and ethylenic unsaturation may be prepared using anionic initiators or polymerization catalysts. Such polymers may be prepared using bulk, solution or emulsion techniques. In any case, the polymer containing at least ethylenic unsaturation will, generally, be recovered as a solid such as a crumb, a powder, a pellet or the like, but it also may be recovered as a liquid such as in the present invention. Polymers containing ethylenic unsaturation and polymers containing both aromatic and ethylenic unsaturation are available commercially from several suppliers.
• copolymers of conjugated dienes and alkenyl aromatic hydrocarbons are prepared by contacting the monomer or monomers to be polymerized simultaneously or sequentially with an anionic polymerization initiator such as group IA metals, their alkyls, " amides, silanolates, naphthalides, biphenyls or anthracenyl derivatives. It is preferred to use an organo alkali metal (such as sodium or potassium) compound in a suitable solvent at a temperature within the range from -150°C to 300°c, preferably at a temperature within the range from 0°C to 100°C.
• Particularly effective anionic polymerization initiators are organo lithium compounds having the general formula:
• R is an aliphatic, cycloaliphatic, aromatic or alkyl-substituted aromatic hydrocarbon radical having from 1 to 20 carbon atoms and n is an integer of 1 to 4.
• Conjugated dienes which may be polymerized anionically include those conjugated dienes containing from 4 to 24 carbon atoms such as 1,3-butadiene, isoprene, piperylene, methylpentadiene, phenyl-butadiene, 3,4-dimethyl-l,3-hexadiene, 4,5-diethyl-l,3-octadiene and the like.
• Isoprene and butadiene are the preferred conjugated diene monomers for use in the present invention because of their low cost and ready availability.
• Alkenyl aromatic hydrocarbons which may be copolymerized include vinyl aryl compounds such as styrene, various alkyl-substituted styrenes, alkoxy-substituted styrenes, vinyl napthalene, alkyl-substituted vinyl naphthalenes and the like.
• polymers are epoxidized, whether they are hydrogenated or not, and it is preferred that the epoxidation take place only to the extent that 0.1 to 3 milliequivalents of epoxide per gram of polymer (0.1 to 3 Meq epoxide/g) are generated.
• the preferred epoxidized polymer has an epoxide equivalent weight of between 10,000 and 333.
• the epoxidized polydiene has the formula:
• a and B are polymer blocks which may be homopolymer blocks of conjugated diene monomers, copolymer blocks of conjugated diene monomers, copolymer blocks of diene monomers and monoalkenyl aromatic hydrocarbon monomers or homopolymer blocks of monoalkenyl aromatic hydrocarbon monomers; and the A blocks have a molecular weight of from 100 to 3,000 and the B blocks have a molecular weight of from 1000 to 15,000; and n is greater than 0, r is 0 or 1, m is greater than or equal to 0, and n + m ranges from 1 to 100. p and q may be 0 or 1.
• a blocks should have a greater concentration of more highly substituted aliphatic double bonds than the B blocks have.
• Suitable randomly epoxidized star polymers, based on at least one conjugated diene monomer have more than four arms wherein each arm has a molecular weight from 1500 to 15,000.
• the star polymers contained di-, tri-, or tetrasubstituted olefinic epoxides (1,1-disubstituted, 1,2-disubstituted, 1,1,2-trisubstituted and 1,1,2,2-tetrasubstituted olefinic epoxides) in a concentration of from 0.05 to 5 milliequivalents of epoxide per gram of polymer.
• blends of the epoxy resins and epoxidized polymers described above are incompatible.
• compatibility will be taken to mean able to form at least a well dispersed two phase mixture that is homogeneous in appearance.
• an anhydride curing agent may be generally described as any compound containing one or more anhydride functional groups. Most commonly used anhydrides have an aromatic or cycloaliphatic structure.
• Examples include phthalic anhydride, tetrahydrophthalic anhydride, nadic methyl anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, and dodecenylsuccinic anhydride.
• multifunctional carboxylic acids will provide similar performance.
• Preferred anhydride curing agents are those with an aliphatic character to increase compatability with the epoxidized polydiene.
• Dodecenylsuccinic anhydride and hexahydrophthalic anhydride have been found to work well in compatibilizing blends of epoxy resins and epoxidized polydienes.
• the compatibilizing agent is also a curing agent for the materials of the blend. This eliminates the use of extra materials and also allows the compatibilization and the curing to take place in one step.
• a curing accelerator In order to cure this blend, a curing accelerator must be added. Suitable curing accelerators include trialkyl amines, hydroxyl-containing compounds and imidazoles. Benzyldimethylamine has been found to work well in curing the blends of the present invention. - The actual curing of the blends of the present invention should take place under the following conditions: cure temperature from 93-232 °C with sufficient time to obtain a well cured material, generally from 20 minutes to 4 hours.
• the cured blends of the present invention may be used in structural adhesive compositions.
• Epoxy resins are known for their utility in such compositions.
• the blends of the present invention should be more flexible and have a higher impact strength when used in a structural adhesive than structural adhesives using epoxy resins alone.
• Various types of fillers can be included in the structural adhesive formulation.
• a wide variety of fillers can be used. Suitable fillers include calcium carbonate, clays, talcs, zinc oxide, titanium dioxide and the like.
• the amount of filler usually is in the range of 0 to 65%w based on the solvent free portion of the formulation depending on the type of filler used and the application for which the adhesive is intended.
• An especially preferred filler is titanium dioxide.
• Stabilizers known in the art may also be incorporated into the adhesive composition. These may be for protection during the life of the article against, for example, oxygen, ozone and ultra-violet radiation.
• 204 is a linear isoprene-styrene/butadiene-isoprene molecule containing 38.7% styrene. It has been partially hydrogenated and then epoxidized to a level of 1.0 meq/g.
• 205 is an isoprene-butadiene star polymer which has been coupled with 6% divinylbenzene (DVB) . It also has been partially hydrogenated and then epoxidized to a level of 0.8 meq/g.
• 103 is a radial isoprene-butadiene polymer which has been coupled using silicon tetrachloride and has been epoxidized. Two versions of 103 were made: 103A was epoxidized to a level of 0.4 meq/g and 103B was epoxidized to a level of 1.0 meq/g.
• EPON 828 (EPON is a trade mark) resin and with EPON 825 resin.
• the former resin is described above and 825 is a higher purity version of 828.
• Blends containing 90, 75, 50, 25, and 10 percent epoxidized polydiene polymer were made. The results are shown in
• EPON 828 90,75,50,25,10% 90,75,50,25,10% 90,75,50,25,10% 90,75,50,25,10% immiscible immiscible immiscible
• Polymer 103 A 0 20 40 60 80 100
• Blends of EPON 828 resin with the epoxidized polydiene polymers described in Example 1 were made at a ratio of 80 weight percent epoxy resin/20 weight percent epoxidized polydiene resin.
• a stoichiometric amount of dodecenylsuccinic anhydride was added as a compatibilizing and curing agent.
• One part per hundred of benzyl dimethyl amine was used as the accelerator (catalyst) .
• the curing reactions were carried out by using the same procedure described in Example 2.
• Blends of EPON 828 resin with the epoxidized polydiene polymers described in Example 1 were made at a ratio of 80 weight percent epoxy resin/20 weight percent epoxidized polydiene resin.
• a stoichiometric amount of hexahydrophthalic anhydride was added as a compatibilizing and curing agent.
• One part per hundred of benzyl dimethyl amine was used as the accelerator (catalyst) .
• the curing reactions were carried out using the same procedure described in Example 2. The results are shown in the following table.

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• 1993
  • 1993-07-12 US US08/090,856 patent/US5332783A/en not_active Expired - Fee Related
• 1994
  • 1994-07-05 TW TW083106152A patent/TW295595B/zh active
  • 1994-07-08 MX MX9405227A patent/MX9405227A/es not_active Application Discontinuation
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