Classifications

• • 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
• • 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
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/91—Polymers modified by chemical after-treatment
• • 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
  • C08G59/12—Polycondensates containing more than one epoxy group per molecule of polycarboxylic acids with epihalohydrins or precursors thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
  • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
  • C08G65/3324—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof cyclic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/02—Polyalkylene oxides

Definitions

• epoxy resins are cross-linked
• the cross-linking that gives epoxy resins many of their favorable physical and chemical properties also limits the application of epoxy resins to uses where the brittle properties of cross-linked resins are not a handicap
• This 10 invention provides a reactive external flexibilizer for epoxy resins, and epoxy resins which incorporate the reactive external flexibi zer
• Non-reactive external flexibilizers for epoxy resin systems are frequently considered as plasticizers including natural or synthetic rubbers, such as styrene-butadiene, acrylonitrile-butadiene polymers, or dibutylphthalate High boiling point solvents such as benzyl alcohol are sometimes used as plasticizers
• Reactive external flexibilizers for epoxy resin systems include products such as DESMOCAPTM marketed by BAYER AG Such external flexibilizers may be prepared from polyalkylene oxides bound to a common backbone such as t ⁇ metholpropane A similar reactive external stabilizer is reported in German Patent DE 3202300 There a polyalkylene oxide component having a molecular weight of from 500 to 3500 is described To the hydroxyl groups of the polyalkylene oxide, a cyclic carboxylic acid anhydride is added to generate a carboxyl group The polyalkylene oxide component is derived from the addition reaction of an alkyl oxide such as ethylene oxide or propylene oxide to an active hydrogen compound such as a mono- or polyalcohol
• Efforts to impart flexibility to cross-linked epoxy resins by chemical modification of the epoxy backbone include incorporation of aliphatic components in generally aromatic epoxy resins by reaction of aromatic epoxy resins with aliphatic acids
• a different means of internally flexibiiizing epoxy resins is the incorporation of diglycidyl ether of a polyol according to EP 0 253 404
• polyalkylene oxide blocks of less than 500 molecular weight provide good flexibility to epoxy resin systems and provide additional properties including surprising resistance to hydrocarbon solvents
• the external reactive flexibilizers of the instant invention may be prepared starring from polyoxyalkylene oxide blocks having molecular weights less than 500.
• suitable starting materials are polyether polyols such as the series marketed under the trademark VORANOL by The Dow Chemical Company.
• the polyether polyol may be prepared by the addition of an alkylene oxide to a polyalcohol such as glycerine.
• the resulting polyoxyalkylene oxide may advantageously then be reacted with a cyclic carboxylic acid anhydride to yield a half-ester of the cyclic carboxylic acid.
• the invention provides a compound of the Formula I:
• A is the residue of an alcohol having a hydroxyl functionality from 1 to 5
• W is a divalent residue derived from a difunctional anhydride
• L is a leaving group, for example OH or halogen
• X is hydrogen, a branched or linear alkyl group of from 1 to 10 carbon atoms, or an alkyl group of from 1 to 10 carbon atoms substituted by a halogen
• n is from 1 to 10
• a is from 0 to 4
• b is from 1 to 5, provided that a + b is from 1 to 5.
• Component A may be derived from a mono or a polyfunctional alcohol.
• A may have from 1 to 30 carbon atoms, and preferably A is derived from a polyalcohol or a polyphenol.
• other possible sources are compounds containing acid hydrogen, such as compounds containing carboxyl or hydroxyl groups or CH groups which are activated by adjacent carbonyl groups.
• Residues of polyphenols such as bisphenol A, bisphenol F, or phenol novolac are also suitable as component A in Formula I.
• Monohydric to pentahydric aliphatic alcohols of from 1 to 5 carbon atoms are preferred.
• Such preferred alcohols include dihydric alcohols, such as ethylene glycol, propylene or butylene glycol, trihydric alcohols such as glycerol, 1,1,1 -tris- (hydroxymethyl)-propane, 1 ,3,5-tris- (2-hydroxyethyl)-isocyanuric acid tetrahydric alcohols such as pentaerythritol, or pentahydric alcohols, such as arabitol.
• dihydric alcohols such as ethylene glycol, propylene or butylene glycol
• trihydric alcohols such as glycerol, 1,1,1 -tris- (hydroxymethyl)-propane, 1 ,3,5-tris- (2-hydroxyethyl)-isocyanuric acid tetrahydric alcohols such as pentaerythritol, or pentahydric alcohols, such as arabitol.
• X may be hydrogen, a branched or linear alkyl group having from 1 to 10 carbon atoms, or an alkyl group of from 1 to 10 carbon atoms substituted by a halogen.
• n is from 1 to 10, preferably from 2 to 4. Further, the combination of the variable X, and the number n in segment
• W is a divalent-radical derived from a cyclic anhydride such as C 2 -C 20 alkane-diyl or alkylene-diyl, a C 4 -C 10 1 ,2-cycloalkylene or cycloalken-1 ,2-ylene, a C 6 -C, 0 cycloalkadien-1 ,2-ylene, and is derived from a dicarboxylic acid cyclic anhydride or its chemical equivalent, such as an acid halide.
• the cyclic ring may or may not be substituted with one or more C,-C 6 hydrocarbon residues.
• W is alternatively an ortho-arylene derived from a 1 ,2-aromatic dicarboxylic acid anhydride.
• Preferred sources for component W include known anhydrides reactive with epoxy groups as are summarized by Lee and Neville at pages 12-3, to 12-7.
• Preferred anhydrides include the alkyl, alkylene, and aromatic anhydrides succinic anhydride, maleic anhydride, phthalic anhydride, dichloromaleic anhydride, dodecenylsuccinic anhydride, glutaric anhydride, tetrahydrophthalic anhydride, 3,6-dimethyltetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydro-phthalic anhydride pyromellitic dianhydride, cis-cyclopentanetetra carboxylic acid dianhydride, hemimellitic anhydride, trimellitic anhydride, and naphthalene-1 ,8-dicarboxylic acid anhydride.
• Formula I provides an available carboxylic acid group for the reaction of an oxirane ring of an epoxide and a carboxylic acid to generate a second ester linkage from the anhydride.
• a second oxirane ring is available to react with the external flexibiiizing compound into the epoxy resin system.
• the flexibilized epoxy resin compounds of the invention may be represented by the following Formula II: Formula II
• Component B is generally derived from an epoxy resin having more than one epoxy group. B may correspond to one of Formulas IX to XII
• R 1 is separately in each occurrence C,. 10 alkane-diyl, C, . , 0 haloalkylene, C 410 cycloalkylene, carbonyl, sulfonyl, sulfinyl, oxygen, sulfur, or a direct bond.
• R' is preferably C, 3 alkylene, C 1 3 haloalkylene, carbonyl, sulfur, or a direct bond; more preferably a direct bond, isopropylidene, or fluorinated isopropylidene (-C(CF 3 ) 2 -); and most preferably isopropylidene.
• R 2 is separately in each occurrence C, 3 alkyl or a halogen; R 2 is preferably methyl, bromo or chloro; and most preferably methyl or bromo.
• R 3 is separately in each occurrence C,. 10 alkylene or C ⁇ cycloalkylene; R 3 is preferably C 1 3 alkylene or polycyclic moiety corresponding to Formula VIII
• a is independently at each occurrence 0 to 4; and m is independently at each occurrence from 0 to 4.
• m is from 0 to 2.
• variable m' is independently at each occurrence from 0 to 3.
• n is as previously defined, that is, from 1 to 10.
• variable s is from 0 to 8; and more preferably from 0 to 4.
• the variable r is from 0 to 40.
• r is from 0 to 10, and most preferably 0 to 5.
• the symbols: a, b, m, m', n, r, and s may represent an average number, as the compounds to which they refer are generally found as a mixture of compounds with a distribution of the units to which they refer.
• X is as previously defined.
• the external reactive flexibilizer described when combined with polyepoxides, forms a flexibilized epoxy resin system.
• the chosen amount of flexibilizer may be added to the total epoxy resin of the system to be so flexibilized, or it may be combined with a fraction of the total epoxy resin of an epoxy resin system to be flexibilized.
• the portion comprising the flexibilizer, according to Formula II will comprise from 5 to 70 per 100 parts by weight of the epoxy resin of the system.
• a lesser amount of flexibilizer generally yields insufficient flexibilization to be useful in the resin properties.
• more than 75 parts flexibilizer is incorporated into the resin system it is found that chemical resistance becomes unacceptable.
• the epoxy resin as modified with the flexibilizer may be cured to form a hardened useful resin by means of any of the known curing agents such as: dicyandiamide and its derivatives; polycarboxylic acid anhydrides, such as those previously mentioned; aromatic polyamines such as m- phenylenediamine or cycloaliphatic polyamines.
• the epoxy resin systems may be cured by polyami ⁇ oamides, polyaminoimidazoline, aliphatic polyamines or polyether-polyamines.
• Useful curing agents are taught by Lee and Neville at Chapters, 7-12.
• the epoxy resin systems described, and acrylation or methacrylation reaction products thereof are useful for the purposes for which epoxide resins have found utility generally.
• the epoxide resin systems are particularly useful where impact resistance is required such as fiber reinforced composite articles such as boats, recreational vehicle body parts, automotive body parts, helmets and sport rackets.
• the flexibilized epoxy resins described also find use as coatings where the substrate is subject to deflection.
• the polyalkylene oxide half-ester flexibiiizing agent may be prepared according to the following procedure. Measurements are in parts by weight, unless otherwise stated.
• a polypropylene glycol prepared from the reaction of glycerin and propylene oxide to form a three-functional polypropylene glycol in the quantity indicated is introduced into an appropriately sized reaction vessel.
• the indicated quantity of the designated dicarboxylic acid anhydride is added to the reaction vessel.
• the gas volume of the reactor was purged with Nitrogen gas.
• the reaction mixture was heated to 130°C to 140°C with stirring for 2 to 3 hours. At time intervals, the reaction mixture was tested to determine the acid number of the reaction mixture. When the acid number approached the theoretical acid number calculated for the expected reaction product, the reaction vessel was cooled.
• the acid number was defined for this purpose as the mg KOH per gram of resin necessary to neutralize the resin in a simple titration using phenolphthaleme as a color indicator KOH was conveniently 0 1 N in water
• the resin aliquot was dissolved in a solvent such as acetone
• the flexibilized epoxy resin systems of the invention incorporating the polyalkylene oxide components prepared according to Examples 1 to 4 may be prepared as follows. To an appropriately sized reaction vessel there was charged a measured quantity of a polyepoxide A measured quantity of polyalkylene oxide flexibiiizing agent was added to the reactor. Sufficient known catalyst was added to catalyze the reaction of the epoxide groups of the polyepoxide with the carboxylic acid groups of the polyalkylene oxide-anhydride adduct.
• tetramethylammonium chloride was suitable at 0 3 weight percent Ethyl-tnphenylphosphonium acetate was used in these examples At a temperature of 120°C to 125°C polyacid and epoxy resin were reacted for 1 5 to 2 hours
• Epoxidized flexibilizer is incorporated into an epoxy resin system by room temperature blending according to the ratios in Table II
• a hardener for resins of Examples 5 to 11 there was used a reaction product of isophorone diamine and a liquid epoxy resin which was a 50 50 blend of diglycidyl ether of bisphenol A and diglycidyl ether of bisphenol F, having an amine hydrogen equivalent weight [AHEW] of 96, 10.7 parts; benzylalcohol 36.6 parts; isophorondiamine 356 parts; m- xylenediamine 9.0 parts; salicylic acid 5.4 parts and nonylphenol 2.7 parts.
• epoxide resin compositions having segments of polyalkylene oxide of molecular weight less than 500 provide flexibility comparable to epoxide resin compositions having molecular weight in excess of 500.
• the epoxide resin compositions having polyalkylene oxide segments of molecular weight less than 500, Examples 9, 10, and 11 provide superior resistance to organic solvents, and without sacrifice of resistance to acids or mechanical properties.

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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)
• Epoxy Resins (AREA)

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• 1996
  • 1996-07-10 GB GBGB9614436.5A patent/GB9614436D0/en active Pending
• 1997
  • 1997-07-07 JP JP10505341A patent/JP2000514480A/ja active Pending
  • 1997-07-07 EP EP97932557A patent/EP0910600A1/de not_active Withdrawn
  • 1997-07-07 KR KR1019997000090A patent/KR20000067856A/ko not_active Application Discontinuation
  • 1997-07-07 WO PCT/US1997/011938 patent/WO1998001495A1/en not_active Application Discontinuation
  • 1997-07-07 BR BR9710157A patent/BR9710157A/pt active Search and Examination
  • 1997-07-07 CA CA002259901A patent/CA2259901A1/en not_active Abandoned
  • 1997-07-10 CO CO97038624A patent/CO4820410A1/es unknown

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