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
  • C08G59/18—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
  • C08G59/687—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 sulfur
• • 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
  • C08G65/04—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 from cyclic ethers only
  • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
  • C08G65/08—Saturated oxiranes
  • C08G65/10—Saturated oxiranes characterised by the catalysts used
  • C08G65/105—Onium 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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/06—Preparatory processes
  • C08G77/08—Preparatory processes characterised by the catalysts used
• • 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
  • C08G85/00—General processes for preparing compounds provided for in this subclass
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers

Definitions

• the present invention relates to heat curable compositions comprising a cationically polymerizable organic material, for example, an epoxy resin, a dialkyl hydroxyarylsulfonium salt and an organic oxidant.
• a cationically polymerizable organic material for example, an epoxy resin, a dialkyl hydroxyarylsulfonium salt and an organic oxidant.
• organic resins for example, epoxy resins can be thermally cured by using an effective amount of an aromatic onium salt such as an aryl iodonium salt and a reducing agent, for example, a thiophenol.
• an aromatic onium salt such as an aryl iodonium salt
• a reducing agent for example, a thiophenol.
• the present invention is based on the discovery that such organic resin also can be thermally cured with an organic oxidant, such as an organic peroxide in combination with an effective amount of certain hydroxyaryldialkyl sulfonium salts, for example,
• thermo curing agent consisting essentially of an organic oxidant and a dialkyl hydroxy aryl sulfonium salt.
• dialkylhydroxyarylsulfonium salts which can be used in the practice of the present invention are compounds having the formula, where R is a C (6-20 ) aromatic radical having from 1 to 3 nuclearly bonded hydroxy radicals, R can be the same or different C (1-8) alkyl radical or an alkylene radical capable of forming a cycloaliphatic or heterocyclic ring, Y is a non-nucleo philic anion, a is an integer equal to 1 or 2, and when R 1 is alkyl, a is 2, and when R is alkylene, a is 1.
• Radicals included by R of formula (1) are, for example,
• R 1 radicals include CH 3 -,-C 4 H 9 -, C 2 H 5 -, CH 3 O- , (CH 3 ) 3 C-,
• the salts included by formula (1), are
• R 1 , M, Q and d are as previously defined, and R 2 -R 6 are monovalent radicals selected from hydrogen, C (1-8) alkyl,
• Dialkyl hydroxyphenylsulfonium salts included by formulas (1) and (2) are,
• Organic oxidants which can be used in the practice of the invention incombination with the dialkylhydroxy arylsulfonium salts of formulas 1 and 2 to effect the cure of the cationically polymerizable organic material are, for example, organic peroxides such as ketone peroxides, peroxy acids, dibasic acid peroxides, aldehyde peroxides, alkyl peroxides, hydroperoxides, alkyl peroxyesters, diperoxide derivatives, for example, t-butyl peroxypivalate, 2,4-dichlorobenzoyl peroxide, caprylyl peroxide, lauroyl peroxide, decanoyl peroxide, propionyl peroxide, acetyl peroxide, t-butyl peroxyisobutyrate, p-chlorobenzoyl peroxide, benzoyl peroxide, hydroxyheptyl peroxide, cyclohexanone per
• organic oxidants which also can be used in the practice of the invention include azo-bis alkyl nitriles and other azo zompounds, such as
• OMPI ⁇ .
• WIPO iodoso aromatic compounds such as iodosobenzene, 4-nitroiodosobenzene, iodosobenzene diacetate, 4,chloroiodosobenzene, 4-methoxyiodosobenzene, 4-iodosobiphenyl, 2-chloroiodosobenzene diacetate, etc.
• Cationically polymerizable organic materials which can be used to make the heat curable compositions of the present invention include epoxy resins, thermosetting organic condensation resins of formaldehyde, vinyl organic prepolymers, cyclic ethers, etc.
• epoxy resin as utilized in the description of the cationically polymerizable compositions of the present invention, includes any monomeric, dimeric or oligomeric or polymeric epoxy material containing one or a plurality of epoxy functional groups.
• those resins which result from the reaction of bisphenol-A (4,4'-isopropylidenediphenol) and epichlorohydrin, or by the reaction-of low molecular weight phenol formaldehyde resin (Novolak resin) with epichlorohydrin can be used alone or in combination with an epoxy containing compound as a reactive diluent.
• Such diluents as phenyl glycidyl ether, 4-vinylcyclohexene dioxide, limonene dioxide, 1,2-cyclohexene oxide, glycidyl acrylate, glycidyl methacrylate, styrene oxide, allyl glycidyl ether, etc., may be added as viscosity modifying agents.
• the range of these compounds can be extended to include polymeric materials containing terminal or pendant epoxy groups.
• examples of these compounds are vinyl copolymers containing glycidyl acrylate or methacrylate as one of the comonomers.
• Other classes of epoxy containing polymers amenable to cure using the above catalysts are epoxy- siloxane resins, epoxy-polyurethanes and epoxy-polyesters. Such polymers usually have epoxy functional groups at the endsof their chains. Epoxy-siloxane resins and method for making are more particularly shown by E. P. Plueddemann and G. Fanger, J. Am. Chem. Soc. 802632-5 (1959).
• epoxy resins can also be modified in a number of standard ways such as reaction with amines, carboxylic acids, thiols, phenols, alcohols, etc., as shown in patent 2,935,488; 3,235,620; 3,369,055, 3,379,653; 3,398,211, 3,403,199; 3,563,840; 3,567,797; 3,677,995; etc.
• Further coreactants which can be used with epoxy resins are hydroxy terminated flexibilizers such as hydroxyl terminated polyethers, hydroxy terminated polyesters, etc., shown in the Encyclopedia of Polymer Science and Technology, Vol. 6, 1967, Interscience Publishers, New York, pp. 209-271 and particularly p. 238.
• thermosetting organic condensation resins of formaldehyde which can be used in the practice of the present invention are, for example, urea type resins, such as
• x and n are integers having a value of 1 or greater;
• alkoxy silanes having the formula
• R 7 is a C (1 _ 7) alkyl radical
• R 8 is selected from R 7 radicals and C (6-13) aryl radicals and halogenated derivatives
• m is an integer equal to 1 to 4
• n is an integer equal to 0 to 3 inclusive and m + n is equal to 4.
• melamine thiourea resins melamine, or urea aldehyde resins, cresol-formaldehyde resins and combinations with other carboxy, hydroxyl, amino and mercapto containing resins, such as polyesters, alkyds and polysulfides.
• a further category of the organic materials which can be used to make the polymerizable compositions are cyclic ethers which are convertible to thermoplastics. Included by such cyclic ethers are, for example, oxetanes such as 3,3-bis-chloromethyloxetane, alkoxyoxetanes as shown by Schroeter Patent 3,673,216, assigned to the same assignee as the present invention; oxolanes such as tetrahydrofuran, oxepanes, oxygen containing spiro compounds, trioxane, dioxolane, etc.
• oxetanes such as 3,3-bis-chloromethyloxetane, alkoxyoxetanes as shown by Schroeter Patent 3,673,216, assigned to the same assignee as the present invention
• oxolanes such as tetrahydrofuran, oxepanes, oxygen containing spiro compounds, triox
• cyclic esters such as ⁇ -lactones, for example propiolactone
• cyclic amines such as 1,3,3-trimethyl-azetidine
• organosilicone cyclics for example, materials inlcuded by the formula, where R" can be the same or different monovalent organic radical such as methyl or phenyl and p is an integer equal to 3 to 8 inclusive.
• R" can be the same or different monovalent organic radical such as methyl or phenyl and p is an integer equal to 3 to 8 inclusive.
• organosilicon cyclic is hexamethyl trisiloxane, octamethyl tetrasiloxane, etc.
• the products made in accordance with the present invention are high molecular weight oils and gums.
• the heat curable compositions of the present invention can be made by blending the cationically polymerizable organic material with an effective amount of the thermal curing agent.
• the resulting curable, composition can be in the form of a varnish having a viscosity of from 1 to 100,000 centipoises at 25oC or a free flowing powder, depending upon the nature of the cationically polymerizable organic material.
• the curable compositions can be applied to a variety of substrates by conventional means and cured to the tack-free state within 0.5 to 20 minutes, depending upon the temperature employed.
• an organic solvent such as nitromethane, acetonitrile
• the dialkyl hydroxy arylsulfonium salts can be formed in situ if desired.
• the curable compositions may contain inactive ingredients, such as silica, talc, clay, glass fibers, extenders, hydrated alumina, carbon fiber process aids, etc., in amounts of up to 500 parts of filler per 100 parts of cationically polymerizable organic material.
• the curable compositions can be applied to such substrates as metal; rubber, plastic, molded parts or films, paper, wood, glass, cloth, concrete, ceramic, etc.
• curable compositions of the present invention are, for example, protective, decorative and insulating coatings, potting compounds, printing inks, sealants, adhesives, molding compounds, wire insulation, textile coatings, laminates, impregnated tapes, varnishes, etc.
• protective, decorative and insulating coatings potting compounds, printing inks, sealants, adhesives, molding compounds, wire insulation, textile coatings, laminates, impregnated tapes, varnishes, etc.
• Example 3 The procedure of Example 1 was repeated, except that Celanese SU8, epoxy novolak resin was substituted for the diglycidyl ether bisphenol-A epoxy resin. The resuting heat curable composition required eight minutes to harden at 120oC. Example 3.
• Methylon ® resin a phenolformaldehyde resole of the General Electric Company
• 3 parts of t-butyl hydroperoxide were then heated at 150oC.
• the mixture having the t-butyl hydroperoxide cured to a hard crosslinked insoluble resin.
• the mixture free of the organic oxidant remained substantially unchanged.

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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)
• Epoxy Resins (AREA)
• Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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Applications Claiming Priority (2)

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Citations (7)

• 1979
  • 1979-02-12 US US06/011,102 patent/US4230814A/en not_active Expired - Lifetime
• 1980
  • 1980-02-01 WO PCT/US1980/000097 patent/WO1980001723A1/en not_active Ceased
  • 1980-02-01 DE DE8080900361T patent/DE3070910D1/de not_active Expired
  • 1980-02-01 JP JP50048580A patent/JPS56500496A/ja active Pending
  • 1980-08-25 EP EP80900361A patent/EP0023912B1/en not_active Expired

Patent Citations (7)

Non-Patent Citations (1)

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