Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
  • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
  • C08F299/026—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from the reaction products of polyepoxides and unsaturated monocarboxylic acids, their anhydrides, halogenides or esters with low molecular weight
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
  • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
  • C08F299/04—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyesters
  • C08F299/0442—Catalysts

Definitions

• a variety of additives are taught by the art as useful in controlling the gelation and/or cure of ' unsaturated resins, such as vinyl ester resins or unsaturated polyester resin.
• the time it takes for a resin to gel decreases as the temperature increases.
• the ten ⁇ dency to gel is also dependent on the nature of the resin, on the kind and amount of monomer which is generally mixed with the resin, on the catalyst/promoter system and on other factors.
• Fabrication techniques vary widely. In some instances, it may be desirable to have a very short pot life and a very fast cure. In other instances, such as in hand lay up techniques, it is desirable to have a
• Ol ⁇ Tl long pot life and a quick cure on demand may have different optimum schedules. It would be a great help to the for ulator and fabricator if flexibility could be built into a formulation to avoid the necessity of a special mixture for each schedule.
• U.S. Patent No. 3,584,076 teaches that the rate of polymerization initiation of unsaturated poly ⁇ ester resins and other monomers by redox reactions involving- peroxide such as methyl ethyl ketone peroxide and tert-butyl perbenzoate with soluble salts of redox active metals such as cobalt octoate is greatly acceler ⁇ ated in the presence of enolizable ketones such as 2,4-pentanedione.
• This invention is directed to a process for controlling the gelation and cure rates of free radical curable resins comprising admixing (1) a vinyl ester of a polyglycidyl ether'of a polyhydric compound, an unsaturated polyester or a mixture thereof, (2) a peroxide selected from ketone peroxides, tertiary hydroperoxides or peroxyesters, (3) a redox reactive metal salt soluble in the curable resin, and (4) an enolizable beta-diketone characterized in that the vinyl ester, the unsaturated polyester or a mixture thereof has a pH greater than 5.7 measured as a 10 percent methanol solution and further characterized by maintaining the mixture at a temperature less than 130°F (54°C) to extend the nongelled state and subse- quently raising the temperature above 130°F (54°C) to achieve acceleration of the cure rate.
• a vinyl ester of a polyglycidyl ether'of a polyhydric compound an unsaturated polyester
• Vinyl ester resins are described in U.S. Patent No. 3,367,992 wherein dicarboxylic acid half esters of hydroxyalkyl acrylates or ethacrylates are reacted with polyepoxide resins.
• Bowen in U.S. Patent Nos. 3,066,112 and 3,179,623 describes the preparation of vinyl ester resins from monocarboxylic acids such as acrylic and methacrylic acid.
• Bowen also describes alternate methods of preparation wherein a glycidyl methacrylate or acrylate is reacted with the sodium salt of a dihydric phenol such as bisphenol- A.
• Vinyl ester resins based on epoxy novolac resins are described in U.S. Patent No.
• OMPI and terminal, polymerizable vinylidene groups are classified as vinyl ester resins.
• any of the known polyepoxides may be employed in the preparation of the vinyl ester resins of this invention.
• Useful polyepoxides are glycidyl polyethers of both polyhydric alcohols and polyhydric phenols, epoxy novolacs, epoxidized fatty acids or drying oil acids, epoxidized diolefins, epoxidized diunsaturated acid esters as well as epoxides of unsat- urated polyesters, as long as they contain more than one oxirane group per molecule.
• Preferred polyepoxides are glycidyl poly ⁇ ethers of polyhydric alcohols or polyhydric phenols having weights per epoxide group from 150 to 2000. These polyepoxides are usually made by reacting at least about two moles of an epihalohydrin or glycerol dihalohydrin with one mole of the polyhydric alcohol or polyhydric phenol, and a sufficient amount of a caustic • alkali to combine with the halogen of the halohydrin. The products are characterized by the presence of more than one epoxide group per molecule, i.e., a 1,2-epoxy equivalency greater than one.
• Unsaturated monocarboxylic acids include, for example, acrylic acid, methacrylic acid, halogenated acrylic or methacrylic acid, cinnamic acid and mixtures thereof. Also included within the term "unsaturated carboxylic acids" are the hydroxyalkyl acrylate or methacrylate half esters of dicarboxyl acids as described in U.S. Patent No. 3,367,992 wherein the hydroxyalkyl group, preferably has from 2 to 6 carbon atoms.
• unsaturated polyesters are readily available or can be prepared by methods well- known to the art. Such polyesters result from the con ⁇ densation of polybasic carboxylic acids and compounds having two or more hydroxyl groups.
• an ethylenically unsaturated dicarboxylic acid such as, for example, maleic acid, fumaric acid, or itaconic acid is inter- esterified with an alkylene glycol or polyalkylene glycol having a molecular weight of up to 2000.
• dicarboxylic acids free of ethylenic unsatura- tion such as, for example, phthalic acid, isophthalic acid, adipic acid, or succinic acid may be employed within a molar range of 0.25 to as much as 15 moles per mole of the unsaturated dicarboxylic acid. It will be understood that the appropriate acid anhydrides when they exist may be used and usually are preferred when available.
• glycol or polyhydric alcohol component of the polyester is usually stoichiometric or in slight * excess with respect to the sum of the acids-
• the excess of polyhydric alcohol seldom will exceed 20 to 25 percent and usually is 10 to 15 percent.
• Vinyl ester/unsaturated polyester resin blends are also effectively stabilized.
• the blends may be prepared either by physically mixing the two resins in the desired proportions or by preparing said vinyl ester resin in the presence of said unsaturated polyester.
• the resin phase is blended with a copolymerizable monomer.
• Suitable monomers include vinyl aromatic com ⁇ pounds such as, for example, styrene, vinyl toluene, or divinyl benzene.
• Other useful monomers include the esters of saturated alcohols such as, for example, methyl, ethyl, isopropyl, and octyl, with acrylic acid or methacrylic acid; vinyl acetate, diallyl maleate, dimethallyl fumarate; mixtures of the same and all other monomers which are capable of copolymerizing with the vinyl ester resin.
• Catalysts that may be used for the curing or polymerization are ketone peroxides, such as methyl ethyl ketone peroxide, tertiary peroxides such as cumene hydroperoxide, or peroxyesters such as 2,5-dimethyl-2,5-bis(2-ethylhexoylperoxy)hexane.
• the amount of the catalyst added will vary preferably from 0.5 percent to 3.0 percent by weight of the resin phase.
• the cure system also includes known redox reactive metal salts accelerating agents in an amount to provide from 0.0001 to 0.1 parts metal per 100 parts resin.
• Such salts include, for example, the naphthenate or octoate salts of cobalt, manganese, nickel, vanadium and molybdenum.
• accelerators and promoters such as, for example, dimethylaniline or N,N-dimethyltoluidine, may be employed in addition to the metal salts.
• the amount of these amines will vary, preferably from 0.0 to 0.5 percent by weight of the resin phase.
• the final essential part of the cure system is an enolizable beta-diketone.
• a preferred species is 2,4-pentadione.
• the amount of the beta-diketone will vary preferably from 0.001 to 2.0 percent by weight of the resin phase.
• Optimum ratios of the resin and cure system ingredients can be easily determined by preliminary tests.
• the cure system varies the gel and cure times depending upon temperature.
• the inventive concept provides a choice of gel and cure times.
• the resin can be formulated to remain an ungelled liquid for several hours at less than 130°F (54°C).
• the exotherm of the reaction raises the temperature of the resin above 130°F (54°C) resulting in an acceleration of the cure rate.
• the tempera ⁇ ture of the resin can be raised above 130°F (54°C) by the application of heat to achieve rapid gel and cure.
• heat can be added to that being generated by the exotherm to raise the temperature above 130°F (54°C) and achieve fast cure.
• Resin B was a vinyl ester resin prepared by reacting 1 equivalent of methacrylic acid with 0.75 equivalent of an epoxy novolac having an epoxide equiva ⁇ lent weight between 175 and 182 and 0.25 equivalent of a diglycidyl ether of bisphenol A having an EEW between 186 and 192.
• the above reactants were heated to 115°C with catalyst and hydroquinone present until the carboxy- lic acid content reached 1 percent.
• the reactants were cooled and then styrene containing 50 pp of t-butyl catechol was added until the styrene content was 36 percent.
• the final resin diluted with styrene had a pH of 7.3.
• Resin C was a vinyl ester resin prepared by catalytically reacting 0.05 equivalent of bisphenol A with 0.25 equivalent of the diglycidyl ether of bisphenol A having an EEW between 186 and 192 to form a polyepoxide having an EEW of 275. After cooling 1 equivalent of an epoxy novolac having an EEW between 172 and 182 and 1.05 equivalent of methacrylic acid are added and reacted to an acid content of 1 percent.
• Resin D was a vinyl ester resin prepared by catalytically reacting 1 equivalent of bisphenol A and 100 parts of a carboxy terminated butadiene-acrylonitrile rubber with 2.25 equivalents of the diglycidyl ether of bisphenol A having an EEW between 180 and 185 to form a polyepoxide having an EEW of 550. Then, 1.2 equivalents of methacrylic acid are added and reacted to an acid
• Resin E was a vinyl ester resin prepared by catalytically reacting 1 equivalent of tetrabromobis ⁇ phenol A with 0.9 equivalent of the diglycidyl ether of tetrabro'mobisphenol A advanced with tetrabromobisphenol A to an EEW of 460 and 1.5 equivalents of the diglycidyl ether of bisphenol A having an EEW between 182 and 192, the reaction product having an EEW of 700. This reaction product was then reacted with 1.4 equivalents of meth ⁇ acrylic acid to an acid content of 1 percent and an epoxide content of 0.4 percent. The final resin, diluted with styrene containing 50 ppm of t-butyl catechol to a styrene content of 37.5 percent, had a pH of 7.7.
• Resin F was a commercially available isophthalic unsaturated polyester having a pH of 4.8.
• Resin B parts 100 100 96 96 94 94 0 0
• compositions were made and tested as in the previous examples and comparative runs using Resin E.
• the curing system based upon 100 parts of resin, was 5 1.0 part methyl ethyl ketone peroxide, 0.1 part dimethyl- aniline, and in Comparative Run K and Example 7, 0.25 part cobalt naphthenate; in Comparative Run L and Example 8, 0.125 part cobalt octoate.
• Comparisons were made with 0.2 part 2,4-pentadione in Examples 7 and 8 and without • 10 that compound in Comparative Runs K and L. The results are shown in Table ' III.
• compositions were prepared from. Resins A and F using the procedures of the preceding examples and comparative runs.
• Example 9 and Comparative Runs M, N, and O reported in the following Table IV(a)
• the cure system based upon 100 parts of resin, is 1 part cumene hydroperoxide, 0.03 part cobalt naphthenate and with or without 2,4-pentanedione.
• Comparative Runs P, Q, R and S reported in Table IV(b)
• the cure systems, based upon 100 parts of resin is 1 part benzoyl peroxide, 0.1 part dimethylaniline and with or without 2, -pentanedione.
• Resin F F A A 2,4-P, phr 0 0.1 0 0.1 Gel Time, min. 840' 1010 260 510 Peak Time, min. >1440 1203 382 664 Peak Exotherm, °C 146 134 124

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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)
• Macromonomer-Based Addition Polymer (AREA)
• Polymerization Catalysts (AREA)

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• 1983
  • 1983-08-03 WO PCT/US1983/001191 patent/WO1984000765A1/en not_active Ceased
  • 1983-08-03 JP JP58502756A patent/JPS59501511A/ja active Granted
  • 1983-08-03 AU AU18888/83A patent/AU1888883A/en not_active Abandoned
  • 1983-08-03 EP EP19830902670 patent/EP0115522A4/de not_active Withdrawn

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