WO2016069161A1 - Composition durcissable - Google Patents

Composition durcissable Download PDF

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Publication number
WO2016069161A1
WO2016069161A1 PCT/US2015/052616 US2015052616W WO2016069161A1 WO 2016069161 A1 WO2016069161 A1 WO 2016069161A1 US 2015052616 W US2015052616 W US 2015052616W WO 2016069161 A1 WO2016069161 A1 WO 2016069161A1
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Prior art keywords
composition
curable composition
resin
reactive diluent
viscosity
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PCT/US2015/052616
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English (en)
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Joseph Gan
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Blue Cube Ip Llc
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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
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C08G59/1461—Unsaturated monoacids
    • C08G59/1466—Acrylic or methacrylic acids
    • 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
    • C08L63/10—Epoxy resins modified by unsaturated compounds

Definitions

  • the present invention is related to a curable thermosetting resin composition containing a vinyl ester resin monomer diluent.
  • Vinyl ester resins are known to be employed as thermosetting (i.e., curable) resins to form cured thermoset structures because cured resins from VER exhibit excellent properties such as toughness and corrosion resistance properties.
  • curable VER compositions are prepared and mixed with styrene, a polymerizable monomer and a common reactive diluent.
  • Styrene is typically used in large quantities, for example at quantities of greater than (>) 30 weight percent (wt %) in thermosetting liquid resins, such as VER, to reduce the viscosity of such thermosetting liquid resins.
  • thermosettable resin has to be sufficiently low (e.g., as low as ⁇ 3,000 mPa-s and more commonly as low as ⁇ 1,000 mPa-s) to be able to process the resin in a conventional molding operation.
  • the curable VER composition is cured, the styrene present in the composition becomes a part of the resin system to produce a rigid cross- linked structure with desirable toughness and corrosion resistance properties.
  • styrene is a volatile organic compound (VOC); and, compositions containing styrene produce an undesirable quantity of styrene emissions (e.g., > 5 wt %) into the atmosphere when such compositions containing styrene are processed. Therefore, it would be beneficial to replace the styrene diluent used as a reactive diluent in thermosetting compositions or at least reduce the styrene content of said compositions in order to reduce styrene emissions. For example, it would be an advantage to reduce the styrene content of curable composition to less than about 40 wt % in order to reduce styrene emissions to less than about 5 wt %.
  • VOC volatile organic compound
  • U.S. Patent No. 5,378,743 discloses a stable, low level styrene emission vinyl ester or unsaturated polyester resin composition containing a stabilizing agent.
  • This known resin system demonstrates a reduced polymerizable styrene emission of less than 5 wt %; and the stabilizing agent can be a nonionic surfactant or a copolymer of maleic acid half ester of a polyethylene glycol and a monoalkenyl aromatic monomer.
  • the stable, low polymerizable monomer emission resin composition disclosed in the above patent includes (a) a vinyl ester or an unsaturated polyester resin, (b) a polymerizable monomer, (c) a film forming wax material, (d) an adhesion promoter, and (e) a stabilizer of a copolymer of maleic acid half ester of a polyethylene glycol arid a monoalkenyl aromatic monomer.
  • the resin system disclosed in U.S. Patent No. 5,378,743 has the disadvantage of providing interlayer adhesion which has poor properties because of the wax film formation between the different layers.
  • U.S. RE43983E discloses the properties of a multi-modal vinyl ester resin such as fracture toughness, processing viscosity, and VOC emissions.
  • the known multi-modal vinyl ester resin is the reaction product of a liquid or crystalline epoxy and an amorphous, solid epoxy, as determined at 25° C, with a vinyl carboxylic acid.
  • the multi-modal vinyl ester resin may contain a reactive diluent such as styrene at a lower content than that required for similar, commercially available vinyl ester resins; and the exhibits good fracture properties and low VOC emissions while maintaining low resin viscosity.
  • the multi-modal vinyl ester resin disclosed in U.S. RE43983E has the disadvantage of employing relatively costly raw materials such crystalline epoxy; and thus, such process would be uneconomical.
  • a curable a vinyl ester resin (VER) thermosetting resin composition having a reactive diluent, i.e., a VER monomer composition useful as a reactive diluent in the resin composition.
  • the present invention provides a VER reactive diluent that (1) exhibits a viscosity sufficiently low enough (e.g., a viscosity of less than about 2,000 mPa-s) to be effectively used as a reactive diluent; and (2) can be used to replace, or at least minimize the content of styrene which may be present in a VER curable composition to minimize styrene emissions.
  • One embodiment of the present invention is directed to a curable (thermosettable) resin composition or formulation including: (I) at least one thermosetting base resin forming the resin matrix of the composition; and (II) a reactive diluent.
  • the reactive diluent may be a vinyl ester resin (VER) monomer composition; and the VER monomer composition may be derived from the reaction product of: (A) at least one epoxide compound; and (B) at least one unsaturated acid compound.
  • the present invention includes a VER monomer composition reactive diluent having a viscosity of, for example, less than ( ⁇ ) about 2,000 mPa-s at 25 °C.
  • the VER monomer composition reactive diluent can also be used to replace styrene.
  • the low viscosity VER monomer of the present invention can be used as a reactive diluent additive in a curable composition and thus resulting in a curable
  • the resulting curable composition preferably has a viscosity of lower than about 3,000 mPa-s at 25 °C.
  • the resulting curable composition preferably has a low styrene content (e.g., less than about 25 wt %); and advantageously, a composition having a low concentration of styrene also achieves a corresponding low emission of styrene (e.g., ⁇ about 5 wt %) into the environment.
  • Another embodiment of the present invention is directed to a process for preparing the above curable composition.
  • Still another embodiment of the present invention is directed to a thermoset prepared from the above curable composition.
  • the curable composition and the thermoset product can be useful in various applications such as for producing a composite.
  • Some of the advantages of the curable composition of the present invention include for example, low styrene content, better flexibility, better interlayer adhesion, and lower shrinkage.
  • the present invention includes a curable resin formulation or composition including: (I) at least one thermosetting resin forming the base resin or resin matrix of the composition; and (II) a VER monomer as a reactive diluent.
  • the curable resin composition of the present invention may include at least one thermosetting base resin forming the resin matrix of the composition.
  • the at least one thermosetting base resin forming the resin matrix of the composition, component (I) may include for example: (i) an epoxy resin, (ii) a vinyl ester resin, (iii) an unsaturated polyester, (iv) a dicyclopentadiene, (v) a cyanate ester, (vi) a bismalaeic triazine, (vii) an unsaturated acid anhydride, (viii) other unsaturated compounds; or (iv) mixtures thereof.
  • the epoxy compound useful in the present invention when used as component (I) for preparing the curable composition, may include, for example, any one or more conventional epoxy compounds.
  • the epoxy compound can be any one of the same or different epoxy compounds described above with reference to component (A) used to make the VER monomer.
  • One embodiment of the epoxy compound used in the composition of the present invention may be for example a single epoxy compound used alone; or a combination of two or more epoxy compounds known in the art such as any of the epoxy compounds described in Lee, H. and Neville, K., Handbook of Epoxy Resins, McGraw-Hill Book Company, New York, 1967, Chapter 2, pages 2-1 to 2-27, incorporated herein by reference.
  • the epoxy resin useful in the composition of the present invention may include for example one or more bisphenol A liquid epoxy resins, bisphenol F epoxy resins, phenol epoxy novolac epoxy resins, oxazolidone-containing epoxy resins, and commercially available epoxy resins such as DER 330, DER 354, DEN 438, DER 858, DER 852 available from The Dow Chemical Company, and the like; and mixtures thereof.
  • Other epoxy resins useful in the present invention may include for example epoxidized bisphenol A novolac, epoxidized phenol novolac of dicyclopentadiene, epoxidized amino compounds, and mixtures thereof.
  • the amount of epoxy resin used in the composition may be for example, from 10 wt % to about 85 wt % in one embodiment; from about 15 wt % to about 75 wt % in another embodiment; and from about 20 wt % to about 65 wt % in still another embodiment.
  • thermosetting resin of the present invention when used as component (I) for preparing the curable composition, may be (ii) a vinyl ester resin.
  • the vinyl ester can be used alone, or in combination with another different thermosetting resin to form the thermosetting base resin forming the resin matrix of the composition.
  • the vinyl ester useful in the composition of the present invention, when used as component (I), may include for example vinyl esters of DER 330, vinyl esters of DEN 438, vinyl esters of DER 671, vinyl esters of DER 560, vinyl esters of DER 542, and mixtures thereof.
  • the amount of vinyl ester resin used in the composition may be for example, from 20 wt % to about 85 wt % in one embodiment, from about 25 wt % to about 80 wt % in another embodiment; from about 30 wt % to about 75 wt % in still another embodiment, and from about 35 wt % to about 70 wt % in yet another embodiment.
  • the thermosetting resin of the present invention when used as component (I) for preparing the curable composition, may be (ii) an unsaturated polyester.
  • the unsaturated polyester can be used alone, or in combination with another different thermosetting resin to form the thermosetting base resin forming the resin matrix of the curable composition.
  • the unsaturated polyester useful in the curable composition of the present invention when used as component (I), may include for example any one or more of the unsaturated polyesters described in WO1999054393A1, incorporated herein by reference, such as in page 8 of WO1999054393A1.
  • the unsaturated polyesters which can be employed in the practice of the present invention are well known.
  • the unsaturated polyesters contain carboxylic ester groups and carbon-carbon double bonds as recurring units along the polymer backbone.
  • the unsaturated polyesters are usually prepared by condensation of (a) ethylenically unsaturated dicarboxylic or polycarboxylic acids or anhydrides to impart the unsaturation, (b) saturated dicarboxylic acids to modify the resin, and (c) diols or polyols.
  • the unsaturated polyesters may include those having the general structural formula:
  • R and R' are alkylene or arylene radicals in the diol and saturated acid respectively, and x and y are variable numbers which depend upon the composition and condensation conditions.
  • Typical di- or polycarboxylic acids or anhydrides thereof used in the preparation of the unsaturated polyesters may include for example phthalic acids, iso- or terephthalic acid, adipic acid, succinic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, chloromaleic acid, allylsuccinic acid, itaconic acid, mesaconic acid, citric acid, pyromellitic acid, trimesic acid, tetrahydrophthalic acid, thiodiglycollic acid, and mixtures thereof.
  • the above acids and anhydrides may be independently used alone or in combination.
  • Typical di- or polyhydric compounds used in the preparation of the unsaturated polyesters may include for example ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, glycerol, 2-butene-l ,4-diol, hydrogenated bisphenol A, bisphenol dioxyethyl ether, bisphenol dioxypropyl ether, and neopentyl glycol.
  • the amount of unsaturated polyester used in the curable composition may be for example, from 20 wt % to about 85 wt % in one embodiment, from about 25 wt % to about 80 wt % in another embodiment; from about 30 wt % to about 75 wt % in still another embodiment; and from about 35 wt % to about 70 wt % in yet another embodiment.
  • thermosetting resin of the present invention when used as component (I) for preparing the curable composition, may be for example (iii) a dicyclopentadiene (DCPD) resin.
  • DCPD is the dimer of cyclopentadiene (CPD) formed by Diels-Alder addition reaction.
  • CPD cyclopentadiene
  • DCPD is commercially available as a product of about 97 or greater percent purity.
  • DCPD is also commercially available as a Cio hydrocarbon concentrate prepared by dimerizing a crude Q stream from the cracking of hydrocarbons as taught in U.S. Patent No. 3,556,239, incorporated herein by reference.
  • the DCPD concentrate described in U.S. Patent No. 3,556,239 has as the main reactive component from about 70 percent by weight to about 90 percent by weight of DCPD, and from about 5 percen by weight to about 30 percent by weight of the mixed Diels-Alder (timers of diolefins such as butadiene, cis- and trans -piperylene, isoprene, cyclopentadiene and methyl cyclopentadiene.
  • the remainder of the DCPD concentrate generally includes residual C5 hydrocarbons and oligomers of the above diolefins.
  • dimers which have been identified of the DCPD concentrate are the Diels-Alder adducts of two moles of isoprene (isoprene dimers), the adduct of cyclopentadiene and piperylene, and the like.
  • DCPD DCPD concentrate
  • DCPD concentrate DCPD concentrate
  • the DCPD resin or DCPD concentrate can be used alone, or in combination with another different thermosetting resin, to form the thermosetting base resin forming the resin matrix of the curable resin composition.
  • the DCPD resin useful in the composition of the present invention when used as component (I), may include for example a DCPD product commercially available from The Dow Chemical Company such as for example DCPD Resin Grade.
  • a description of DCPD products can be found in a publication entitled "Dicyclopentadiene Products, A Guide to Product Handling and Use", Form No. 778-04301, incorporated herein by reference.
  • DCPD polymer resins are also described, for example, in U.S. Patent Nos. 3,933,757; 3,347,806; 3,883,612; 4,029,848: 4,148,765; 4,348,499; and 4,246,367, the teachings of which are incorporated herein by reference.
  • the amount of DCPD used in the curable composition may be for example, from 20 wt % to about 85 wt % in one embodiment, from about 25 wt % to about 80 wt % in another embodiment; from about 30 wt % to about 75 wt % in still another embodiment, and from about 35 wt % to about 70 wt % in yet another embodiment.
  • thermosetting resin of the present invention when used as component
  • (I) for preparing the curable composition may be (v) a cyanate ester.
  • the cyanate ester resin can be used alone, or in combination with another different thermosetting resin, to form the thermosetting base resin forming the resin matrix of the composition.
  • the cyanate ester resin useful in the composition of the present invention, when used as component (I), may include for example cyanate esters obtained from polyhydric compounds such as bisphenol-A, bisphenol-F, phenol novolacs, bisphenol-A novolacs, DCPD structures containing phenol novolacs, and mixtures thereof.
  • cyanate ester compounds useful in the present invention are described for example in U.S. Patent No. 5,186,880, incorporated herein by reference.
  • useful polyfunctional cyanate ester compounds useful in the present invention include compounds having at least two cyanato groups in its molecule such as those represented by the formula:
  • R is an aromatic organic group and the cyanato groups are directly bonded to the aromatic ring; and m is an integer of from 2 to 5.
  • polyfunctional cyanate compounds useful in the present invention may include 1,3- or 1 ,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, 1,3-, 1,4-, 1,6-, 1,8-, 2,6- or 2,7-dicyanatonaphthalene, 1 ,3,6-tricy anatonaphthalene, 4,4'- dicyanatobiphenyl, bis(4-dicyanatophenyl)methane, bis(3,5-dimethy!-4- dicyanatophenyl)methane, 2,2-bis(4-cyanatophenyl)propane, 2,2-bis(3,5-diehloro-4 ⁇ cyanatophenyl)propane, 2,2-bis(3,5-dibrome-4-cyanatophenyl)propane, 2,2 ⁇ bis(3,5 ⁇ dirnethyl-4-cyanatophenyl)propane, bis(4-eyanatophenyl)ether, bis(4-cyanatophenyl
  • Patent No. 4,578,439 obtained by reacting a pyridine with a halogenated cyanide, a cyanate obtained by reacting a halogenated cyanide (see for example, U.S. Patent No. 4,026,913 and German Patent No. 2,61 1 ,796) with a poly functional phenol in which the phenol is bonded to dicyclopentadiene and mixtures thereof.
  • Other cyanate ester compounds employed in the practice of the present invention are given in U.S. Patent Nos. 3,553,244; 3,755,402; 3,740,348; 3,595,900; 3,694,410; 4,097,455 and 4, 1 16,946 and British Patent Nos.
  • the preferred components include for example 1,3- or 1,4-dicyanatobenzene monomers and 1,3,5-tricyanatobenzene monomer (which are liquid or semi-solid at a temperature of not more than 50 °C); and oligomers (which are liquid or semi-solid at a temperature of not more than 50 °C) including oligomers obtained through a sym-triazine ring by heating bis(4-dicyanatophenyl)methane, 2,2-bis(4-cyanatophenyl)propane or bis(3,5-dimethyl-4- dicyanatophenyl)methane (which are solid at room temperature).
  • the amount of cyanate ester used in the composition may be for example, from 20 wt % to about 85 wt % in one embodiment; from about 25 wt % to about 80 wt % in another embodiment; from about 30 wt % to about 75 wt % in still another embodiment; and from about 35 wt % to about 70 wt % in yet another embodiment.
  • thermosetting resin of the present invention when used as component (I) for preparing the curable composition, may be for example (vi) a bismalaeic triazine ester.
  • the bismalaeic triazine ester resin can be used alone, or in combination with another different thermosetting resin, to form the thermosetting base resin forming the resin matrix of the composition.
  • the bismalaeic triazine ester resin useful in the composition of the present invention, when used as component (I) may include for example the compounds described in U.S. Patent No. 4,438,280, incorporated herein by reference.
  • the amount of bismalaeic triazine ester used in the curable composition may be for example, from 20 wt % to about 85 wt % in one embodiment; from about 25 wt % to about 80 wt % in another embodiment; from about 30 wt % to about 75 wt % in still another embodiment; and from about 35 wt % to about 70 wt % in yet another embodiment.
  • thermosetting resin of the present invention may also include a mixture of two or more of (i) epoxy resins, (ii) vinyl ester resins, (iii) unsaturated polyesters, (iv) dicyclopentadiene, (v) a cyanate ester, and (vi) a bismalaeic triazine.
  • the total amount of the combined thermosetting resins used in the composition may be for example, from 20 wt % to about 85 wt % in one embodiment; from about 25 wt % to about 80 wt % in another embodiment; from about 30 wt % to about 75 wt % in still another embodiment; and from about 35 wt % to about 70 wt % in yet another embodiment.
  • the low viscosity epoxy reactive diluent used in the curable composition of the present invention includes the low viscosity reactive diluent VER monomer composition prepared as described below.
  • the low viscosity VER monomer can be used as the sole reactive diluent.
  • the low viscosity VER monomer can be used in combination with one or more different conventional reactive diluent(s).
  • the curable resin composition of the present invention includes, as component (II), a vinyl ester resin (VER) monomer composition, i.e., as a reactive diluent.
  • a vinyl ester resin (VER) monomer composition i.e., as a reactive diluent.
  • the vinyl ester reactive diluent may be derived from, for example, the reaction product of: (A) an epoxy resin compound having a low viscosity (e.g., ⁇ 1,500 mPa-s at room temperature or about 25 °C); and (B) an unsaturated acid compound.
  • the VER monomer composition is useful as a reactive diluent for a curable resin composition such as an epoxy resin thermosetting resin composition.
  • the epoxy resin compound, component (A), i.e., the first component of the at least two-component VER monomer reactive diluent formulation or composition includes for example (a) at least one epoxy resin compound.
  • the epoxy compound, component (A), useful in preparing the VER monomer composition of the present invention may include, for example, any one or more conventional epoxy compounds.
  • the epoxy compound may be for example a single epoxy compound used alone; or a combination of two or more epoxy compounds known in the art such as any of the epoxy compounds described in Lee, H. and Neville, K., Handbook of Epoxy Resins, McGraw-Hill Book Company, New York, 1967, Chapter 2, pages 2-1 to 2-27, incorporated herein by reference.
  • the epoxy compound may include for example epoxy resins based on reaction products of polyfunctional alcohols, phenols, cycloaliphatic carboxylic acids, aromatic amines, or aminophenols with epichlorohydrin.
  • a few non-limiting embodiments include, for example, C12-C14 or C13-C15 alcohol glycidyl ether, ortho-cresol glycidyl ether, resorcinol diglycidyl ether, and triglycidyl ethers of para- aminophenols, cycloaliphatic epoxy resins (such as for example ERL 4221 commercially available from The Dow Chemical Company), divinylbenzene diglycidyl ether, and mixtures thereof.
  • ERL 4221 commercially available from The Dow Chemical Company
  • epoxy resins known in the art include for example reaction products of epichlorohydrin with o-cresol, p-tertial butylphenol, 2-ethylhexyl alcohol, butanediol, polypropylene glycol, hexanediol, cyclohexane dimethanol, neopentyl glycol, trimethylolpropane, polyglycerine, and mixtures thereof.
  • the epoxy compound useful in the present invention may also be selected from commercially available epoxy resin products such as for example, DER 721,
  • epoxy resins useful in the present invention can be selected from commercially available epoxy resins from Momentive such as HELOXYTM Modifier 107, HELOXY Z8, HELOXY KR, HELOXY AQ, CarduraTM Glycidyl Esters, and mixtures thereof.
  • Momentive such as HELOXYTM Modifier 107, HELOXY Z8, HELOXY KR, HELOXY AQ, CarduraTM Glycidyl Esters, and mixtures thereof.
  • Still other epoxy resins useful in the present invention can include for example epoxy compounds commercially available from Huntsman such as Araldite GY 298, Araldite DY-D, Araldite DY-G, Araldite DY-J, Araldite DY-K, Araldite DY-CNO, Araldite MY 721, Araldite MY 0510, Araldite MY 0610, Araldite CY 179, Araldite CY 184, Araldite CY 192, Araldite CY 9729, and mixtures thereof.
  • Araldite GY 298 Araldite DY-D, Araldite DY-G, Araldite DY-J, Araldite DY-K, Araldite DY-CNO, Araldite MY 721, Araldite MY 0510, Araldite MY 0610, Araldite CY 179, Araldite CY 184, Araldite CY 192, Araldite CY 9729, and mixtures thereof.
  • the above epoxy resins have a low viscosity generally in the range of less than about 2,000 mPa-s in one embodiment, less than about 1,500 mPa-s in another embodiment, less than about 1,200 mPa-s in still another embodiment, less than about 1,000 mPa-s in yet another embodiment, and less than 800 mPa-s in even still another embodiment.
  • the amount of epoxy resin used to prepare the VER monomer composition may be for example, from 40 wt % to about 95 wt % in one embodiment, from about 50 wt % to about 85 wt % in another embodiment; and from about 60 wt % to about 75 wt % in still another embodiment.
  • the unsaturated acid compound, component (B), useful for preparing the VER monomer composition of the present invention may include, but is not limited to, for example one or more of acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, sorbic acid, monomethyl maleate, monobutyl maleate, half esters of unsaturated dibasic acids, and mixtures thereof.
  • the above unsaturated acid compounds may be used alone or in combinations of two or more.
  • the amount of unsaturated acid used to prepare the VER monomer may include for example, from 60 wt % to about 5 wt % in one embodiment; from about 50 wt % to about 10 wt % in another embodiment; from about 40 wt % to about 15 wt % in still another embodiment; and from about 30 wt % to about 20 wt % in yet another embodiment.
  • the optional compounds that can be added to the composition for preparing the VER monomer of the present invention may include methacrylation agents, acrylation agents, polymerization initiators, catalysts, de-molding agents, accelerators, a solvent to lower the viscosity of the reactive diluent formulation further, other resins such as a phenolic resin that can be blended with the epoxy resin of the formulation, curing agents, fillers, pigments, toughening agents, flow modifiers, adhesion promoters, stabilizers, plasticizers, catalyst de-activators, flame retardants, and mixtures thereof.
  • the optional compounds that can be added to the composition for preparing the VER monomer of the present invention may include methacrylation agents, acrylation agents, polymerization initiators, catalysts, de-molding agents, accelerators, a solvent to lower the viscosity of the reactive diluent formulation further, other resins such as a phenolic resin that can be blended with the epoxy resin of the formulation, curing agents, fillers,
  • the amount of other optional components, when used in the present invention to prepare the VER monomer composition of the present invention may be for example, from 0 wt % to about 99.9 wt % in one embodiment; from about 0.01 wt % to about 99 wt % in another embodiment; from about 0.1 wt % to about 90 wt % in still another embodiment; from about 1 wt % to about 80 wt % in yet another embodiment; and from about 2 wt % to about 70 wt % in even still another embodiment.
  • the process for preparing the VER reactive diluent monomer of the present invention includes admixing and reacting (a) the epoxy compound described above; (b) the unsaturated acid described above, and (c) any optional ingredients as needed or desired.
  • the preparation of the VER monomer formulation of the present invention is achieved by blending, in known mixing equipment, an epoxy compound having a viscosity at 25 °C lower than about 2,000 mPa-s such as a diglycidyl ether of a polyetherpolyol, an unsaturated acid such a carboxylic acid, and optionally any other desirable additives.
  • an epoxy compound having a viscosity at 25 °C lower than about 2,000 mPa-s such as a diglycidyl ether of a polyetherpolyol
  • an unsaturated acid such a carboxylic acid
  • any of the above-mentioned optional additives may be added to the composition during the mixing or prior to the mixing to form the diluent composition
  • n is a number from 0 to 20; and “R” is hydrogen (H), an alkyl group of from CI to about C20 carbon atoms, an aromatic phenyl group, or a cycloaliphatic group.
  • the VER monomer composition of the present invention such as the above VER monomer illustrated as Structure (I) can be obtained for example by reacting (a) a low viscosity epoxy resin compound such as a diglycidyl ether of a polyether polyol with (b) an unsaturated acrylic acid such as a carboxylic acid.
  • a low viscosity epoxy resin compound such as a diglycidyl ether of a polyether polyol
  • an unsaturated acrylic acid such as a carboxylic acid.
  • the reaction step to manufacture VER monomer composition can be illustrated by the following general reaction Scheme (I) wherein the epoxy resin shown is a diglycidyl ether of a polyether polyol and the unsaturated acid is a carboxylic acid such as methacrylic acid:
  • All the compounds of the VER monomer reactive diluent composition are typically mixed and dispersed at a temperature enabling the preparation of an effective the reactive diluent having the desired balance of properties for a particular application.
  • the temperature during the mixing of the above reactive diluent components may be generally from about 10 °C to about 80 °C in one embodiment, from about 15 °C to about 50 °C in another embodiment, and from about 20 °C to about 40 °C in still another embodiment.
  • the preparation of the VER monomer reactive diluent of the present invention, and/or any of the steps thereof, may be a batch or a continuous process.
  • the mixing equipment used in the process may be any vessel and ancillary equipment well known to those skilled in the art.
  • the preparation of the final VER can be done in one step by blending together the different epoxy components such as bisphenol A or bisphenol F or multifunctional novolac based resins together with the low viscosity reactive diluents, followed by the reaction with the unsaturated acids to form a mixture of a low viscosity resin system which would only require a low styrene content to reach the required viscosity.
  • the different epoxy components such as bisphenol A or bisphenol F or multifunctional novolac based resins together with the low viscosity reactive diluents
  • the beneficial properties or characteristics of the VER monomer composition of the present invention include: (1) improved adhesion due to the presence of polar group (e.g., hydroxyl), (2) flexibility due to the aliphatic soft segment, and (3) higher vinyl functionality.
  • the VER monomer composition exhibits, for example, (4) a viscosity of less than about 2,000 mPa-s; and (5) a styrene content of less than about 30 wt %.
  • the low viscosity VER monomer can be used as the sole reactive diluent; or the low viscosity VER monomer can be used in combination with one or more different conventional reactive diluent(s).
  • the second or co-reactive diluent(s), different from the above-described low viscosity VER monomer of the present invention, useful in the curable resin composition of the present invention may include for example one or more of the compounds listed in Table I as follows:
  • the amount of reactive diluent used alone (i.e., without being used in combination with a second reactive diluent) in the curable resin composition may be for example, from 5 wt % to about 70 wt % in one embodiment; from about 10 wt % to about 65 wt % in another embodiment; from about 15 wt % to about 60 wt % in still another embodiment; and from about 20 wt % to about 55 wt % in yet another embodiment.
  • the curable composition of the present invention may include a mixture of two or more reactive diluents—the first reactive diluent being the low viscosity reactive diluent VER monomer composition of the present invention; and the second reactive diluent being the one or more different conventional reactive diluent(s) such as the reactive diluent(s) listed above in Table I.
  • the total amount of the combined reactive diluents used in the curable resin composition may be for example, from 5 wt % to about 70 wt % in one embodiment; from about 10 wt % to about 65 wt % in another embodiment; from about 15 wt % to about 60 wt % in still another embodiment; and from about 20 wt % to about 55 wt % in yet another embodiment.
  • the curable composition of the present invention may include other optional compounds such as a curing catalyst to speed up the curing process of curable composition.
  • the optional compounds that may be added to the curable composition of the present invention may include compounds that are normally used in resin formulations known to those skilled in the art for preparing curable compositions and thermosets.
  • the other optional compounds that may be added to the curable epoxy resin composition of the present invention may include additives generally known to be useful for the preparation, storage, application, and curing of epoxy resin compositions.
  • epoxy resin composition of the present invention may be added to epoxy resin composition of the present invention including, for example, one or more of the following compounds: inhibitors, solvents, pigments, fillers, leveling assistants, and the like, or mixtures thereof.
  • the solvent can be selected from, for example, ketones, ethers, aromatic hydrocarbons, glycol ethers, cyclohexanone, and combinations thereof.
  • one preferred embodiment of the curable composition of the present invention includes one or more of the following components: (1) a second reactive diluent different from the above VER monomer; (2) an unsaturated acid; (3) a vinyl monomer; (4) a curing agent (also referred to as a hardener or crosslinking agent); (5) an inhibitor; and/or (6) a catalyst.
  • the amount of optional component when used in the present invention, may be for example, from 0 wt % to about 40 wt % in one embodiment; from about 0.01 wt % to about 30 wt % in another embodiment; from about 0.1 wt % to about 20 wt % in still another embodiment; from about 1 wt % to about 15 wt % in yet another embodiment; and from about 2 wt % to about 10 wt % in even still another embodiment.
  • the curable resin formulation or composition of the present invention includes (I) at least one thermosetting resin forming the base resin or resin matrix of the composition; and (II) a VER monomer as a reactive diluent.
  • the VER monomer reactive diluent is formed separately and added into the thermosetting resin to form the curable composition.
  • the curable composition or formulation can include a mixture of: (I) at least one thermosetting base resin forming the resin matrix of the composition; (II) a reactive diluent; (III) an unsaturated acid; (IV) a vinyl monomer; and (V) optionally, other additives such as a catalyst.
  • thermosetting base resin can be one or more of (i) an epoxy resin
  • the amount of thermosetting base resin used in the composition may be for example, from 5 wt % to about 50 wt % in one embodiment; from about
  • the reactive diluent used in this alternative embodiment can be one or more of the reactive diluents described above including for example, component (II) the VER monomer reactive diluent, or any one or more of the reactive diluents listed in
  • the amount of reactive diluent used in the composition may be for example, from 5 wt % to about 50 wt % in one embodiment; from about 10 wt % to about 40 wt % in another embodiment; from about 15 wt % to about 35 wt % in still another embodiment; and from about 20 wt % to about 30 wt % in yet another embodiment.
  • the unsaturated acid useful in the composition of the present invention may include, but is not limited to, for example one or more of acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, sorbic acid, monomethyl maleate, monobutyl maleate, and half esters of unsaturated dibasic acids, and mixtures thereof.
  • the unsaturated acid may be used alone or in combinations of two or more.
  • the amount of unsaturated acid used in the composition may be for example, from 5 wt % to about 50 wt % in one embodiment; from about 10 wt % to about 40 wt % in another embodiment; from about 15 wt % to about 35 wt % in still another embodiment; and from about 20 wt % to about 30 wt % in yet another embodiment.
  • the vinyl monomer useful in the composition of the present invention may include, but are not limited to, for example one or more of vinyl monomers that are inert towards epoxide groups under the reaction conditions used in the process of the present invention, such as styrene, ring-chlorinated and -alkylated or -alkenylated styrenes, where the alkyl groups contain 1-4 carbon atoms such as vinyl-toluene, di vinyl-benzene, a-methyl-styrene, tert-butyl-styrene, and chlorostyrenes; vinyl esters of carboxylic acids with 2-6 carbon atoms such as vinyl acetate, -pyridine, -naphthalene, -cyclohexane, and acrylic acid esters and methacrylic acid esters without functional groups; allyl compounds such as allyl-benzene; allyl esters such as allyl acetate, phthalic acid-diallyl esters
  • the amount of vinyl monomer used in the composition may be for example, from 5 wt % to about 50 wt % in one embodiment; from about 10 wt % to about 40 wt % in another embodiment; from about 15 wt % to about 35 wt % in still another embodiment; and from about 20 wt % to about 30 wt % in yet another embodiment.
  • optional compounds may be added to the overall composition including for example a catalyst to facilitate the reaction process.
  • the catalyst useful in the present invention may include any one or more of the catalysts described above.
  • Other optional compounds that may be added to the composition of the present invention may include any one or more of the optional compounds that are normally used in resin formulations for a particular enduse application known to those skilled in the art such as those optional compounds described above.
  • the amount of optional component when used in the present invention, may be for example, from 0 wt % to about 10 wt % in one embodiment; from about 0.01 wt % to about 8 wt % in another embodiment; from about 0.1 wt % to about 6 wt % in still another embodiment; from about 0.5 wt % to about 4 wt % in yet another embodiment; and from about 1 wt % to about 2 wt % in even still another embodiment.
  • the process for preparing the curable composition of the present invention includes admixing (I) at least one thermosetting compound; (II) the VER monomer described above, and (III) optionally, other optional ingredients as needed.
  • the preparation of the curable resin formulation of the present invention is achieved by blending, in known mixing equipment, the thermosetting compound such as an epoxy compound, the VER monomer composition reactive diluent, and optionally any other desirable additives. Any of the above-mentioned optional additives may be added to the composition during the mixing or prior to the mixing to form the curable composition.
  • the temperature during the mixing of all components may be generally from about 0 °C to about 40 °C in one embodiment, from about 5 °C to about 35 °C in another embodiment, and from about 10 °C to about 30 °C in still another embodiment.
  • Lower mixing temperatures help to minimize reaction of the reactive group of the thermosetting resin and hardener in the composition to maximize the pot life of the composition.
  • the preparation of the curable formulation of the present invention, and/or any of the steps thereof, may be a batch or a continuous process.
  • the mixing equipment used in the process may be any vessel and ancillary equipment well known to those skilled in the art.
  • curable composition examples include for example, lower styrene emission, better flexibility, better impact resistance, better adhesion to fiber reinforcement, interlayer adhesion, smaller shrinkage, and other benefits described herein.
  • the curable composition is "styrene - free", i.e., has a styrene concentration of zero or at least as close to zero as possible.
  • the vinyl esters of the low viscosity resins of the present invention can be used and cured without any other co-reactive diluents such as styrene. This is one reason the styrene concentration can be zero or close to zero.
  • styrene is a readily available diluent and, in other embodiments, some concentration of styrene may be present in the curable composition.
  • the styrene concentration of the curable composition may be from 0 wt % to about 50 wt %, from 0 wt % to about 40 in still another embodiment, from 0 wt % to about 30 wt % in still another embodiment, and from 0 wt % to about 10 wt % in yet another embodiment, based on the weight of all the components in the curable composition.
  • the curable composition may have a styrene concentration of from about 0.1 wt % to about 50 wt %, from about 0.1 wt % to about 40 wt % in still another embodiment, from about 0.1 wt % to about 30 wt % in yet another embodiment, and from about 0.1 wt % to about 10 wt % in even still another embodiment, based on the weight of all the components in the curable composition.
  • the process of the present invention includes curing the curable resin composition to form a thermoset or cured composition.
  • the curable composition including the base thermosetting resin and the reactive diluent of the present invention can "self-cure", i.e., the composition can cure at a predetermined temperature and for a predetermined period of time without the aid of a curing agent added to the curable composition.
  • a curing agent can be added to the curable composition to aid in curing the composition.
  • the process of curing of the curable composition may be carried out at a predetermined temperature and for a predetermined period of time sufficient to cure the composition but the curing may be dependent on the hardeners used in the formulation.
  • the temperature of curing the formulation, with or without a curing agent may be from about 10 °C to about 200 °C in one embodiment; from about 100 °C to about 190 °C in another embodiment; and from about 125 °C to about 175 °C in still another embodiment.
  • the curing time for the process of curing the curable composition, with or without a curing agent may be chosen between about 1 minute to about 4 hours in one embodiment, between about 5 minutes to about 2 hours in another embodiment, and between about 10 minutes to about 1.5 hours in still another embodiment. Below a period of time of about 1 minute, the time may be too short to ensure sufficient reaction under conventional processing conditions; and above about 4 hours, the time may be too long to be practical or economical.
  • curable composition examples include for example a pultrusion process, a RTM process, an infusion process, a hand lay-up process, a filament winding process, and a RIM process; and other processes known in the art.
  • the cured product (i.e., the cross-linked product made from the curable composition) of the present invention shows several improved properties over conventional epoxy cured resins.
  • the cured product of the present invention may advantageously have a high glass transition temperature (Tg).
  • the cured product of the present invention exhibits a glass transition temperature generally between about 0 °C and about 200 °C in one embodiment, between about 40 °C and about 180 °C in another embodiment, between about 60 °C and about 160 °C in still another embodiment, and between about 80 °C and about 140 °C in yet another embodiment.
  • the Tg of the cured product can be measured by any method known to those skilled in the art such as for example a process described in
  • the curable composition of the present invention may be used to manufacture cured thermoset products such as composites, electronic materials, coatings, films, laminates, materials for marine applications, and coatings.
  • cured thermoset products such as composites, electronic materials, coatings, films, laminates, materials for marine applications, and coatings.
  • composites manufactured from the epoxy resin curable composition of the present invention exhibit a balance of advantageous properties including for example mechanical performance, electrical performance, and adhesion which make the composites ideal for use in automotive, wind blades, boats, leisure composites, insulation panels and other articles where such properties are useful.
  • MAA methacrylic acid
  • MEHQ stands for monomethyl ether of hydroquinone.
  • PTZ stands for phenothiazine
  • Tg glass transition temperature
  • DMP30 is tris-2,4,6-(dimethylaminomethyl) phenol commercially available from Air Product.
  • Hycat 3000S is a chromium(III) carboxylate commercially available from Dimension Technology Chemical Systems, Inc.
  • D.E.R.TM 732 is an epoxy resin having an EEW of 320 and commercially available from The Dow Chemical Company.
  • D.E.R.TM 736 is an epoxy resin having an EEW of 190 and commercially available from The Dow Chemical Company.
  • EEW epoxy equivalent weight
  • Viscosity is measured according to the following process described in
  • Solution 1 was added, by funnel drop by drop at 80 °C, into the reactor in 60 minutes (min). The temperature of the reactor was controlled below 110 °C during the addition of Solution 1 into the reactor. After addition of the Solution 1 to the reactor, MAA (124.67 g) was added, drop by drop, to the reactor during a period of another 2 hours (hr). The temperature of the reactor was kept below 115 °C. Additional MEHQ (0.29 g) was then added to the reactor and the temperature of the resultant solution was maintained below 115 °C for another 1 hr.
  • a sample of the resultant solution was taken from the reactor and the EEW of the sample was measured. If EEW of the sample was ⁇ 4,500, the above reaction was continued for another 30 min. If EEW of the sample was > 4,500, the temperature of the reactor was dropped to a temperature of below 85 °C and then the resultant resin product was taken out of the reactor.
  • the resultant resin product prepared according to the above procedure is a reactive diluent and referred to herein as "736- VER".
  • the reactive diluent 736-VER exhibits the following properties: an EEW of 7,166 and a viscosity @ 25 °C of
  • a sample of the resultant solution was taken from the reactor and the EEW of the sample was measured. If EEW of the sample was ⁇ 4,500, the above reaction was continued for another 30 min. If EEW of the sample was > 4,500, the temperature of the reactor was dropped to a temperature of below 85 °C and then the resultant resin product was taken out of the reactor.
  • the resultant resin product prepared according to the above procedure is a reactive diluent and referred to herein as "732- VER".
  • the reactive diluent 732-VER exhibits the following properties: an EEW of 4,684 and a viscosity @ 25 °C of 563 mPa-s. Examples 3 - 7 and Comparative Examples A - C - Viscosity of Various Blends
  • both 736- VER and 732-VER have a low viscosity and each of the resins can be used as a reactive diluent to at least partially replace some styrene which may present in a resin formulation when styrene is used as a diluent in the final resin composition.
  • a blend of a thermosetting resin and a reactive diluent is prepared by first heating VER 383 to a temperature of about 80 °C and then mixing the VER 383 with various reactive diluents as described in Table II. The resulting blend of components are mixed together at the concentration ratios described in Table II at room temperature with stirring for 30 min to obtain a homogeneous mixture. The viscosity of the homogeneous mixture is measured and summarized in Table II.
  • the viscosity of the blends containing VER-732 and VER-736 at 15 wt % is significantly higher than the reference system containing 30 wt % styrene (Comparative Example C)
  • the viscosity of the blends containing VER-732 and VER-736 is manageable and the viscosity can be further decreased with higher levels of styrene.
  • the VER of mono reactive diluents such as VER of DER 723 (glycidyl ether of o-cresol), of DER 727 (glycidyl ether of p-tert-butyl phenol), of DER 728 (glycidyl ether of 2ethylhexylalcohol), and of DER 721(glycidyl ether of C12-C14) will have a lower viscosity and better dilution effect for the VER resins.
  • VER of mono reactive diluents such as VER of DER 723 (glycidyl ether of o-cresol), of DER 727 (glycidyl ether of p-tert-butyl phenol), of DER 728 (glycidyl ether of 2ethylhexylalcohol), and of DER 721(glycidyl ether of C12-C14) will have a lower viscosity and
  • a partial acrylation and methacrylation of the above reactive diluents can provide a lower viscosity to a VER composition than a fully acrylation and methacrylation of VER.
  • These partial (me th) acrylation VERs can be used as a partial replacement for styrene. It is further theorized that the presence of a secondary hydroxyl group in the above VERs obtained from the reactive diluents can improve the adhesion of the VER
  • composition to reinforcing fibers for example, glass fibers, carbon fibers or other known fibers.

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Abstract

L'invention concerne une composition durcissable comprenant : (I) une résine thermodurcissable ; et (II) un diluant réactif, le diluant réactif comprenant le produit de réaction d'une composition monomère de résine d'ester vinylique de : (A) au moins un composé époxyde ayant une viscosité inférieure à environ 2 000 mPa-s à 25 °C ; et (B) un composé acide insaturé ; moyennant quoi la composition durcissable a une viscosité inférieure à environ 3 000 mPa-s à 25 °C. L'invention concerne également un procédé de préparation de ladite composition durcissable, et un article thermodurci préparé avec ladite composition durcissable.
PCT/US2015/052616 2014-10-28 2015-09-28 Composition durcissable WO2016069161A1 (fr)

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