WO2016176568A1 - Composition de durcisseur - Google Patents

Composition de durcisseur Download PDF

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Publication number
WO2016176568A1
WO2016176568A1 PCT/US2016/030084 US2016030084W WO2016176568A1 WO 2016176568 A1 WO2016176568 A1 WO 2016176568A1 US 2016030084 W US2016030084 W US 2016030084W WO 2016176568 A1 WO2016176568 A1 WO 2016176568A1
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Prior art keywords
amine
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composition
hardener composition
component
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PCT/US2016/030084
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English (en)
Inventor
Markus Schroetz
Marcus PFARHERR
Eva-Maria Michalski
Susanne Maier
Christina Fritsche
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Blue Cube Ip Llc
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Publication of WO2016176568A1 publication Critical patent/WO2016176568A1/fr

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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
    • C08G59/18—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
    • C08G59/182—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 using pre-adducts of epoxy compounds with curing agents
    • C08G59/184—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 using pre-adducts of epoxy compounds with curing agents with amines
    • 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
    • C08G59/40—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 curing agents used
    • C08G59/50—Amines
    • 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
    • C08G59/40—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 curing agents used
    • C08G59/50—Amines
    • C08G59/5006—Amines aliphatic
    • C08G59/502—Polyalkylene polyamines
    • 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
    • C08G59/40—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 curing agents used
    • C08G59/50—Amines
    • C08G59/5026—Amines cycloaliphatic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on 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
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/50—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing nitrogen, e.g. polyetheramines or Jeffamines(r)

Definitions

  • the present disclosure generally relates to hardener compositions
  • Epoxy resins are widely used for a variety of applications including coating formulations. Such coating formulations are used in various end uses such as for the protection of metal and concrete substrates; for flooring, potting, encapsulation applications; and similar end uses.
  • aminic adduct hardener formulations are used in epoxy resin based curable compositions to provide a curable coating compositions.
  • the aminic adduct hardener formulations contain up to 50 percent (%) monomeric amine.
  • the monomeric amine also lowers the viscosity of the hardener formulation.
  • VOCs volatile organic compounds
  • Benzyl alcohol is added to hardener formulations to reduce the viscosity of the formulation and improve the surface appearance of a cured system produced from a curable composition.
  • a non-reactive material or a modifier is also used in hardener formulation in amounts up to 75 %. These non-reactive materials such as nonylphenol reduce the viscosity of the hardener formulation and enhance the flexibility property of a cured system. However, these non-reactive materials adversely impact the mechanical properties of the cured system.
  • VOC-free formulations are known and are used primarily in waterborne hardener formulations. Examples of these VOC-free formulations are described in EP0995767 and EP1 136509.
  • the compositions of EP0995767 and EP1 136509 require polyalkylene oxide moieties in order to achieve homogeneity in the compositions in water. However, after water evaporation from the compositions, the polyalkylene oxide moieties will be present in an order of magnitude that will weaken the polymeric matrix. Furthermore, these weakened polymeric matrices reduce the chemical resistance of the coating made from the compositions.
  • WO201 1059500 also discloses curable coating compositions containing no VOCs.
  • Such compositions include an epoxy resin component, a Mannich base; and adducts of (1) epoxy compounds and (2) amines as hardeners.
  • WO2011059500 discloses coated articles made from the above curable coating compositions.
  • Mannich bases are conversion products of (alkyl) phenols with amines and formaldehyde. These conversion products can achieve a degree of chemical resistance.
  • these Mannich bases are labeled with exposure risk designated "risk phrase R 62" which corresponds to a "risk of impaired fertility” due to the presence of (alkyl) phenols in the coating compositions. Accordingly, it would be advantageous to provide a curable coating composition without the use of a Mannich base as disclosed in WO201 1059500 and provide lowered exposure risk and improved chemical resistance.
  • Adducts, distilled adducts, and the above-mentioned modifiers are also known in the art.
  • m-Xylylenediamine (MXDA)-adducts are disclosed in Vandezande et al., Epoxy Hardeners for 2K Systems, FATIPEC Congress (2010), 30th (Vol. 2), 620- 629; in Marks et al., ACS Applied Materials & Interfaces (2009), 1 (4), 921-926; and in Mirchandani, Girish, "Assessment of Relative Reactivities and Kinetics of Various Polyamines, and Polyamide Hardeners with Epoxy Resins for Designing High
  • EP1213312B1 discloses isolated (e.g., distilled) adducts of
  • EP1213312B1 does not teach the use of cresylglycidylether (CGE) or 2-methylpentamethylenediamine (MPMD) in such adducts.
  • CGE cresylglycidylether
  • MPMD 2-methylpentamethylenediamine
  • a hardener formulation wherein the hardener formulation exhibits a combination of desired beneficial properties including, but not limited to, (1) a low VOC content (e.g., about 0-5 g/L; according to the boiling point [b.p.] definition, a substance with a b.p. of less than [ ⁇ ] 250 °C is considered to be a VOC); (2) a low free amine content (e.g., ⁇ 20 weight percent [wt %]); (3) a low viscosity (e.g., ⁇ 1,500 mPa s at 25 °C); and (4) improved chemical resistance.
  • a low VOC content e.g., about 0-5 g/L; according to the boiling point [b.p.] definition, a substance with a b.p. of less than [ ⁇ ] 250 °C is considered to be a VOC
  • a low free amine content e.g., ⁇ 20 weight percent [wt %]
  • a low VOC, cold curing hardener compositions comprise four components: an adduct of a first amine compound and a polyfunctional epoxy compound (component A), an adduct of a second amine compound and a
  • component B monofunctional epoxy compound
  • component C a third amine adduct based on a polyalkylene oxide
  • component C a cycloaliphatic, aliphatic or araliphatic amine
  • curable compositions comprising at least one epoxy compound and at least one cold curing hardener wherein the curable composition has a low VOC content.
  • methods for preparing the cold curing hardener compositions comprise admixing the four components, component A, component B, and component C, and a modifier. Other additives known to the skilled artisan may also be added.
  • cured products prepared by curing the low viscosity, low VOC, curable composition.
  • Figure 1 is a graphical illustration showing the chemical resistance testing of a cured system comprising a combination of a hardener (Formulation #1 1) of the present invention and D. E. R.TM 3531 as the epoxy resin.
  • Figure 2 is a graphical illustration showing the chemical resistance testing of a cured system comprising a combination of another hardener (Formulation #12) of the present invention and D.E. R. 3531 as the epoxy resin.
  • Figure 3 is a graphical illustration showing the chemical resistance testing of a cured system comprising a combination of a hardener (Formulation #1) not of the present invention and D. E. R. 3531 as the epoxy resin.
  • Figure 4 is a graphical illustration showing the results of flexibility testing (E-modulus ⁇ E(b) [GPa] ⁇ ) of one of the Examples (Formulation #1 1) of the present invention: Formulation 1 1.
  • cold curing hardener compositions comprise four components; component A, component B, component C, and a modifier.
  • Component A comprises an adduct comprising at least one of a first amine and at least one polyfunctional epoxy compound having a monomeric amine content less than 20 wt%.
  • Component B comprises an adduct comprising at least one of a second amine and a monofunctional epoxy compound having a monomeric amine content less than 20 wt%.
  • Component C comprises an adduct of third amine based on a polyalkylene oxide.
  • the cold curing hardener composition and at least one epoxy resin compound provide a curable composition. After the curable compositions are applied and cured, the resulting coatings or thermosets have many beneficial aspects such as low volatile organic compound (VOC), enhanced flexibility, a shiny, undistorted, smooth appearance, improved chemical resistance, and an E modulus below 2.5 MPa.
  • VOC low volatile organic compound
  • the cold curing hardener composition comprises four components.
  • the cold curing composition has a monomeric amine content less than 20 wt%.
  • component A in the cold curing hardener composition comprises (a) at least one of a first amine compound; and (b) at least one polyfunctional epoxy compound, wherein the adduct has a monomeric amine content of less than about 20 weight %.
  • the first amine compound used in component A may include for example, m-xylylenediamine (MXDA), isophoronediamine (IPDA), diethylenetriamine (DETA), triethylenetetramine (TETA) trimethylpentamethylenediamine (TMD), and mixtures thereof.
  • MXDA m-xylylenediamine
  • IPDA isophoronediamine
  • DETA diethylenetriamine
  • TETA triethylenetetramine trimethylpentamethylenediamine
  • TMD trimethylpentamethylenediamine
  • the first amine compound may be MXDA.
  • MXDA may be sensitive to blushing, and may yield good chemical resistant coatings.
  • the concentration of the first amine compound may range generally from 10 wt % to about 90 wt %. In various embodiments, the concentration of the first amine compound may range from 10 wt% to about 90 wt%, from 20 wt % to about 80 wt %, from 25 wt % to about 75 wt %, or from 30 wt% to about 70 wt %. If a concentration is less than about 10 wt % of the amine compound, then the viscosity of the hardener formulation may be too high. If a concentration is greater than about 90 wt % of the amine compound, then the blushing may increase due to reaction of the monomeric amine with CCVwater from the air during the hardening reaction.
  • the polyfunctional epoxy compound in component A may include, for example, adducts of liquid epoxy resins (LER).
  • the LERs may include for example bisphenol A diglycidyl ether (BADG E); bisphenol F diglycidyl ether (BFDGE); low (e.g., ⁇ 500-800 g/mole) molecular weight (MW) novolacs; and mixtures thereof.
  • the adduct hardener composition may include BADG E such as D.E. R. 331 and D. E. R. 330, epoxy resins commercially available from The Dow
  • composition may be based on D.E. R. 331 because this polyfunctional epoxy compound exhibits a higher viscosity and a higher EEW (e.g., in comparison to D.E. R. 330), but produces a slightly lower viscous adduct (e.g., at a fixed rate epoxy/amine) due to less epoxy groups by weight.
  • the concentration of the polyfunctional epoxy compound may range generally from 10 wt % to about 90 wt %. In various embodiments, the concentration of the polyfunctional epoxy compound used in component A may range from 10 wt% to 90 wt%, from 20 wt% to 80 wt%, from 25 wt% to 75 wt%, or from 30 wt% to 70 wt%.
  • the resultant composition will exhibit a high viscosity (e.g., 50,000 mPa s at 25 °C).
  • component B second amine adduct
  • Component B in the cold curing hardener composition comprises a second amine compound and a monofunctional epoxy compound wherein the adduct has a monomeric amine content of less than about 20 weight %. (i) . second amine compound
  • the second amine compound used in component B may include any of the same amines described above with reference to the first amine.
  • all distillable amines known in the art e.g., amines which are distillable at moderate conditions such as 200 °C and 5 mbar.
  • the second amine compound may be methylpentamethylenediamine (MPMD). MPMD produces adducts (e.g., at a given ratio of epoxy to amine) with the lowest viscosity.
  • the concentration of the second amine compound may range generally from 10 wt % to about 90 wt %.
  • the concentration of the first amine compound may range from 10 wt% to about 90 wt%, from 20 wt % to about 80 wt %, from 25 wt % to about 75 wt %, or from 30 wt% to about 70 wt %. based on the total weight of the components in the hardener composition.
  • the monofunctional epoxy compound may include any glycidyl ether (GE).
  • glycidyl ethers may be o-cresylglycidyl ether (CGE), para-tert- butylphenylglycidylether, a mixture of glycidyl ethers such as a mixture of (i) a 1- dodecanol (C12 alkyi) glycidylether and (ii) a 1-tetradecanol (C14 alkyi) glycidylether (C12/C14 alkyi GE mixture), 1,4 butandiolglycidylether (BDDG E), 1,6- hexandiolglycidylether (HDDGE), a C12 to C14-alky glycidylether, 2-ethylhexyl glycidylether; and mixtures thereof.
  • CGE o-cresylglycidyl ether
  • the monofunctional epoxy compound can be for example CGE.
  • CGE is monofunctional; and therefore, CGE produces per se lower viscous adducts (e.g., compared to D.E. R. 331 or other epoxy resin compounds).
  • CGE has an aromatic backbone, (e.g., similar to D.E. R. 331 ); and therefore, the chemical resistance of a coating cured with an adduct containing CGE can be increased.
  • the concentration of the monofunctional epoxy compound may range generally from 10 wt % to about 90 wt %. In various embodiments, the
  • concentration of the first amine compound may range from 10 wt% to about 90 wt%, from 20 wt % to about 80 wt %, from 25 wt % to about 75 wt %, or from 30 wt% to about 70 wt %. based on the total weight of the components in the hardener composition.
  • the objective of the reaction mixture is to obtain a 1 : 1 mole:mole adduct between the second amine compound and the monofunctional epoxy compound. Therefore, 2 moles of amine are reacted with 1 mole of the monofunctional epoxy compound.
  • the excess of 0.2 to 1 mole of the second amine is removed by distillation, and the residual monomelic amine content of the composition is below about 2 wt %. If the reaction mixture contains a mole ratio below 1 : 1, then more higher adducts of type (CGE)x-(MPMD)1 , for x > 1 are formed which are undesirable. If the reaction mixture contains a mole ratio above 1 : 1 , then an undesirable increased amount of amine is required to be distilled from the reaction mixture.
  • component C third amine adduct
  • the third amine adduct, Component C may be based on a polyalkylene oxide, a cycloaliphatic, aliphatic, araliphatic amine, or a combination thereof.
  • component C may be a polyoxyalkylene amine such as Jeffamine D-230 and Jeffamine D-400 which are commercially available from Huntsman. These polyoxyalkylene amines assist in improving the flexibility and the surface appearance of the cured product.
  • the concentration of Component C, the third amine adduct, used in the cold curing hardener composition may range generally from 1 wt % to about 20 wt %. In various embodiments, the concentration of Component C may range from 1 wt% to about 20 wt%, from 1 wt % to about 15 wt % from 1 wt % to about 10 wt % and from 2 wt % to about 5 wt % based on the total weight of the components in the hardener composition. When Component C is used beyond 20 wt %, the chemical resistance of the coating made using the hardener is lowered. Conversely, if
  • Component C is used at a concentration of less than 1 wt %, the composition exhibits a high viscosity.
  • the cold curing hardener composition may use a high boiling point modifier (b.p. > 250 °C, no VOC) which is compatible with the epoxy and amine mixture.
  • high boiling modifiers may include styrenated phenol, diisopropylnaphthaline (Dl), and mixtures thereof.
  • the high boiling modifier compound may be Dl since Dl works well in terms of compatibility with the amines, adducts of amines, the epoxy resin, and the cured system.
  • the concentration of the high boiling modifier compound used in the cold curing hardener composition may range from 1 wt % to about 50 wt %. In various embodiments, the concentration of the high boiling point modifier may range from 1 wt% to 50 wt%, from 5 wt % to about 40 wt %, from 10 wt % to about 30 wt %, and from 15 wt % to about 25 wt % based on the total weight of the components in the hardener composition. When the high boiling modifier compound is used beyond 50 wt %, the mechanical properties of the coating produced using the modifier are lowered. Conversely, if the modifier is used at a concentration of less than 1 wt %, the modifier is used at a concentration of less than 1 wt %, the concentration of the high boiling point modifier may range from 1 wt% to about 50 wt %. In various embodiments, the concentration of the high boiling point modifier may range from 1 wt% to 50 wt%, from 5
  • composition exhibits a high viscosity.
  • an optional additive may be added to the cold curing hardener composition.
  • optional additives may be an accelerator such as salicylic acid, 2,4,6-tris(N,N,-dimethylamino)phenol (e.g., DMP-30), or mixtures thereof.
  • the concentration of the optional additives may range from 0 wt % to about 5 wt %. In various embodiments, the concentration of the optional additives may range from 0 wt% to 5 wt%, from 0.1 wt % to about 2.5 wt %, and from 0.1 wt % to about 1 wt %.
  • the cold curing hardener composition before curing may be a liquid.
  • the viscosity of the cold curing hardener composition may range from 100 mPa s to about 1500 m Pa s at 25°C. In various embodiments, the viscosity of the cold curing hardener composition may range from 100 m Pa s to about 1500 mPa s at 25°C, from 200 mPa s to about 1 ,400 m Pa s at 25°C; from 300 mPa s to about 1 ,300 m Pa s at 25° C; and from 400 mPa s to about 1 ,200 mPa s at 25° C.
  • the cold curing hardener composition advantageously has no VOC content or a low VOC content (according to the > 250 °C boiling point definition).
  • the content of non-reactive material in the cold curing composition may range from 1 wt % to about 50 wt %. In various embodiments, the content of non- reactive material may range from 1 wt % to about 50 wt %, from about 5 wt % to about 40 wt %; and from about 10 wt % to about 30 wt %.
  • the content of the free amine in the cold curing hardener composition may range from 1 wt % to about 20 wt %. In various embodiments, the content of the free amine may range from 1 wt% to 20 wt%, from 5 wt % to about 20 wt %, and from 10 wt % to about 20 wt %.
  • curable composition comprising (I) at least one epoxy resin and (II) the cold curing hardener described above.
  • Other optional additives (III) may be added to the curable compositions.
  • the curable composition using the cold curing hardener composition includes at least one epoxy resin compound.
  • the epoxy resin compound, component (I) may be any conventional epoxy resin compound.
  • the epoxy resin may be a single epoxy resin compound or a mixture of two or more epoxy compounds used in combination, i.e., component A of the curable epoxy resin coating composition which is cured to form the coating material of the present invention includes at least one epoxy resin.
  • Non-limiting examples of the at least one epoxy resin may include aliphatic epoxy resins, cycloaliphatic epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, phenol novolac epoxy resins, cresol-novolac epoxy resins, biphenyl epoxy resins, polyfunctional epoxy resins, naphthalene epoxy resins, divinylbenzene dioxide, 2- glycidylphenylglycidyl ether, dicyclopentadiene-type epoxy resins, phosphorous containing epoxy resin, multi aromatic resin type epoxy resins, and mixture therefore.
  • Other non-limiting examples of the at least one epoxy resin may include
  • halogen for example, chlorine or bromine
  • Suitable commercially available epoxy resin compounds may include D.E. R.TM 300 series, the D.E.N.TM 400 series, the D. E. R.TM 500 series, the D.E. R.TM 600 series and the D. E.R.TM 700 series of epoxy resins commercially available from The Dow Chemical Company.
  • Other non-limiting examples of epoxy resins may include liquid epoxy resins (LERs), such as D.E. R. 331 (a bisphenol A diglycidyl ether,
  • D.E. R. 354 (a bisphenol F diglycidyl ether), D. E. R. 324 (a diluent modified epoxy resin), other low viscosity epoxy resin blends, and other well-known epoxy resins and blends or mixtures of the above known epoxy resins.
  • D.E. R. 324, D. E. R. 330, D.E. R. 331 , D. E. R. 332, and D. E. R. 354 are commercially available epoxy resins from The Dow Chemical Company.
  • Other commercially available epoxy resin compounds may include for example BADG E with a MW ⁇ 700.
  • the at least one epoxy resin compound useful in the present invention may include a liquid epoxy resin, such as D. E. R. 331 a diglycidylether of bisphenol A (DGEBPA) having an epoxide equivalent weight of from about 170 to about 190 a viscosity of about 10 Pa-s and a density of about 1.2 g/cc.
  • the cold curing hardener compound, component (II), (also referred to as a curing agent or crosslinking agent) can be selected from one or more of the cold curing hardener compositions described above.
  • an equivalent ratio of the epoxy resin compound (I) to the hardener composition (II) is sufficient to form a coating or a thermoset.
  • the equivalent ratio of the epoxy resin (I) to the hardener composition (II) such that the epoxy/hardener is in a ratio of 1 epoxy -equivalent to 1 amine-equivalent.
  • the epoxy-equivalent to amine-equivalent ratio may be generally from about 1: 1 to about 1 :0.9, or from about 1 : 1 to about 1 : 1.1. The use of any concentration outside the above ranges may weaken the network formed.
  • Non- limiting examples of the other optional compounds or additives may include dispersant additives; deformer additives; flowing additives; catalysts; solvents; fillers; pigments; toughening agents; flexibilizing agents, processing aides; flow modifiers; adhesion promoters; diluents; stabilizers; plasticizers; catalyst de-activators; flame retardants; aromatic hydrocarbon resins, coal tar pitch; petroleum pitch; carbon nanotubes;
  • the amount of the optional compounds or additives may be from 0 wt % to about 5 wt %. In various embodiments, the amount of the optional compounds or additives may be from 0 wt % to about 5 wt %, from 0.1 wt % to about 2.5 wt %, and from 0.1 wt % to about 1 wt %. (d). properties of the curable composition
  • the curable composition exhibits a low viscosity sufficient to allow the curable composition to be easily processed and handled in conventional formulation equipment.
  • the curable composition prepared by the above process advantageously exhibits a low viscosity of less than or equal to about 5,000 mPa s at 25°C.
  • the viscosity of curable composition may be from 500 mPa s to about 5,000 mPa s, from 1,000 mPa s to about 4,000 mPa s in, and from 2,000 mPa s to about 2,500 mPa s at 25°C.
  • the curable composition with a viscosity of greater than about 5,000 mPa s leads to bad de-aeration which in turn leads to the formation of bubbles in the composition.
  • curable composition capable of being cold cured at a temperature of less than room temperature, i.e., from about 10°C to 25°C to form a thermoset; and a curable composition capable of being cured at efficient curing speeds (for example a curable composition that cures within hours at room temperature and at 13°C).
  • the curing temperature of the curable composition may range from 0°C to about 50°C.
  • curing temperature of may range from 0°C to about 50°C, from 5°C to about 40°C, and from 10°C to about 30°C. If the temperature of cure is below about 0 °C, the curing speed may be too low; and if the temperature of cure is above 50 °C, the curing speed may be too fast for reaction control.
  • One embodiment includes curing the curable composition discussed above to form a cured product such as a coating or a thermoset.
  • the 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 to form a cured coating material.
  • the processes for preparing the above described cold curing hardener composition generally includes the steps of preparation of each component; preparation of component A then removing the excess monomeric amine by distillation, preparation of component B then removing the excess monomeric amine by distillation, and component C. These components, A, B, and C, are admixed (mixed) together with the modifier and optional additives.
  • Component A is prepared by admixing the first amine compound (a)(i) and polyfunctional epoxy compound (a)(ii) at a temperature from 70°C to about 90°C. The excess monomeric amine is removed from the reaction mixture by vacuum distillation (for example at 200 °C and 5 mbar).
  • Component B is prepared by admixing the second amine compound (b)(i) and the monofunctional epoxy compound (b)(ii). The excess monomeric amine is removed from the reaction mixture by vacuum distillation (for example at 200 °C and 5 mbar).
  • the curable composition comprising the components, A, B, and C, may be mixed with the modifier and any other desired optional additive at a temperature of from about 20° C to about 100°C.
  • the preparation of the curable composition of the present invention may be achieved by blending, in known mixing equipment, the first amine adduct, component A, the second amine adduct, component B, and the third amine adduct, component C, and the modifier. These components may be admixed in a sequential order, in a random order, or sequentially. 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.
  • All the compounds used in preparing the curable composition are typically mixed and dispersed at a temperature enabling an effective curable composition having the desired balance of properties for a particular application.
  • the temperature during the mixing of all components may be generally from about 20°C to about 100°C.
  • the temperature during the mixing may range from 20°C to about 100°C, from 30°C to about 90°C, from 40°C to about 80°C, or from 50°C to about 70° C.
  • the preparation of cold curing hardener composition 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 curable composition is produced by first admixing, blending or mixing: (I) the epoxy resin described above, and (II) at least one of the cold curing hardener compounds described above; and then heating the mixture at a temperature sufficient to mix the components and produce a curable coating composition, which can subsequently be cured by heating.
  • the curable composition may include any one or more of the optional additives (III) as desired and as described above.
  • the preparation of the composition may be achieved by blending, in known mixing equipment, (I) at least one epoxy resin; and (II) at least one of the cold curing hardener compounds described above; and optionally (III) 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.
  • All the compounds of the composition are typically mixed and dispersed at a temperature enabling the preparation of an effective curable composition having the desired balance of properties for a particular application.
  • the temperature during the mixing of all components may be generally from about 0 °C to about 50 °C in one embodiment, and from about 0 °C to about 30 °C in another embodiment.
  • the preparation of curable composition 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.
  • Another aspect of the present disclosure provides processes for preparing a cured composition.
  • the processes comprise providing a curable composition, which is detailed above, and exposing the curable composition to heat to form the cured coating.
  • the curable is applied to at least a portion of a surface of an article to be coated, prior to subjecting it to heat for curing.
  • an article comprising a cured or uncured curable composition adhering to at least one portion of the substrate.
  • the article in broad terms, may be defined as a material wherein the curable composition is initially applied and adheres to at least a portion of at least one surface of the substrate.
  • the curable epoxy resin composition may be cured at a exposing the composition to heat to form a therm oset or cured composition such that the coating bonds to the substrate.
  • the article may be any material that can withstand the curing temperature to form a cured coating.
  • the article may be a metal.
  • the article, as defined herein, may be a single metal or an alloy of various metals.
  • Non-limiting examples of these metals include cast iron, aluminum, tin, brass, steel, copper, zinc aluminum alloy, nickel, or combinations thereof.
  • the substrate may be a cellulose product.
  • cellulose products may be paper, paperboard, paper cardstock, cardboard, and wood.
  • the substrate may be a plastic.
  • plastics may be bakelite, polyester, polyethylene terephthalate, polyethylene, high density polyethylene, polyvinyl chloride, polyvinylidene chloride, polypropylene, polystyrene, polyamides (Nylon), acrylonitrile butadiene styrene, polycarbonates, polyurethanes, and combinations thereof.
  • the article may be a stone.
  • stones may be granite, brick, limestone, concrete, and combinations thereof.
  • the article may be flooring.
  • flooring may be cement, acrylic flooring, vinyl flooring, laminate flooring, wood flooring, ceramic tile, and linoleum.
  • the article may be in various configurations.
  • Non-limiting configuration examples of the article may be a roll, a coil, a plate, a sheet, a tube, a brick, a slab, a boulder, or a pipe.
  • the configuration of the article may be of various dimensions, shapes, thicknesses, and weights.
  • the process further comprises applying the curable composition to a portion of at least one surface of an article.
  • Suitable articles are detailed above.
  • the coating composition may be applied through various means.
  • the coating composition may be applied using a drawdown bar, a roller, a knife, a paint brush, a sprayer, dipping, or other methods known to the skilled artisan.
  • the curable coating composition may be applied to one or more surfaces of the article to be coated.
  • the process further comprises curing the curable epoxy resin composition to a portion of at least one surface of an article.
  • the curable composition as detailed herein, may be cured by exposing the composition to heat to form a cured composition or therm oset.
  • the process for producing the cured coating material includes carrying out the curing reaction at process conditions to enable the preparation of an effective cured material having the desired balance of properties for a particular application, particularly for forming the coating product.
  • the temperature for curing the curable composition may range from -10°C to about 50°C. In various embodiments, the temperature for curing may range from -10°C to about 50°C, from -5°C to about 50°C, from 0°C to about 45°C, and from 5°C to about 40°C.
  • the curing time can and will vary. In various embodiments, the curing time to may range from 0.1 hour to about 7 days, from 0.5 hours to about 1 day, and from 1 hour to about 6 hours.
  • the preparation of the cured coating material and/or any of the steps thereof, may be a batch or a continuous process.
  • the equipment employed to carry out the reaction includes equipment known to those skilled in the art.
  • Non-limiting examples of end use products of the cured composition may include coatings, lacquer paints, potting, encapsulation applications, flooring, thermosets, and primers.
  • thermoset product prepared by curing the above curable
  • composition containing the hardener composition exhibits unexpected and unique properties.
  • the cured thermoset product such as a coating exhibits enhanced flexibility; a shiny, undistorted, smooth surface when cured at room
  • thermoset produced from a curable composition containing the hardener composition exhibits at least "medium” chemical resistance (3 days in the cotton pad test); and E modulus below 2.5 MPa.
  • the cured coating (i.e. the cross-linked coating product made from the curable composition) shows several improved and beneficial performance properties over conventional cured coating products made from conventional curable compositions containing conventional curing agents.
  • the cured composition may exhibit increased flexibility.
  • the cured coating may exhibit a flexibility property generally between 1 and 2.5. In various embodiments, flexibility property may be range from 1 to about 2.5, from 1.2 to about 2.2, and from 1.5 to about 2.
  • the flexibility properties of the cured coating material can be determined using a 3-point bending test according ATSM D 790.
  • the cured coating may also advantageously exhibit good surface appearance. In general, the cured coating may exhibit a surface appearance property generally from fair to good, from good to medium, and from medium to about fair. The surface properties of the cured coating material can be determined by visual inspection.
  • the cured coating may also advantageously exhibit at least "medium” (3 days cotton pad testing, "good” is 7 days) chemical resistance.
  • the cured coating of the present invention exhibits a chemical resistance property from "medium to good”.
  • the chem ical resistance properties of the cured coating material can be measured using a cotton pad testing method.
  • the cured product may also exhibit improved chem ical resistance compared to other cured products not util izing the cold curing hardener composition.
  • the percent change in Shore D hardness was determined with the initial hardness and the final hardness after 168 hours of exposure to the solutions.
  • the percent change in Shore D hardness was calculated as (1 - (final hardness/initial hardness))*100, where a negative percent change in hardness indicated a greater value for initial hardness than final hardness.
  • Elongation or "tensile elongation,” as used herein, refer to a mechanical property of a polymer to deform or change shape when under tensile stress. When a polymer sample deforms by stretching, it becomes longer. Elongation is typically expressed as percent (%) elongation, which is the length of the polymer sample after it is stretched (L), divided by the original length of the sample (Lo), and then multiplied by 100. Elongation at yield refers to the point at which an increase in stress does not result in an increase in length. "Elongation at break” corresponds to the point of rupture.
  • the "glass transition temperature” is the temperature at which a polymer transitions from a hard, glassy material to a soft, rubbery material.
  • the "cold crystallization temperature” is the temperature at a polymer crystallizes.
  • tensile modulus or “Young's modulus” refer to the stiffness of a material, and are used to describe the elastic properties of the material. Tensile modulus is defined as the ratio of stress (force per unit area) along an axis to strain (ratio of deformation over initial length) along that axis.
  • tensile strength at break refers to the tensile stress at the moment at which a test sample breaks. Tensile strength is the force placed on the test sample divided by the cross-sectional area of the sample.
  • low volatile organic compounds (VOC) content refers to a composition with 0-5 g/L of VOC in the hardener composition.
  • low free amine content refers to a composition with less than 20 wt % of free amine in the hardener composition.
  • low viscosity refers to a composition with less than 1,500 mPa s at 25°C for the viscosity of the hardener composition.
  • cold curing refers to a temperature of curing in the range of about 0°C to about 50°C.
  • good surface appearance refers to a composite with a shiny, glossy, undistorted, light yellowish, no whitening or blushing/blooming surface of a composite.
  • fair surface appearance refers to a composite with a slightly distorted with a bit of blushing, silk-mate surface of a composite.
  • thermoset or composite where a cured material can withstand at least for 3 days in a cotton pad chemical testing procedure without deterioration.
  • the term "flexibility” refers to a composite with an E-Modulus of ⁇ about 2.5 GPa of a composite.
  • alkyl as used herein describes saturated hydrocarbyl groups that contain from 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and most preferably 1 -10 carbon atoms. They may be linear, branched, or cyclic, may be substituted as defined below, and include methyl, ethyl, propyl, isopropyl, butyl, hexyl, heptyl, octyl, nonyl, and the like.
  • alkenyl as used herein describes hydrocarbyl groups which contain at least one carbon-carbon double bond and contain from 1 to 30 carbon atoms. They may be linear, branched, or cyclic, may be substituted as defined below, and include ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, hexenyl, and the like.
  • alkoxide or "alkoxy” as used herein is the conjugate base of an alcohol.
  • the alcohol may be straight chain, branched, cyclic, and includes aryloxy compounds.
  • alkynyl as used herein describes hydrocarbyl groups which contain at least one carbon-carbon triple bond and contain from 1 to 30 carbon atoms. They may be linear or branched, may be substituted as defined below, and include ethynyl, propynyl, butynyl, isobutynyl, hexynyl, and the like.
  • aromatic as used herein alone or as part of another group denotes optionally substituted homo- or heterocyclic conjugated planar ring or ring system comprising delocalized electrons. These aromatic groups are preferably monocyclic (e.g., furan or benzene), bicyclic, or tricyclic groups containing from 5 to 14 atoms in the ring portion.
  • aromatic encompasses "aryl” groups defined below.
  • aryl as used herein alone or as part of another group denote optionally substituted homocyclic aromatic groups, preferably monocyclic or bicyclic groups containing from 6 to 10 carbons in the ring portion, such as phenyl, biphenyl, naphthyl, substituted phenyl, substituted biphenyl, or substituted naphthyl wherein "substituted" substituents include moieties in which a carbon chain atom or carbon atoms is (are) substituted with a heteroatom such as nitrogen, oxygen, silicon, phosphorous, boron, or a halogen atom, and moieties in which the carbon chain comprises additional substituents.
  • substituents include alkyl, alkoxy, acyl, acyloxy, alkenyl, alkenoxy, aryl, aryloxy, amino, amido, acetal, carbamyl, carbocyclo, cyano, ester, ether, halogen, heterocycio, hydroxyl, keto, ketal, phospho, nitro, and thio.
  • hydrocarbon and “hydrocarbyl” as used herein describe organic compounds or radicals consisting exclusively of the elements carbon and hydrogen.
  • moieties include alkyl, alkenyl, alkynyl, and aryl moieties. These moieties also include alkyl, alkenyl, alkynyl, and aryl moieties substituted with other aliphatic or cyclic hydrocarbon groups, such as alkaryl, alkenaryl and alkynaryl. They may be straight, branched, or cyclic. Unless otherwise indicated, these moieties preferably comprise 1 to 20 carbon atoms.
  • substituted hydrocarbyl moieties described herein are hydrocarbyl moieties which are substituted with at least one atom other than carbon or hydrogen, including moieties in which a carbon chain atom is substituted with a heteroatom such as nitrogen, oxygen, silicon, phosphorous, boron, or a halogen atom, and moieties in which the carbon chain comprises additional substituents.
  • substituents include alkyl, alkoxy, acyl, acyloxy, alkenyl, alkenoxy, aryl, aryloxy, amino, amido, acetal, carbamyl, carbocyclo, cyano, ester, ether, halogen, heterocycio, hydroxyl, keto, ketal, phospho, nitro, and thio.
  • a MXDA adduct is prepared which can be generally described as 4,4'-isopropylidenediphenol, oligom eric reaction products with 1-chloro- 2,3-epoxypropane, reaction products with m-phenylenebis(methylamine) in accordance with the following general procedures:
  • Part B Larger Scale
  • 600 g of the amine (MXDA) was placed in a flask with a heating jacket; the amine was stirred; and while being stirred the amine was heated to a temperature of 80°C.
  • the epoxy compound 400 g (D. E. R. 331) was then added to the flask from above. The epoxy compound was added to the flask at a rate of addition sufficient to maintain the temperature at about 80-90°C. If necessary, the flask was cooled by removing the heating jacket. After addition of the epoxy compound, a post-reaction was performed for at least 25 min at the reaction temperature of 80°C.
  • the hardeners were mixed with a D.E. R. 3531, a diluted epoxy resin which is a blend of bisphenol A epoxy resin, bisphenol F epoxy resin with a mixture of dodecanol and tetradecanol mono glycidyl ether as a reactive diluent at 1 epoxy equivalent to 1 amine equivalent at room temperature to yield a curable composition.
  • the above hardener/epoxy resin curable composition was then cured at a curing temperature of 13°C and 23° C.
  • the water drop test was performed as follows: a water drop is placed on the not fully cured surface of a thermoset substrate, and the water evaporates leaving white carbamates on the surface of the thermoset. If the water does not evaporate leaving white carbamates on the surface of the non-fully cured thermoset, the hardener is insensitive to the water drop, which is desired.
  • the films were tested by exposing the films to different test liquid solutions for 7 days (168 hr) by placing a cotton pad that is saturated with the solution on the sample and covering the pad and sample with a plastic lid. After 1 day (24 hr) of exposure, 2 days (48 hr) of exposure, and 7 days (168 hr) of exposure, the Shore D hardness of each of the samples was measured according to the procedure described in ASTM D2240. The Shore D hardness measurements are shown in Figures 1 and 2, and the percent change in Shore D hardness, as shown as percent delta (% A), was determined by measuring the initial hardness and the final hardness after 168 hr of exposure to the solutions. The percent change in Shore D hardness was calculated using the following equation: (1 - [final hardness/initial hardness])*100; where a negative percent change in hardness indicated a greater value for initial hardness than a value for final hardness.
  • test liquids used in the chemical resistance comparisons were acetic acid, sulfuric acid, sodium hydroxide, gasoline, Bau- und Prditionsatze civil 5b (B. P.G. 5b), xylene, and methylisobutyl ketone (MIBK).
  • the specific compounds used for testing included the follows:
  • acetic acid, sulfuric acid, and sodium hydroxide were of analytical grade and are commercially available from Merck KGaA.
  • Bau- und Prditional Art 5b of the DIBT (Policy for Construction and Testing Group 5b of the German Institute for Construction Technique) (hereinafter designated as "B.P.G. 5b") is a mixture of 48 volume percent methanol, 48 volume percent isopropanol, and 4 volume percent water.
  • the methanol and isopropanol used were of analytical grade and commercially available from Merck KGaA.
  • the gasoline used for testing is commercially available from Esso (Exxon).
  • MIBK methylisobutyl ketone
  • Hardeners were produced by (physical) mixing/blending, at 23°C.
  • the ingredients in the formulations used in Examples 5-12 (Formulation #5-#12) of the present invention and in Comparative Examples 1-4 (Formulations #1-#4) are described in Table II.
  • IPD Isophoronediamine
  • TMD Trimethylhexamethylenediamine 3 2 3
  • Mass hardener (g) 12 12 12 12 12 12 12
  • thermoset
  • thermoset
  • compositions #4 to #12 are the most efficient composition.

Abstract

La présente invention concerne des compositions de durcisseur avec durcissement à froid comprenant : un composant A, au moins un adduit d'un premier composé aminé et d'au moins un composé époxy polyfonctionnel ; un composant B, au moins un adduit d'un deuxième composé aminé et d'au moins un composé époxy monofonctionnel ; un composant C, au moins un adduit d'un troisième composé aminé basé sur un poly(oxyde d'alkylène) ; sur une amine cycloaliphatique, aliphatique ou araliphatique ; et un modificateur, les compositions de durcisseur possédant une faible teneur en COV, une faible teneur en amines libres et une faible viscosité. Les compositions durcissables comprennent (a) au moins une résine époxy et (b) au moins une des compositions de durcisseur avec durcissement à froid ci-dessus. L'invention concerne également des procédés pour préparer les compositions de durcisseur et les compositions durcissables.
PCT/US2016/030084 2015-04-30 2016-04-29 Composition de durcisseur WO2016176568A1 (fr)

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