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WO2018146670A1 - Adhésifs structuraux et composites comprenant des époxydes bromés - Google Patents

Adhésifs structuraux et composites comprenant des époxydes bromés Download PDF

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Publication number
WO2018146670A1
WO2018146670A1 PCT/IL2017/051384 IL2017051384W WO2018146670A1 WO 2018146670 A1 WO2018146670 A1 WO 2018146670A1 IL 2017051384 W IL2017051384 W IL 2017051384W WO 2018146670 A1 WO2018146670 A1 WO 2018146670A1
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WO
WIPO (PCT)
Prior art keywords
curing agent
epoxy
epoxy component
brominated
mixture
Prior art date
Application number
PCT/IL2017/051384
Other languages
English (en)
Inventor
Hanna Dodiuk-Kenig
Samuel Kenig
Maria SHEINBAUM
Lizzie SHEINBAUM
Orli WEIZMAN
Shay DICHTER
Eyal EDEN
Original Assignee
Bromine Compounds Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bromine Compounds Ltd. filed Critical Bromine Compounds Ltd.
Publication of WO2018146670A1 publication Critical patent/WO2018146670A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives 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
    • 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
    • C08G59/20—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 epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
    • C08G59/308—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing halogen atoms
    • 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
    • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen

Definitions

  • the invention is directed to structural adhesives and composites having high brominated epoxy contents.
  • the invention is further directed to methods for preparing such structural adhesives and composites.
  • An epoxy resin is a thermoset polymer that contains epoxied groups and forms a polymeric network by crosslinking the epoxied molecules with a curing agent.
  • Many epoxy adhesives are prepared using diglycidyl ether of bisphenol A (DGEBA) as a monomer and amino compounds or formaldehyde-phenol condensates as curing agents.
  • DGEBA diglycidyl ether of bisphenol A
  • Aromatic tetraglycidylamine (TGMDA), trifunctional epoxies based on meta and para aminophenol, epoxy novolacs, as well as epoxies based on trisphenol may also be used when high glass transition temperature (Tg) values are required.
  • TGMDA Aromatic tetraglycidylamine
  • trifunctional epoxies based on meta and para aminophenol, epoxy novolacs, as well as epoxies based on trisphenol may also be used when high glass transition temperature (Tg) values are required.
  • Tg glass transition temperature
  • Epoxy resins are known to have high chemical resistance to various substances, enhanced dielectric and insulation properties, high chemical compatibility with a wide range of substances, low shrinkage on cure, dimensional stability, and fatigue resistance, and therefore are widely used in the formulation of adhesives and protective coatings.
  • Epoxy adhesives are highly cross-linked and amorphous materials when polymerized, thus providing high failure strength and modulus, high temperature durability, and low creep. Yet, such a micro structure leads to less advantageous properties, including poor resistance to crack initiation and growth that leads to brittle materials. Therefore, toughening the epoxy resins may be required to enable resistance to peel, impact, and fatigue.
  • aliphatic and aromatic polyamines as well as anhydride and sulfone based materials, such as diamino diphenyl sulfone (DDS), have been incorporated into epoxy resins, providing enhanced toughness, decreased brittleness, without significantly lowering the Tg.
  • DDS diamino diphenyl sulfone
  • Fillers may also be incorporated into the epoxy resin in order to improve the impact strength of the product; however the use of fillers may decrease the tensile and flexural strength and modulus of the modified epoxies.
  • an epoxy resin that is highly tough and not brittle, while still having a high Tg, high chemical resistance to various substances, enhanced dielectric and insulation properties, high chemical compatibility with a wide range of substances, low shrinkage on cure, dimensional stability, and fatigue resistance.
  • Such an epoxy resin could be formulated as structural adhesives and/or as a matrix for composite materials.
  • Embodiments of the invention are directed to a structural adhesive comprising an epoxy component and a curing agent, wherein the epoxy component comprises at least 10% w/w of a brominated epoxy.
  • the epoxy component comprises between about 30-60% w/w of a brominated epoxy.
  • Further embodiments of the invention are directed to a process for preparing a structural adhesive comprising an epoxy component and a curing agent, wherein the epoxy component comprises at least 10% w/w of a brominated epoxy, wherein the process comprises: mixing a brominated epoxy with a non-brominated epoxy to provide an epoxy component, wherein the provided epoxy component comprises at least 10% w/w of the brominated epoxy;
  • the epoxy component and curing agent mixture at a temperature of between about 25-130°C when the epoxy component and curing agent mixture comprises an aliphatic curing agent, and between about 170-220°C when the epoxy component and curing agent mixture comprises an aromatic curing agent.
  • the process of the invention further comprises: either
  • the curing agent is an aromatic curing agent.
  • the curing agent is an aliphatic curing agent.
  • the curing agent is poly-diethyl triamine (DETA), poly-triethylenetetramine (TETA), polyoxypropylenediamine (JEFF AMINE D-230), poly-diamino diphenylsulfone (DDS), or any combination of aliphatic curing agents or any combination of aromatic curing agents.
  • DETA poly-diethyl triamine
  • TETA poly-triethylenetetramine
  • JEFF AMINE D-230 polyoxypropylenediamine
  • DDS poly-diamino diphenylsulfone
  • the epoxy component comprises at least about 50% w/w of a brominated epoxy compound.
  • the brominated epoxy compound is a polymer of brominated diglycidyl ether of bisphenol-A (BDGEBA).
  • the epoxy component includes a polymer of no n- brominated diglycidyl ether of bisphenol-A (DGEBA).
  • the epoxy component includes a tri-functional epoxy, a tetra-functional epoxy, or any combination thereof.
  • the invention is further directed to a process for preparing a structural adhesive comprising an epoxy component and a curing agent, wherein the epoxy component comprises between about 30-60% w/w of a brominated epoxy.
  • Further embodiments of the invention are directed to a composite comprising an epoxy component and a curing agent, wherein the epoxy component comprises at least 10% w/w of a brominated epoxy compound. According to some embodiments, the epoxy component comprises between about 30-60% w/w of a brominated epoxy.
  • some embodiments of the invention are directed to a process for preparing a composite comprising an epoxy component and a curing agent, wherein the epoxy component comprises at least 10% w/w of a brominated epoxy compound, the process comprising: mixing a brominated epoxy with a non-brominated epoxy to provide an epoxy component, wherein the provided epoxy component comprises at least 10% w/w of the brominated epoxy;
  • the fiber reinforced epoxy component and curing agent mixture at a temperature of between about 25-130°C when the fiber reinforced epoxy component and curing agent mixture comprises an aliphatic curing agent, and between about 170-220°C when the epoxy component and curing agent mixture comprises an aromatic curing agent.
  • the fiber reinforced epoxy component and curing agent mixture is cured under vacuum, thereby providing a degassed and cured fiber reinforced epoxy component and curing agent mixture.
  • the vacuum is provided by way of an autoclave or a vacuum bag.
  • Embodiments of the invention are directed to a composite prepared according to the process of the invention, as detailed herein.
  • the curing agent in the composite is an aromatic curing agent.
  • the curing agent in the composite is an aliphatic curing agent.
  • the curing agent in the composite is poly-diethyl triamine (DETA), poly-triethylenetetramine (TETA), polyoxypropylenediamine (JEFFAMINE D-230), poly-diamino diphenylsulfone (DDS), or any combination of aliphatic curing agents or any combination of aromatic curing agents.
  • the epoxy component in the composite comprises at least about 50% w/w of a brominated epoxy compound.
  • the brominated epoxy compound in the composite is a polymer of brominated diglycidyl ether of bisphenol-A (BDGEBA).
  • the epoxy component in the composite includes a polymer of non- brominated diglycidyl ether of bisphenol-A (DGEBA).
  • the epoxy component in the structural adhesive includes a tri-functional epoxy, a tetra-functional epoxy, or any combination thereof.
  • the epoxy component in the composite includes a tri-functional epoxy, a tetra-functional epoxy, or any combination thereof.
  • the invention is further directed to a process for preparing a composite comprising an epoxy component and a curing agent, wherein the epoxy component comprises between about 30-60% w/w of a brominated epoxy.
  • Figure 1 presents the initial storage modulus of DGEBA1/BDGEBA1 blends with TETA, obtained from a DMA test (25°C RT);
  • Figure 2 presents the flexural stress curve obtained by a three-point bending test for DGEBA1/BDGEBA1 with DETA and TETA curing agents;
  • Figure 3 presents the flexural elongation to break for DGEBA1/BDGEBA1 with DETA and TETA curing agents
  • Figure 4 presents the flexural modulus curve obtained by a three-point bending test for DGEBA1/BDGEBA1 with DETA and TETA curing agents;
  • Figure 5 presents the flexural stress curve obtained by a three-point bending test for DGEB A 1 /B DGEB A 1 / JEFF AMINE D-230 blends;
  • Figure 6 presents the flexural strain curve obtained by a three-point bending test for DGEB A 1 /B DGEB A 1 / JEFF AMINE D-230 blends;
  • Figure 7 presents the flexural modulus curve obtained from a three-point bending test for DGEB A 1 /B DGEB A 1 /JEFF AMINE D-230 blends;
  • Figure 8 presents the glass transition temperature (Tg (°C)) curve obtained from a DMA test for DGEBA1/BDGEBA1/JEFF AMINE D-230 blends;
  • Figure 9 presents the storage modulus of the DGEBAl/BDGEBAl blend, when DDS was used as the curing agent;
  • Figure 10 presents the flexural stress curve obtained from a three-point bending test for DGEBA1/BDGEBA1/DDS blends
  • Figure 11 presents the flexural strain curve obtained from a three-point bending test for DGEBA1/BDGEBA1/DDS blends
  • Figure 12 presents the flexural modulus curve obtained from a three-point bending test for DGEBA1/BDGEBA1/DDS blends
  • Figure 13 presents the Tg, flexural modulus, flexural strength, elongation to brake and E' (storage modulus) at 25°C ratios, compared to the control group results (neat DGEBA), using the DDS curing agent;
  • Figure 14 presents the effect of the temperature on the viscosities of the DGEBAl/BDGEBAl blends at different ratios
  • Figures 15 A, 15B, 15C and 15D present SEM micrographs of the fracture surface of DGEBAl/BDGEBAl blends, cured with DETA, wherein the epoxy component in the blend comprises ( Figure 15A) BDGEBA1 0 wt%, ( Figure 15B) BDGEBA1 40 wt%, and ( Figure 15C) BDGEBA1 50 wt%, ( Figure 15D) BDGEBA1 60 wt%, prepared by mechanical mixing;
  • Figures 16 A, 16B and 16C present SEM micrographs of the fracture surfaces of DGEBAl/BDGEBAl blends, cured with TETA, wherein the epoxy component in the blend comprises ( Figure 16A) BDGABEl 40 wt%, ( Figure 16B) BDGABEl 50 wt%, and ( Figure 16C) BDGABEl 60 wt%, prepared by mechanical mixing;
  • Figure 17 presents the tensile shear strength values obtained from a lap shear test for DGEBAl/BDGEBAl/JEFFAMINE D-230 mixtures;
  • Figures 18A and 18B present T-peel average adhesive strength values of the prepared DGEBAl/BDGEBAl/JEFFAMINE D-230 blend ( Figure 18 A) and of the prepared DGEBAl/BDGEBAl/JEFFAMINE T-403 blend ( Figure 18B);
  • Figure 19 presents the Tg, stress at max. load, stress at break, modulus and % elongation at brake, of neat DGEBA and DGEBAl/BDGEBAl blends, when the JEFF AMINE T-403 curing agent was used;
  • Figure 20 presents the Tg, tensile shear strength, T-PEEL max. strength and T- PEEL avg. strength, of neat DGEBA and DGEBA1/BDGEBA1 blends, when the JEFF AMINE T-403 curing agent was used;
  • Figures 21A, 21B and 21C present SEM micrographs of the fracture surface of DGEBA1/BDGEBA1 blends, cured with JEFF AMINE T-403, wherein the epoxy component in the blend comprises ( Figure 21A) BDGEBAl 10 wt%, ( Figure 21B) BDGEBAl 40 wt%, and ( Figure 21C) BDGEBAl 60 wt%, prepared by mechanical mixing; and
  • Figures 22A, 22B, 22C and 22D present SEM micrographs of the fracture surface of DGEBA1/BDGEBA1 blends, cured with DDS, comprising ( Figure 22A) BDGEBAl 0 wt%, ( Figure 22B) BDGEBAl 50 wt%, ( Figure 22C) BDGEBAl 70 wt%, ( Figure 22D) BDGEBAl 90 wt%.
  • the term “about” is defined to cover a range of +10% of the disclosed values.
  • the terms “blend”, “mixture” and the like are interchangeable. It is noted that, unless mention otherwise, the wt% provided relate to the percentages of the brominated and non- brominated epoxies as part of the epoxy component, without taking the curing agent, or other possible additives, into account. Further, unless mentioned otherwise, or unless would have been understood otherwise by a person skilled in the art, the terms “brominated epoxy compounds”, “brominated epoxy” and “brominated epoxies” are interchangeable. Likewise, the terms “epoxy compounds”, “epoxies” and “epoxy” are interchangeable.
  • Embodiments of the invention are directed to structural adhesives and composites comprising an epoxy component and a curing agent, wherein at least 10% w/w of the epoxy component is brominated epoxy compounds. According to some embodiments, at least 15% of the epoxy component is brominated epoxy compounds. According to some embodiments, at least 20% of the epoxy component is brominated epoxy compounds. According to some embodiments, at least 25% of the epoxy component is brominated epoxy compounds. According to some embodiments, at least 30% of the epoxy component is brominated epoxy compounds. According to some embodiments, at least 35% of the epoxy component is brominated epoxy compounds. According to some embodiments, at least 40% of the epoxy component is brominated epoxy compounds.
  • At least 50% of the epoxy component is brominated epoxy compounds.
  • at least 60% of the epoxy component is brominated epoxy compounds.
  • the amount of the brominated epoxy compounds in the epoxy component is between about 5-65%.
  • the amount of the brominated epoxy compounds in the epoxy component is between about 5-15%.
  • the amount of the brominated epoxy compounds in the epoxy component is between about 15-25%.
  • the amount of the brominated epoxy compounds in the epoxy component is between about 25-35%.
  • the amount of the brominated epoxy compounds in the epoxy component is between about 35-45%.
  • the amount of the brominated epoxy compounds in the epoxy component is between about 45-55%. According to some embodiments, the amount of the brominated epoxy compounds in the epoxy component is between about 55- 65%. According to some embodiments, the amount of the brominated epoxy compounds in the epoxy component is between about 30-60%.
  • At least 70% of the epoxy component is brominated epoxy compounds. According to some embodiments, at least 80% of the epoxy component is brominated epoxy compounds. According to some embodiments, at least 90% of the epoxy component is brominated epoxy compounds.
  • the brominated epoxy compound is a polymer of brominated diglycidyl ether of bisphenol-A (BDGEBA), formulated as follows:
  • the molecular weight of the polymeric BDGEBA is between about 300 to 10000 daltons. According to some embodiments, the molecular weight of the polymeric BDGEBA is between about 300-1000 daltons. According to some embodiments, the molecular weight of the polymeric BDGEBA is between about 1000-2000 daltons. According to some embodiments, the molecular weight of the polymeric BDGEBA is between about 2000-3000 daltons. According to some embodiments, the molecular weight of the polymeric BDGEBA is between about 3000-4000 daltons. According to some embodiments, the molecular weight of the polymeric BDGEBA is between about 4000-5000 daltons.
  • the molecular weight of the polymeric BDGEBA is between about 5000-6000 daltons. According to some embodiments, the molecular weight of the polymeric BDGEBA is between about 6000-7000 daltons. According to some embodiments, the molecular weight of the polymeric BDGEBA is between about 7000-8000 daltons. According to some embodiments, the molecular weight of the polymeric BDGEBA is between about 8000-9000 daltons. According to some embodiments, the molecular weight of the polymeric BDGEBA is between about 9000-10000 daltons. According to some embodiments, the molecular weight of the polymeric BDGEBA is between about 500-900 daltons.
  • the molecular weight of the polymeric BDGEBA is between about 600- 8000 daltons. According to some embodiments, the molecular weight of the polymeric BDGEBA is between about 650-750 daltons. According to some embodiments, the molecular weight of the polymeric BDGEBA is about 700 daltons.
  • the brominated epoxy compound is a polymer of halogenated epoxies, such as chlorinated epoxy.
  • the brominated epoxy compound is a curable epoxy resin having at least two functional epoxide groups, wherein the epoxy resin may be grafted with a bromine atom.
  • the brominated epoxy compound may be selected from brominated bisphenol F, brominated novo lac epoxy, brominated glycidyl ether of tetraphenolethane epoxy, or any combination thereof.
  • the epoxy component comprises brominated and non-brominated epoxy compounds.
  • the non-brominated epoxy compound is a polymer of diglycidyl ether of bisphenol- A (DGEBA), formulated as follows: o O
  • the epoxy compound is a curable epoxy resin having at least two functional epoxide groups.
  • the epoxy compound may be selected from bisphenol F, novo lac epoxy, glycidyl ether of tetraphenolethane epoxy, an aliphatic epoxy, or any combination thereof.
  • the structural adhesives and composites further comprise an epoxy curing agent selected from poly-diethyl triamine (DETA), poly-triethylenetetramine (TETA), polyoxypropylenediamine (JEFFAMINE D-230 and JEFFAMINE T-403), poly-diamino diphenylsulfone (DDS), or any aliphatic, aromatic or anhydride curing agent, or any combination of aliphatic curing agents or any combination of aromatic curing agents.
  • DETA poly-diethyl triamine
  • TETA poly-triethylenetetramine
  • JEFFAMINE D-230 and JEFFAMINE T-403 polyoxypropylenediamine
  • DDS poly-diamino diphenylsulfone
  • any aliphatic, aromatic or anhydride curing agent or any combination of aliphatic curing agents or any combination of aromatic curing agents.
  • the structural adhesives and composites comprise stoichiometric amounts of an epoxy component and a curing agent, wherein the stoichiometric amount is calculated according to the following equations:
  • the structural adhesives and composites further comprise a toughening agent selected from carboxy-terminated polybutadiene/acrylonitrile (CTBN), poly amine terminated butadiene acrylonitrile (ATBN) or any combination thereof.
  • CBN carboxy-terminated polybutadiene/acrylonitrile
  • ATBN poly amine terminated butadiene acrylonitrile
  • the Tg is increased significantly, while preserving the elongation, as exemplified with a formulation cured by DDS in Figure 13. It is noted that, unlike the blends in the instant formulation, usually when the Tg increases, the elongation is decreased; however, in the formulations of the invention, the fracture morphology is such that nodules are formed and therefore, the elongation is preserved.
  • the use of brominated epoxy according to the present invention provides an increase in the Tg, when curing the aromatic or polyetheramine curing agents.
  • the Tg of neat DGEBAl cured using aromatic curing agents, such as DDS is about 172-185°C
  • the Tg of the DGEBA1/BDGEBA1 blends, prepared according to this invention is between about 203-208°C.
  • the Tg of neat DGEBAl, cured using aliphatic curing agents is about 80-115°C
  • the Tg of the DGEBA1/BDGEBA1 blends, prepared according to this invention is in the range of about +10°C compared to neat DGEBAl.
  • the storage modulus at 25°C is increased by about 40%, for formulations comprising 50wt% BDGEBA1, cured with DDS.
  • the storage modulus at 25°C of 50wt% BDGEBA1 formulation cured with DDS is about 2650 Mpa while the storage modulus at 25°C of neat epoxy cured with DDS is about 1890 Mpa.
  • the Tg and the elongation are increased (see, e.g., Figure 6).
  • the Tg of the neat DGEBAl is about 8TC and the Tg of all BDGEBA1 blends is in the range of 82°C to 100 °C.
  • Elongation of 40wt% BDGEBA1 formulation of JEFF AMINE T- 403 presented values of about 13% while neat epoxy presented elongation of about 8%.
  • TETA is used as the curing agent, an increase in the BDGEBAl w/w% results in higher stress at yield, while preserving the elongation.
  • Embodiments of the invention are directed to a process for preparing a structural adhesive comprising an epoxy component and a curing agent, wherein the epoxy component comprises at least 10% w/w of a brominated epoxy, said process comprising: mixing a brominated epoxy with a non-brominated epoxy to provide an epoxy component, wherein the provided epoxy component comprises at least 10% w/w of the brominated epoxy;
  • curing the epoxy component and curing agent mixture at a temperature of between about 25-130°C when said epoxy component and curing agent mixture comprises an aliphatic curing agent, and between about 170-220°C when said epoxy component and curing agent mixture comprises an aromatic curing agent.
  • the process for preparing a structural adhesive comprising an epoxy component and a curing agent, wherein the epoxy component comprises at least 10% w/w of a brominated epoxy further comprises: either
  • the brominated epoxy and non-brominated epoxy are mixed and heated, possibly in an oil bath, for about 5-15 minutes, until fusion is completed.
  • the epoxy component comprises at least 15% w/w of a brominated epoxy. According to some embodiments, the epoxy component comprises at least 20% w/w of a brominated epoxy. According to some embodiments, the epoxy component comprises at least 25% w/w of a brominated epoxy. According to some embodiments, the epoxy component comprises at least 30% w/w of a brominated epoxy. According to some embodiments, the epoxy component comprises at least 35% w/w of a brominated epoxy. According to some embodiments, the epoxy component comprises at least 40% w/w of a brominated epoxy. According to some embodiments, the epoxy component comprises at least 45% w/w of a brominated epoxy.
  • the epoxy component comprises at least 50% w/w of a brominated epoxy. According to some embodiments, the epoxy component comprises at least 55% w/w of a brominated epoxy. According to some embodiments, the epoxy component comprises at least 60% w/w of a brominated epoxy. According to some embodiments, the amount of the brominated epoxy compounds in the epoxy component is between about 5-65%. According to some embodiments, the amount of the brominated epoxy compounds in the epoxy component is between about 5-15%. According to some embodiments, the amount of the brominated epoxy compounds in the epoxy component is between about 15-25%. According to some embodiments, the amount of the brominated epoxy compounds in the epoxy component is between about 25-35%.
  • the amount of the brominated epoxy compounds in the epoxy component is between about 35-45%. According to some embodiments, the amount of the brominated epoxy compounds in the epoxy component is between about 45- 55%. According to some embodiments, the amount of the brominated epoxy compounds in the epoxy component is between about 55-65%. According to some embodiments, the amount of the brominated epoxy compounds in the epoxy component is between about 30-60%.
  • the epoxy component comprises at least 65% w/w of a brominated epoxy. According to some embodiments, the epoxy component comprises at least 70% w/w of a brominated epoxy. According to some embodiments, the epoxy component comprises at least 75% w/w of a brominated epoxy. According to some embodiments, the epoxy component comprises at least 80% w/w of a brominated epoxy. According to some embodiments, the epoxy component comprises at least 85% w/w of a brominated epoxy. According to some embodiments, the epoxy component comprises at least 90% w/w of a brominated epoxy. According to some embodiments, the epoxy component comprises at least 95% w/w of a brominated epoxy.
  • the epoxy component is heated to a temperature of between about 120-130°C.
  • the epoxy component after heating for a predefined length of time, is cooled to a temperature of between about 55-65°C.
  • the epoxy component and curing agent mixture is degassed using a vacuum pump or in a vacuum oven for about 15 minutes to one hour.
  • the degassed mixture when the curing agent is DETA or TETA, the degassed mixture may be maintained in the mold for about 24 hours at room temperature, after which it may be post-cured for about three hours at a temperature between about 70-90°C.
  • the degassed mixture when the JEFF AMINE D- 230 curing agent is used, the degassed mixture may be maintained in the mold at a temperature of about 60-80°C for about three hours, after which it may be let to cool to room temperature and may be maintained at room temperature for about 20 hours. Post-curing may then be performed for about three hours at a temperature between about 100-120°C.
  • the epoxy component and curing agent mixture may be cast into a mold that is preheated to about 130-150°C.
  • the epoxy component and curing agent mixture may then be degassed in the mold for about 30-50 minutes at a temperature between about 140- 160°C.
  • the degassed mixture may then be cured in the mold at a temperature between about 160-180°C for about two hours, possibly followed by post-curing at a temperature of between about 190-210°C for about one hour.
  • Embodiments of the invention are directed to a composite comprising an epoxy component and a curing agent, wherein the epoxy component comprises at least 10% w/w of a brominated epoxy. According to some embodiments, at least 15% of the epoxy component is brominated epoxy compounds. According to some embodiments, at least 20% of the epoxy component is brominated epoxy compounds. According to some embodiments, at least 25% of the epoxy component is brominated epoxy compounds. According to some embodiments, at least 30% of the epoxy component is brominated epoxy compounds. According to some embodiments, at least 35% of the epoxy component is brominated epoxy compounds. According to some embodiments, at least 40% of the epoxy component is brominated epoxy compounds. According to some embodiments, at least 50% of the epoxy component is brominated epoxy compounds.
  • the epoxy component is brominated epoxy compounds.
  • the amount of the brominated epoxy compounds in the epoxy component is between about 5-65%. According to some embodiments, the amount of the brominated epoxy compounds in the epoxy component is between about 5-15%. According to some embodiments, the amount of the brominated epoxy compounds in the epoxy component is between about 15-25%. According to some embodiments, the amount of the brominated epoxy compounds in the epoxy component is between about 25- 35%. According to some embodiments, the amount of the brominated epoxy compounds in the epoxy component is between about 35-45%. According to some embodiments, the amount of the brominated epoxy compounds in the epoxy component is between about 45-55%. According to some embodiments, the amount of the brominated epoxy compounds in the epoxy component is between about 55- 65%. According to some embodiments, the amount of the brominated epoxy compounds in the epoxy component is between about 30-60%.
  • At least 70% of the epoxy component is brominated epoxy compounds.
  • at least 80% of the epoxy component is brominated epoxy compounds.
  • at least 90% of the epoxy component is brominated epoxy compounds.
  • about 95-100% of the epoxy component is brominated epoxy compounds.
  • Embodiments of the invention are directed to a process for preparing composites comprising an epoxy component and a curing agent, wherein the epoxy component comprises at least 10% w/w of a brominated epoxy, said process comprising: mixing a brominated epoxy with a non-brominated epoxy to provide an epoxy component, wherein the provided epoxy component comprises at least 10% w/w of the brominated epoxy;
  • the process for preparing composites comprising an epoxy component and a curing agent, wherein the epoxy component comprises at least 10% w/w of a brominated epoxy further comprises curing the fiber reinforced epoxy component and curing agent mixture under vacuum, thereby providing a degassed and cured fiber reinforced epoxy component and curing agent mixture.
  • the vacuum is provided by way of an autoclave or a vacuum bag.
  • the epoxy component comprises at least 15% w/w of a brominated epoxy. According to some embodiments, the epoxy component comprises at least 20% w/w of a brominated epoxy. According to some embodiments, the epoxy component comprises at least 25% w/w of a brominated epoxy. According to some embodiments, the epoxy component comprises at least 30% w/w of a brominated epoxy. According to some embodiments, the epoxy component comprises at least 35% w/w of a brominated epoxy. According to some embodiments, the epoxy component comprises at least 40% w/w of a brominated epoxy. According to some embodiments, the epoxy component comprises at least 45% w/w of a brominated epoxy.
  • the epoxy component comprises at least 50% w/w of a brominated epoxy. According to some embodiments, the epoxy component comprises at least 55% w/w of a brominated epoxy. According to some embodiments, the epoxy component comprises at least 60% w/w of a brominated epoxy. According to some embodiments, the amount of the brominated epoxy compounds in the epoxy component is between about 5-65%. According to some embodiments, the amount of the brominated epoxy compounds in the epoxy component is between about 5-15%. According to some embodiments, the amount of the brominated epoxy compounds in the epoxy component is between about 15-25%. According to some embodiments, the amount of the brominated epoxy compounds in the epoxy component is between about 25-35%.
  • the amount of the brominated epoxy compounds in the epoxy component is between about 35-45%. According to some embodiments, the amount of the brominated epoxy compounds in the epoxy component is between about 45- 55%. According to some embodiments, the amount of the brominated epoxy compounds in the epoxy component is between about 55-65%. According to some embodiments, the amount of the brominated epoxy compounds in the epoxy component is between about 30-60%.
  • the epoxy component comprises at least 65% w/w of a brominated epoxy. According to some embodiments, the epoxy component comprises at least 70% w/w of a brominated epoxy. According to some embodiments, the epoxy component comprises at least 75% w/w of a brominated epoxy. According to some embodiments, the epoxy component comprises at least 80% w/w of a brominated epoxy. According to some embodiments, the epoxy component comprises at least 85% w/w of a brominated epoxy. According to some embodiments, the epoxy component comprises at least 90% w/w of a brominated epoxy. According to some embodiments, the epoxy component comprises at least 95% w/w of a brominated epoxy.
  • the DGEBAl/TETA and DGEBAl/DETA blends were thoroughly mixed for 15 minutes, after which they were placed in a vacuum pump for 20 minutes, and finally casted into silicone molds. After 24 hours at room temperature and an additional three hours of post curing at 80°C in the molds, the prepared structural adhesives were removed from the molds.
  • the DGEBAl/Jeffamine D-230 and DGEBAl/Jeffamine T-403 blends were also thoroughly mixed for 15 minutes, degassed in a vacuum pump for 20 minutes and casted into molds.
  • the molds were maintained at 70°C for three hours, then at room temperature for 20 hours.
  • the formulations were then post-cured in the molds for three hours at 110°C, after which the prepared structural adhesives were removed from the molds.
  • DGEBA1 and BDGEBAl were prepared using the following ratios, respectively: 100/0, 90/10, 80/20, 70/30, 60/40, 50/50 and 40/60 (DGEBA1/BDGEBA1).
  • DGEBA1/BDGEBA1 the blends were mixed and heated to 125°C in an oil bath for 10 minutes until obtaining absolute fusion. It is noted that some of the samples were mixed manually and some were mixed using a mechanical stirrer, as detailed below.
  • the aliphatic curing agents were added in a stoichiometric amount, as detailed in Table I above and as calculated according to the equations provided above. The curing agents were added when the mixture was approximately at 60°C. The curing process was the same as described above regarding the neat DGEBA1 blends.
  • DGEBA1 and BDGEBAl were prepared in the following ratios: 100/0, 70/30, 50/50, 30/70, 20/80, 10/90 (DGEBA1/BDGEBA1).
  • the DDS curing agent was added to the mixtures and then, for homogenization, the blends were thoroughly stirred using a mechanical stirrer at 60 rpm and heated to approximately 125°C in an oil bath for 30 minutes to obtain a transparent liquid pre-polymer.
  • the obtained pre-polymer was poured into a silicone mold that was preheated to 140°C, degassed in a vacuum oven at 150°C for 40 min, and than cured at 170°C for two hours, followed by a post-curing at 200°C for one hour.
  • the aromatic curing agent was added in a stoichiometric amount according the epoxy equivalent mix equation.
  • the silicone rubber molds used were fit to the DMA test standard. Accordingly, DMA samples were obtained directly from casting. Before testing, the surface and edges of the samples were smoothed using sandpaper in order to remove any surface defects as well as to guarantee that the samples had flat and parallel surfaces. The average dimensions of the test samples used was 30x6x3mm. Each sample was tested using a model Q 800 TA Instruments DMA equipment, operating at its three point flexural mode at lHz of frequency, according to standard ASTM D4065, set to a heating rate of 3°C/min, at temperature range of 25-150°C. The results were registered as curves of the storage modulus ( ⁇ '), loss modulus (E”) and tangent delta (tan ⁇ ).
  • TMDSC Temperature Modulated scanning calorimetry
  • TMDSC measurements were carried under "Quasi- linear heating rate" conditions, with a sinusoidal temperature modulation; the tests were performed under a nitrogen atmosphere at a 5°C/min heating rate with a modulation amplitude of 0.5 °C, between 0°C and 200°C, for aliphatic amine curing agents, and between room temperature and 280°C, for aromatic amine curing agent.
  • the flexural tests were performed using an Instron, model 4481, a universal testing machine.
  • the samples were shaped using a silicone cavity mold yielding the sample geometry of approximately 38x12.7x2mm 3 .
  • the test yielded values of flexural stress, flexural modulus, and flexural strain. All measurements were conducted at three-point bending using a crosshead speed of 1 mm/min, with a span equal to 32 mm.
  • the dimensions of the sample, span and speed of test were based on ASTM D 790-03 protocol. Measurements were performed for each sample at 50% relative humidity at 23°C, and the results average value was taken with standard deviation.
  • Test samples were shaped using dog-bone silicone molds, of the above cured blends. The sample dimensions as well as the span and speed of the test were based on the ASTM D 638-02a protocol for rigid plastics.
  • a Discovery- HR- 1 (hybrid rheometer) was used to determine the viscosities of DGEBA1/BDGEBA1 sample at different ratios of brominated epoxy, in temperature rump mode.
  • the Lap shear adhesion strength tests were performed using an Instron, model 4481. Anodized treated alumina plates, having the size of approximately 25 x 101 x 1.6 mm 3 , were used as adherents. The plates were used in two different forms: with no surface pretreatment and with epoxy silane surface treatment. Then, the various prepared adhesive mixtures, as detailed above, were coated onto two adherents having a surface area of 25 x 13 mm 2 before curing. The coated adherents were adhered and pressed together with a thickness of 0.1 mm and were then cured according to the curing conditions for each mixture, as detailed above. The sample dimensions as well as the span and speed of the test were based on the ASTM D 1002 protocol for metal adherents.
  • the T-peel adhesion strength tests were performed using an Instron, model 4481.
  • Anodized treated alumina plates having the size of approximately 25x305x1.6 mm 3 , were used as adherents.
  • the un-bonded ends Prior to the test, the un-bonded ends were bent away from one another, perpendicular to the adhesion line, for clamping in the grips of the testing machine.
  • the tension test machine was set to a crosshead speed of 250 mm/min. Measurements were performed four times at least and the averages were calculated for the T-peel adhesion strength.
  • Tg Glass transition temperature
  • Tg Tg Tg Tg Tg Tg Tg Tg Tg Tg Tg Tg Tg Tg Tg Tg /BDGEBA1 (°C) (°C) (°C) (°C) (°C) (°C) (°C) (°C) (°C)
  • FIG. 2 presenting flexural strength data of cured DGEBA1/BDGEBA1 blends as a function of the BDGEBAl content comprising DETA and TETA curing agents, wherein the control sample comprises 0% BDGEBAl.
  • TETA was used as the curing agent
  • the cured DGEBA1/BDGEBA1 blends show a higher flexural strength than the control.
  • DETA is the curing agent
  • cured DGEBA1/BDGEBA1 blends under 50wt% BDGEBAl show a higher flexural strength than the control 50% also seems higher if 0% is what you're considering the control.
  • blends with 40wt% BDGEBAl show a decrease in flexural strength, while blends with 60wt% show lower flexural strength than the control.
  • the control related to herein is the sample comprising 0% BDGEBAl.
  • FIG 4 presenting flexural modulus results of cured DGEBAl/BDGEBAl blends as a function of the BDGEBA1 content, using DETA and TETA as the curing agents.
  • the flexural modulus is increased for both DETA and TETA curing agents in all tested DGEBAl/BDGEBAl blends.
  • TETA when used, the modulus values increase with the increase of the BDGEBA1 content, while when DETA is used, there is no specific correlation between the modulus values and the BDGEBA1 content.
  • blends with 40wt% BDGEBA1 present the highest flexural modulus values.
  • FIG. 7 presenting the flexural modulus results obtained from cured DGEBAl/BDGEBAl blends, as a function of BDGEBA1 content, using JEFF AMINE D-230 as the curing agent.
  • the DGEBAl/BDGEBAl blends show a lower flexural modulus than the control; however, there is a trend of increase in the flexural modulus with the increase of the BDGEBA1 content.
  • DGEBAl/BDGEBAl blends when the JEFF AMINE D-230 curing agent was used, obtained from DMA analysis, compared to the control. An increase in Tg values was observed for all blends containing BDGEBA1, compared to the control.
  • the storage modulus of DGEBA1/BDGEBA1 mixtures at 30, 50, 70, 90 wt% BDGEBAl were found to be 935, 1484, 926, and 1415, respectively, at a temperature of about 200°C.
  • the drop in the graph defines the Tg of the material. As can be seen in the graph for the neat samples the Tg was about 160°C, while by mixing with BDGEBA, the Tg was increased to about 200°C.
  • FIG 10 presenting the flexural strength results obtained from cured DGEBA1/BDGEBA1 blends, as a function of BDGEBAl content, using the DDS curing agent.
  • the DGEBA1/BDGEBA1 blends present flexural strengths similar to that of the control, while the 90wt% BDGEBAl blend presents lower flexural strength than the control.
  • Blends with 50wt% and 70wt% BDGEBAl showed similar elongation percentages and flexural modulus compared to the control, while the 30wt% blend showed a decrease in the flexural modulus. All flexural strength ratios exhibited lower values than the control. Blends with 50wt% BDGEBAl exhibit a similar elongation to the control, while blends with 90wt% BDGEBAl present a much lower value.
  • Table V below presents tensile properties, including tensile strength, tensile elongation, and Young's Modulus, wherein the DDS curing agent was used to cure the DGEBA1/BDGEBA1 mixtures.
  • FIG 14 presenting the viscosity results of cured DGEBA1/BDGEBA1 blends, as a function of temperature. As shown in Figure 14, as the BDGEBAl content was increased, the viscosity was higher. This may be caused by the higher molecular weight of the BDGEBAl in comparison to the DGEBA1.
  • Figure 15 presenting the SEM micrographs of the fracture surfaces of various DGEBA1/BDGEBA1 blends, cured by DETA
  • Figures 15 A, 15B, 15C and 15D present the effect of the amount of the brominated epoxy on the morphology of the prepared DGEBA1/BDGEBA1 blend.
  • Figure 15A shows that the surface of the control, in which 100 wt% of the epoxy component is DGEBA1, is a smooth surface having longitudinal lines that characterize neat epoxy at break.
  • the fracture surface of the DGEBA1/BDGEBA1 blend in which 40% of the epoxy component is BDGABEl, presents a spherical shape containing structures different from the surrounding surface areas.
  • Figures 15C and 15D reveal that 50 and 60% w/w of the epoxy component provide surfaces having a nodular- like structure.
  • the circular border lines encompass a center point from which lines extend in a radial direction towards the circular border lines.
  • Such structures, as shown in Figures 15C and 15D are known to be obtained by a toughening mechanism, which appears during crack propagation, in epoxy systems.
  • Figure 16A presents nodular-like shapes (40 wt% BDGEBAl).
  • Figure 16B 50 wt% BDGEBAl
  • Figure 16C 60 wt% BDGEBAl
  • snow-flake like structures are presented.
  • Tg glass transition temperature
  • non-treated anodized alumina panels present a trend of increase in the tensile shear strength values with the increase of the BDGEBAl content, while the pre-treated anodized alumina panels do not exhibit a certain trend.
  • the 40wt% BDGEBAl blend presents the highest tensile shear strength mean value.
  • Adhesive failure- A Cohesive failure- C; Mixed- M
  • Adhesive failure- A Cohesive failure- C; Mixed- M
  • D-230 as curing-agent lowered the hardness values of the epoxy matrix compared to the other curing agents, possibly due to the presence of etheric groups. Further, an increase in brominated epoxy weight percentage resulted in higher viscosity of the BDGEBA1/DGEBA1 blend. Mechanical mixing resulted in changing the curing behavior, as shown in the results above, possibly attributed to a uniform dispersion of the solid brominated epoxy in the liquid neat epoxy.
  • BDGEBA1/DGEBA1 prepared using the JEFF AMINE T-403 curing agent, exhibited a significant increase in Tg values with an increase of BDGEBA1 content. All blends displayed higher strength values than the control. Blend with 40wt% BDGEBA1 demonstrated an outstanding improvement of elongation (-60%). Peel strength exhibited similar average strength with a cohesive failure mode for all blends. Shear strength values of blends were low compared to control. It should be noted that most of the specimens presented adhesive failure mode. It is suggested that higher viscosities of brominated blends resulted in poor wetting of the aluminum substrates, which caused poor adhesion of the brominated epoxy blends to the substrate. The 60wt% BDGEBA1 blend was the highest brominated epoxy content applicable blend.
  • Figures 22A, 22B, 22C and 22D presents SEM micrographs of the fracture surface of DGEBA1/BDGEBA1 blends, cured with DDS.
  • the Brominated Epoxy component in the blend comprises ( Figure 22A) BDGEBA1 0 wt%, ( Figure 22B) BDGEBA1 50 wt%, ( Figure 22C) BDGEBA1 70 wt%, ( Figure 22C) BDGEBA1 90 wt%.
  • the fracture surface of all of the blends, including the control ( Figure 22A) presented an abundance of nodular structures. Moreover, control specimen exhibited rougher fracture surface compared to all BDGEBA1 blends.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Epoxy Resins (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne un adhésif structural comprenant un constituant époxy et un agent de durcissement, le constituant époxy comprenant au moins 10 % en poids d'un époxyde bromé. L'invention concerne également un procédé de préparation d'un tel adhésif structural. L'invention concerne en outre un composite comprenant un constituant époxy et un agent de durcissement, le composant époxy comprenant au moins 10 % en poids d'un composé époxy bromé. L'invention concerne également un procédé de préparation d'un tel composite.
PCT/IL2017/051384 2017-02-13 2017-12-26 Adhésifs structuraux et composites comprenant des époxydes bromés WO2018146670A1 (fr)

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