WO2018083177A1 - Système époxyde - Google Patents

Système époxyde Download PDF

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Publication number
WO2018083177A1
WO2018083177A1 PCT/EP2017/078055 EP2017078055W WO2018083177A1 WO 2018083177 A1 WO2018083177 A1 WO 2018083177A1 EP 2017078055 W EP2017078055 W EP 2017078055W WO 2018083177 A1 WO2018083177 A1 WO 2018083177A1
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WO
WIPO (PCT)
Prior art keywords
curable composition
epoxy resin
reinforcing fibers
amount
diglycidyl ether
Prior art date
Application number
PCT/EP2017/078055
Other languages
English (en)
Inventor
Matthaeus KOPCZYNSKI
Michael Henningsen
Miran Yu
Original Assignee
Basf Se
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 Basf Se filed Critical Basf Se
Publication of WO2018083177A1 publication Critical patent/WO2018083177A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—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
    • C08G59/5033—Amines aromatic
    • 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
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
    • C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

Definitions

  • the present invention is directed to a curable composition
  • a curable composition comprising an epoxy resin mixture, wherein the epoxy resin mixture comprises an epoxy resin; diethyl methyl benzene diamine (DETDA) as hardener; and at least one compound selected from the group consisting of 1 ,8- diazabicyclo[5.4.0]undec-7-ene (DBU) and 1 ,5-diazabicyclo[4.3.0]non-5-ene (DBN) as catalyst.
  • DETDA diethyl methyl benzene diamine
  • Fiber-reinforced plastics are composite materials made of a polymer matrix reinforced with fibers. Fibers typically used are glass fibers, carbon fibers, aramid fibers or nylon fibers.
  • the matrix system is in many cases a thermosetting polymer, for example, a polyester resin, a vinyl ester resin, a polyurethane resin or an epoxy resin, or a thermoplastic polymer, for example, polyamide, polypropylene or polyethylene.
  • fiber-reinforced plastics especially, if glass fibers are used in combination with a suitable polymer matrix, is the high elongation at break and the elastic energy uptake. Due to their extremely low weight compared to other materials such as steel, glass fiber reinforced plastics are well suited in all areas where the overall weight is a relevant aspect. Most fiber reinforced polymers are also very suitable when in contact with an aggressive environment due to their excellent corrosion resistance. Furthermore, they display good mechanical properties together with a long service life. Thus, fiber reinforced plastics are also used for treatment, storage or transportation of diverse liquids, for example, for processing and cooling systems, for storage or transportation of waste water or in desalination plants. However, problems arise in cases where glass fiber reinforced plastics are in close contact with hot liquids, especially with hot aqueous media; it turned out that especially the polymer matrix is not durable in case of prolonged exposal to hot aqueous media.
  • the present invention has for its object to provide fiber reinforced plastics based on epoxy resins as matrix material that are chemically and physically stable even at exposure to hot liquid media for a prolonged period of time.
  • the underlying curable composition shall further have advantageous properties when the fiber reinforced plastics are prepared according to a wrapping and/or winding method.
  • a curable composition which comprises an epoxy resin mixture, wherein the epoxy resin mixture comprises
  • DBU diazabicyclo[5.4.0]undec-7-ene
  • DBN 1,5-diazabicyclo[4.3.0]non-5-ene
  • these curable compositions after curing i.e. the composite elements prepared from these curable compositions, have good stability against damage caused by hot liquids, especially against hydrolysis caused by hot aqueous media.
  • Said improved stability against damage, especially hydrolysis is significantly reflected by good interlaminar shear strength results even after storage of test specimen in hot water for a prolonged period of time.
  • the durability of a fiber reinforced plastic is largely dependent on the bonding between the reinforcing fiber and matrix material and on the matrix material's chemical and physical stability.
  • the interlaminar shear strength (ILSS) of a fiber reinforced plastic which is a characteristic parameter in determining durability, is influenced primarily by the interfacial bonding between the reinforcing fiber and the matrix material. For example, small changes in the surface of the fiber or in the matrix material can have a dramatic effect on ILSS.
  • composite elements prepared from the curable compositions according to the present invention are well suited to be used for any kind of application which requires contact with hot liquids, especially with hot aqueous media.
  • the catalyst according to c) is DBU or DBN or a mixture of DBU and DBN.
  • the catalyst is DBU.
  • the epoxy resin according to a) comprises at least one epoxy resin selected from the group consisting of diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of hydrogenated bisphenol A and diglycidyl ether of hydrogenated bisphenol F, more preferably at least one diglycidyl ether of bisphenol A.
  • the diglycidyl ether of bisphenol A is a diglycidyl ether of bisphenol A having a viscosity at 25 °C in the range of from 6000 to 18000 mPa s determined according to DIN 53 015 and an Epoxy Equivalent Weight (EEW) in the range of from 174 to 198 g/eq determined according to DIN 16 945.
  • EW Epoxy Equivalent Weight
  • the diglycidyl ether of bisphenol A is a diglycidyl ether of bisphenol A having a viscosity at 25 °C in the range of from 10000 to 14000 mPa s determined according to DIN 53 015 and an EEW in the range of from 182 - 192 g/eq determined according to DIN 16 945 (Epilox A19-03).
  • One preferred embodiment relates to a curable composition, wherein the epoxy resin mixture comprises
  • One further preferred embodiment relates to a curable composition, wherein the epoxy resin mixture comprises
  • the amount of catalyst according to c i.e. the amount of DBU or of DBN or of DBU and DBN, present in the curable composition.
  • the catalyst is present in an amount of from 0.1 to 20 % by weight, preferably of from
  • the amount of DETDA, present in the curable composition is present in an amount of from 1 to 35 % by weight, preferably of from 5 to 30 % by weight, more preferably of from 15 to 25 % by weight, relative to the amount of the epoxy resin.
  • One preferred embodiment relates to a curable composition, wherein the epoxy resin mixture comprises
  • One further preferred embodiment relates to a curable composition, wherein the epoxy resin mixture comprises
  • the epoxy resin mixture comprised in the curable composition can comprise further components in addition to a), b) and c).
  • the epoxy resin mixture comprises
  • the epoxy resin mixture comprises at least one further component e) selected from the group consisting of pigments, dyes, tougheners, anti- foaming agents or flame-retarding agents.
  • the curable composition consists of the epoxy resin mixture, which preferably consists of the components a), b) and c), more preferably of the components a), b), c) and d) or of the components a), b), c) and e).
  • the curable composition consists of the epoxy resin mixture, which preferably consists of the components a), b), c), d) and e).
  • the curable composition has an initial viscosity at 45°C in the range of from 400 to 800 mPa s determined according to DIN 53 015.
  • the measurement is done by a rheometer (Anton Parr).
  • "Initial" in the context of the present invention means that the viscosity is measured as soon as the curable composition, which is preferably admixed at a temperature below 45 °C, more preferably at a temperature in the range of from 5 to 35 °C, more preferably at about 25 °C, reaches the temperature of 45 °C, wherein the increase in temperature is preferably caused by heating.
  • the temperature measurement is also done by the rheometer. According to the present invention, all temperatures or temperature ranges indicated are related to an absolute pressure of 1 bar.
  • the curable composition has a t 0 pe n at 45°C, i.e. a time until the viscosity reaches the double initial viscosity, of 30 minutes or more, preferably in the range of from 40 to 150 minutes.
  • the curable composition comprises reinforcing fibers embedded in the curable composition.
  • the reinforcing fibers are selected from the group consisting of glass fiber, carbon fiber, nylon fiber and aramid fiber, preferably glass fiber.
  • the reinforcing fibers are endless fibers, more preferably in the form of single fibers or ravings.
  • the amount in which the reinforcing fibers are present in the curable composition is not limited.
  • the reinforcing fibers are present in an amount of from 10 to 80 % by volume, preferably of from 25 to 75 % by volume, more preferably of from 30 to 50 % by volume, relative to the total volume of the curable composition.
  • the present invention is further directed to a process for preparing a curable composition, which comprises mixing of
  • the epoxy resin according to a) comprises at least one epoxy resin selected from the group consisting of diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of hydrogenated bisphenol A and diglycidyl ether of hydrogenated bisphenol F, more preferably at least one diglycidyl ether of bisphenol A.
  • the diglycidyl ether of bisphenol A is a diglycidyl ether of bisphenol A having a viscosity at 25 °C in the range of from 6000 to 18000 mPa s determined according to DIN 53 015 and an Epoxy Equivalent Weight (EEW) in the range of from 174 to 198 g/eq determined according to DIN 16 945.
  • EW Epoxy Equivalent Weight
  • the diglycidyl ether of bisphenol A is a diglycidyl ether of bisphenol A having a viscosity at 25 °C in the range of from 10000 to 14000 mPa s determined according to DIN 53 015 and an EEW in the range of from 182 to 192 g/eq determined according to DIN 16 945 (Epilox A19-03).
  • the process for preparing the curable composition preferably comprises mixing of
  • the process for preparing the curable composition preferably comprises mixing of
  • the catalyst according to c) is admixed.
  • the catalyst is admixed in an amount of from 0.1 to 20 % by weight, preferably of from 0.3 to 5 % by weight, relative to the amount of the epoxy resin.
  • the amount in which the hardener according to b) is admixed is admixed.
  • the hardener is admixed in an amount of from 1 to 35 % by weight, preferably of from 5 to 30 % by weight, more preferably of from 15 to 25 % by weight, relative to the amount of the epoxy resin.
  • the process for preparing the curable composition comprises mixing of
  • the process for preparing the curable composition comprises mixing of
  • At least one further diamine preferably selected from the group consisting of cycloaliphatic diamines, / ⁇ e/a-xylenediamine (MXDA) and meta-para- xylenediamine (MPXDA), more preferably selected from the group consisting of methyl cyclohexyl diamine (MCDA), isophorondiamine (IPDA), 4,4'-diamino dicyclohexyl methane (dicykan), 4,4'-methylene biscyclohexyl amine (PACM20), /77efe-xylenediamine (MXDA) and meta-para-xy ⁇ ened ⁇ am ' me (MPXDA) is admixed.
  • MXDA cycloaliphatic diamines
  • MPXDA meta-para- xylenediamine
  • MXDA cycloaliphatic diamine
  • MPXDA meta-para- xylenediamine
  • MCDA methyl cyclohe
  • At least one further component e) selected from the group consisting of pigments, dyes, tougheners, anti-foaming agents or flame-retarding agents is admixed.
  • the process for preparing the curable composition consists of mixing of the components a), b) and c), more preferably of mixing of the components a), b), c) and d) or of the components a), b), c) and e).
  • the process for preparing the curable composition consists of mixing of the components a), b), c), d) and e).
  • the curable composition prepared according to the process above, has an initial viscosity at 45°C in the range of from 400 to 800 mPa s determined according to DIN 53 015. Also preferably, the time in which the viscosity of the curable composition reaches the double initial viscosity (t o e n) is 30 minutes or more, preferably in the range of from 40 to 150 minutes.
  • reinforcing fibers are added to the curable composition in the process described above.
  • the reinforcing fibers are selected from the group consisting of glass fiber, carbon fiber, nylon fiber and aramid fiber, preferably glass fiber.
  • the reinforcing fibers are endless fibers, preferably in the form of single fibers or rovings.
  • the reinforcing fibers are added in an amount of from 10 to 80 % by volume, preferably of from 25 to 75 % by volume, more preferably of from 30 to 50 % by volume, relative to the total volume of the curable composition.
  • the present invention is directed to a curable composition obtained or obtainable by the process for preparing a curable composition as disclosed above.
  • the present invention is directed to a process for the preparation of a cured epoxy resin mixture, which comprises curing a curable composition as disclosed above, preferably by application of thermal energy (heating), more preferably by heating to a temperature above 60 ° C, more preferably to a temperature in the range of from 100 to 160 °C.
  • thermal energy heating
  • the atmosphere is air.
  • the present invention is directed to a cured epoxy resin which is obtained or obtainable by the process for the preparation of a cured epoxy resin mixture as disclosed above.
  • the present invention is directed to a process for the preparation of composite elements, which comprises
  • an epoxy resin mixture wherein the epoxy resin mixture comprises a) an epoxy resin
  • the composite elements prepared from the curable compositions as disclosed above have good stability against damage caused by hot liquids, especially against hydrolysis caused by hot aqueous media. Said improved stability against damage, especially hydrolysis, is significantly reflected by good interlaminar shear strength results even after storage of test specimen in hot water for a prolonged period of time.
  • the durability of a fiber reinforced plastic is largely dependent on the bonding between the reinforcing fiber and matrix material and on chemical and physical stability.
  • the interlaminar shear strength (ILSS) of a fiber reinforced plastic which is a characteristic parameter in determining durability, is influenced primarily by the interfacial bonding between the reinforcing fiber and the matrix material.
  • composite elements prepared from the curable compositions according to the present invention are well suited to be used for any kind of application which requires contact with hot liquids, especially with hot aqueous media.
  • the support element according to iii) has a diameter, a longitudinal extension vertically to the diameter and an outer surface parallel to the longitudinal extension and wherein applying the reinforcing fibers in iii) is done by winding the reinforcing fibers impregnated with the curable composition around the support element's outer surface.
  • the support element having a diameter, a longitudinal extension vertically to the diameter and an outer surface parallel to the longitudinal extension is preferably a cylinder, which functions as mandrel. Fibers or fiber bundles are pulled through a wet bath containing the curable composition as disclosed above and wound over the rotating mandrel in specific orientations. After curing the mandrel can be removed, leaving a final geometric shape but can be left in some cases.
  • the curing according to iv) can be done by any suitable method.
  • curing is done by application of thermal energy (heating), more preferably by heating to a temperature above 60 ° C and keeping this temperature for at least one hour. More preferably, curing is done by heating to a temperature in the range of from 100 to 180 °C and keeping this temperature for at least 0.5 h, more preferably by heating to a temperature in the range of from 120 to 170 °C and keeping this temperature for a time in the range of from 2 to 10 h, more preferably heating to a temperature in the range of from 130 to 160 °C and keeping this temperature for a time in the range of from 2 to 6 h.
  • the atmosphere is air.
  • a pre-curing step is applied before the curing step iv), wherein said pre-curing step comprises heating to a temperature in the range of from 60 to 100 °C and keeping this temperature for at least 0.5 h, more preferably heating to a temperature in the range of from 70 to 90 °C and keeping this temperature for a time in the range of from 0.5 to 10 h, more preferably heating to a temperature in the range of from 75 to 85 °C and keeping this temperature for a time in the range of from 1.5 to 3 h.
  • the process comprises the steps (i), (ii), (iii), and (iv), preferably (i), (ii), (iii), (iv) and (v), more preferably (i), (ii), (iii), (iv), the pre-curing and (v).
  • the process consists of the steps (i), (ii), (iii) and (iv), preferably of the steps (i), (ii), (iii), (iv) and (v), more preferably of (i), (ii), (iii), (iv), the pre-curing and (v).
  • the epoxy resin according to a) comprises at least one epoxy resin selected from the group consisting of diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of hydrogenated bisphenol A and diglycidyl ether of hydrogenated bisphenol F, preferably at least one diglycidyl ether of bisphenol A.
  • the diglycidyl ether of bisphenol A is a diglycidyl ether of bisphenol A having a viscosity at 25 °C in the range of from 6000 to 18000 mPa s determined according to DIN 53 015 and an Epoxy Equivalent Weight (EEW) in the range of from 174 to 198 g/eq determined according to DIN 16 945.
  • EW Epoxy Equivalent Weight
  • the diglycidyl ether of bisphenol A is a diglycidyl ether of bisphenol A having a viscosity at 25 °C in the range of from 10000 to 14000 mPa s determined according to DIN 53 015 and an EEW in the range of from 182 to 192 g/eq determined according to DIN 16 945 (Epilox A19-03).
  • the epoxy resin mixture comprises
  • the epoxy resin mixture comprises
  • the catalyst c) is present in the curable composition according to ii) in an amount of from 0.1 to 20 % by weight, more preferably of from 0.3 to 5 % by weight, relative to the amount of the epoxy resin.
  • the hardener b) is preferably present in the curable composition according to ii) in an amount of from 1 to 35 % by weight, more preferably of from 5 to 30 % by weight, more preferably of from 15 to 25 % by weight, relative to the amount of the epoxy resin.
  • the epoxy resin mixture comprises a) 100 % by weight of a diglycidyl ether of bisphenol A having a viscosity at 25 °C in the range of from 6000 to 18000 mPa s determined according to DIN 53 015 and an EEW in the range of from 174 to 198 g/eq determined according to DIN 16 945 as epoxy resin;
  • the epoxy resin mixture comprises
  • the epoxy resin mixture comprised in the curable composition according to ii) comprises in addition to a), b) and c)
  • At least one further diamine preferably selected from the group consisting of cycloaliphatic diamines, / ⁇ e/a-xylenediamine (MXDA) and meta-para- xylenediamine (MPXDA), more preferably selected from the group consisting of methyl cyclohexyl diamine (MCDA), isophorondiamine (IPDA) 4,4'-diamino dicyclohexyl methane (dicykan), 4,4'-methylene biscyclohexyl amine (PACM20), /77efe-xylenediamine (MXDA) and meta-para-xy ⁇ ened ⁇ am ⁇ ne (MPXDA).
  • MXDA cycloaliphatic diamines
  • MPXDA meta-para- xylenediamine
  • MXDA cycloaliphatic diamine
  • MPXDA meta-para- xylenediamine
  • the epoxy resin mixture can comprise at least one further component e) selected from the group consisting of pigments, dyes, tougheners, anti-foaming agents or flame-retarding agents.
  • the curable composition according to ii) consist of the epoxy resin mixture, which preferably consists of the components a), b) and c), more preferably of the components a), b), c) and d) or of the components a), b), c) and e), more preferably of the components a), b), c), d) and e).
  • the curable composition according to ii) has an initial viscosity at 45°C in the range of from 400 to 800 mPa s determined according to DIN 53 015.
  • the time in which the viscosity of the curable composition according to ii) reaches the double initial viscosity (t o e n) is 30 minutes or more, preferably in the range of from 40 to 150 minutes.
  • the reinforcing fibers are selected from the group consisting of glass fiber, carbon fiber, nylon fiber and aramid fiber, preferably glass fiber.
  • the reinforcing fibers are endless fibers, more preferably in the form of single fibers or ravings.
  • the amount in which the reinforcing fibers are present in the composite element Preferably, the reinforcing fibers are present in an amount of from 10 to 80 % by volume, preferably of from 25 to 75 % by volume, more preferably of from 30 to 50 % by volume, relative to the total volume of the curable composition.
  • the present invention is directed to a composite element which is obtained or obtainable by a process for the preparation of a composite element as disclosed above.
  • the present invention is furthermore directed to the use of a composite element prepared according to the process for the preparation of a composite element as disclosed above for pipes, tubes or vessels, preferably for pipes, tubes or vessels which are used for transportation or storage of liquid media, more preferably for pipes, tubes or vessels which are used for transportation or storage of hot liquid media.
  • the invention is also directed to a method for transporting or storing liquid media, preferably hot liquid media, wherein the pipes, tubes or vessels used for transportation or storage or for transportation and storage comprise the composite element prepared according to the process for the preparation of a composite element as disclosed above.
  • the liquid media are aqueous media, preferably aqueous media comprising water in a content of at least 10 % by weight, preferably in the range of from 10 to 100 % by weight, more preferably in the range of from 50 % by weight to 100 % by weight.
  • hot refers to a temperature of at least 30 °C, preferably at least 50 °C, more preferably at least 80 °C, more preferably in the range of from 80 to ⁇ 100 °C, at an absolute pressure of 1 bar.
  • a curable composition which comprises an epoxy resin mixture, wherein the epoxy resin mixture comprises
  • DBU diazabicyclo[5.4.0]undec-7-ene
  • DBN 1,5-diazabicyclo[4.3.0]non-5-ene
  • the epoxy resin according to a) comprises at least one epoxy resin selected from the group consisting of diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of hydrogenated bisphenol A and diglycidyl ether of hydrogenated bisphenol F, preferably at least one diglycidyl ether of bisphenol A.
  • EW Epoxy Equivalent Weight
  • At least one further diamine preferably selected from the group consisting of cycloaliphatic diamines, / ⁇ e/a-xylenediamine (MXDA) and meta-para- xylenediamine (MPXDA), more preferably selected from the group consisting of methyl cyclohexyl diamine (MCDA) isophorondiamine (IPDA), 4,4'-diamino dicyclohexyl methane (dicykan), 4,4'-methylene biscyclohexyl amine (PACM20), /77efe-xylenediamine (MXDA) and meta-para-xy ⁇ ened ⁇ am ⁇ ne (MPXDA).
  • MXDA cycloaliphatic diamines
  • MXDA meta-para- xylenediamine
  • MPXDA meta-para- xylenediamine
  • the curable composition according to any one of embodiments 1 to 10 wherein the time in which the viscosity reaches the double initial viscosity (t o e n) is 30 minutes or more, preferably in the range of from 40 to 150 minutes.
  • the curable composition according to any one of embodiments 1 to 1 1 comprising reinforcing fibers embedded in the curable composition.
  • reinforcing fibers are selected from the group consisting of glass fiber, carbon fiber, nylon fiber and aramid fiber, preferably glass fiber.
  • a process for preparing a curable composition which comprises mixing of
  • the epoxy resin according to a) comprises at least one epoxy resin selected from the group consisting of diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of hydrogenated bisphenol A and diglycidyl ether of hydrogenated bisphenol F, preferably at least one diglycidyl ether of bisphenol A.
  • the diglycidyl ether of bisphenol A is a diglycidyl ether of bisphenol A having a viscosity at 25 °C in the range of from 6000 to 18000 mPa s determined according to DIN 53 015 and an Epoxy Equivalent Weight (EEW) in the range of from 174 to 198 g/eq determined according to DIN 16 945 (Epilox A19-03).
  • EW Epoxy Equivalent Weight
  • MXDA
  • the process according to any one of embodiments 16 to 26, wherein the time in which the viscosity of the curable composition reaches the double initial viscosity (t o en) is 30 minutes or more, preferably in the range of from 40 to 150 minutes.
  • reinforcing fibers are selected from the group consisting of glass fiber, carbon fiber, nylon fiber and aramid fiber, preferably glass fiber.
  • a curable composition obtained or obtainable by the process of any one of embodiments 26 to 30.
  • a process for the preparation of a cured epoxy resin mixture which comprises curing a curable composition according to any one of embodiments 1 to 15 or according to embodiment 31 , preferably by application of thermal energy (heating), more preferably by heating to a temperature above 60 °C, more preferably to a temperature in the range of from 100 to 160 °C.
  • thermal energy heating
  • a cured epoxy resin which is obtained or obtainable by a process according to
  • the epoxy resin mixture comprises a) an epoxy resin
  • DETDA diethyl methyl benzene diamine
  • DBU diethyl methyl benzene diamine
  • DBN diethyl methyl benzene diamine
  • v) optionally removing the support element.
  • the support element according to iii) has a diameter, a longitudinal extension vertically to the diameter and an outer surface parallel to the longitudinal extension and wherein applying the reinforcing fibers in iii) is done by winding the reinforcing fibers impregnated with the curable composition around the support element's outer surface.
  • the process according to embodiment 34 or 35 which comprises the steps (i), (ii), (iii), (iv) and (v).
  • the process according to any one of embodiments 34 to 36 which consists of the steps (i), (ii), (iii) and (iv), preferably of the steps (i), (ii), (iii), (iv) and (v).
  • the epoxy resin according to a) comprises at least one epoxy resin selected from the group consisting of diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of hydrogenated bisphenol A and diglycidyl ether of hydrogenated bisphenol F, preferably at least one diglycidyl ether of bisphenol A.
  • the diglycidyl ether of bisphenol A is a diglycidyl ether of bisphenol A having a viscosity at 25 °C in the range of from 6000 to 18000 mPa s determined according to DIN 53 015 and an Epoxy Equivalent Weight (EEW) in the range of from 174 to 198 g/eq determined according to DIN 16 945 (Epilox A19-03).
  • EW Epoxy Equivalent Weight
  • At least one further diamine preferably selected from the group consisting of cycloaliphatic diamines, / ⁇ e/a-xylenediamine (MXDA) and meta-para- xylenediamine (MPXDA), more preferably selected from the group consisting of methyl cyclohexyl diamine (MCDA), isophorondiamine (IPDA), 4,4'-diamino dicyclohexyl methane (dicykan), 4,4'-methylene biscyclohexyl amine (PACM20), /77efe-xylenediamine (MXDA) and meta-para-xy ⁇ ened ⁇ am ⁇ ne (MPXDA).
  • MXDA cycloaliphatic diamines
  • MPXDA meta-para- xylenediamine
  • MXDA cycloaliphatic diamine
  • MPXDA meta-para- xylenediamine
  • the epoxy resin mixture comprises at least one further component e) selected from the group consisting of pigments, dyes, tougheners, anti-foaming agents or flame-retarding agents.
  • the curable composition has an initial viscosity at 45°C in the range of from 400 to 800 mPa s determined according to DIN 53 015.
  • the process according to any one of embodiments 34 to 46, wherein the time in which the viscosity of the curable composition reaches the double initial viscosity (t ope n) is 30 minutes or more, preferably in the range of from 40 to 150 minutes.
  • the reinforcing fibers are selected from the group consisting of glass fiber, carbon fiber, nylon fiber and aramid fiber, preferably glass fiber.
  • reinforcing fibers are endless fibers, preferably in the form of single fibers or ravings.
  • embodiments 34 to 50 or of the composite element of embodiment 51 for pipes, tubes or vessels preferably for pipes, tubes or vessels which are used for transportation or storage of liquid media, more preferably for pipes, tubes or vessels which are used for
  • aqueous media comprising water in a content of at least 10 % by weight, preferably in the range of from 10 to 100 % by weight, more preferably in the range of from 50 % by weight to 100 % by weight.
  • Epilox A19-03 diglycidyl ether of bisphenol A having a viscosity at 25 °C in the range of from 10000 to 14000 mPa s determined according to DIN 53 015 and an EEW in the range of from 182 to 192 g/eq determined according to DIN 16 945
  • EMIM-DCA 1 -ethyl-3-methyl-imidazolium dicyanamide
  • DSC differential scanning calorimetry
  • the individual components were mixed in the ratios as indicated in table 2 in order to obtain epoxy resin mixtures. Afterwards, glass fibers were impregnated with the epoxy resin mixtures in fiber direction 0/90° resulting in laminates with a fiber volume content of about 40 %. Curing was done as indicated in Table 2.
  • the fiber-matrix-adhesion of the cured composite elements (plates) was determined in dry state by interlaminar shear strength (ILSS) experiment according to ASTM D2344. Therein, the force necessary for delamination is determined both in warp and in weft direction. 50% of the test specimen was stored for 14 days in water having a

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

L'invention concerne une composition durcissable, qui comprend un mélange de résine époxyde, le mélange de résine époxyde comprenant : a) une résine époxyde ; b) de la diéthylméthylbenzènediamine (DETDA) utilisée comme durcisseur ; c) au moins un composé choisi dans le groupe constitué par le 1,8-diazabicyclo[5.4.0]undéc-7-ène (DBU) et le 1,5-diazabicyclo[4.3.0]non-5-ène (DBN) utilisé comme catalyseur.
PCT/EP2017/078055 2016-11-03 2017-11-02 Système époxyde WO2018083177A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP16197038 2016-11-03
EP16197038.9 2016-11-03

Publications (1)

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WO2018083177A1 true WO2018083177A1 (fr) 2018-05-11

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102617984A (zh) * 2011-01-26 2012-08-01 中国科学院理化技术研究所 一种改性环氧树脂基体材料及改性环氧树脂基复合材料
EP2592099A1 (fr) * 2011-11-10 2013-05-15 Sika Technology AG Durcisseur comprenant des groupes aminés aromatiques pour résines époxydes

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102617984A (zh) * 2011-01-26 2012-08-01 中国科学院理化技术研究所 一种改性环氧树脂基体材料及改性环氧树脂基复合材料
EP2592099A1 (fr) * 2011-11-10 2013-05-15 Sika Technology AG Durcisseur comprenant des groupes aminés aromatiques pour résines époxydes

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