WO2017049578A1 - Composition de résine époxy - Google Patents

Composition de résine époxy Download PDF

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Publication number
WO2017049578A1
WO2017049578A1 PCT/CN2015/090692 CN2015090692W WO2017049578A1 WO 2017049578 A1 WO2017049578 A1 WO 2017049578A1 CN 2015090692 W CN2015090692 W CN 2015090692W WO 2017049578 A1 WO2017049578 A1 WO 2017049578A1
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Prior art keywords
epoxy resin
composition
precursor
epoxy
cardanol
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PCT/CN2015/090692
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English (en)
Inventor
Hongying Chen
Yue Shen
Minglei JI
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Blue Cube Ip Llc
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Priority to PCT/CN2015/090692 priority Critical patent/WO2017049578A1/fr
Priority to TW105130811A priority patent/TW201723072A/zh
Publication of WO2017049578A1 publication Critical patent/WO2017049578A1/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
    • C08G59/68—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

Definitions

  • the present invention is related to an epoxy resin composition for bridge deck pavements; and more specifically, to an epoxy resin composition useful for manufacturing a waterproofing layer for a bridge deck pavement used in the construction of bridges.
  • Epoxy resins are thermosets with a wide range of physical properties such as high strength (greater than or equal to [ ⁇ ] 78 MPa) , low creep, very low cure shrinkage, excellent resistance to chemicals as well as corrosion and appropriate electrical properties. Information on epoxy resins and their properties can be found in Goodman, S. H. Handbook of Thermoset Plastics, 2nd ed., William Andrew Inc., 1998, incorporated herein by reference.
  • epoxy resin thermoset polymers are typically brittle having fracture energy of about two orders of magnitude lower than engineering thermoplastics and three orders lower than metals.
  • using an epoxy as neat resin is impractical in most applications that require, for example, a resin that has an increased flexibility property such as for making a waterproofing layer of a bridge deck pavement.
  • Bridge deck pavements play an important role to ensure durability and traffic efficiency.
  • bridge deck pavements must meet a large number of requirements, such as: resistance to permanent deformation, texture depth, skid resistance, rigidity, evenness, ageing resistance, among other requirements.
  • Bridge deck pavements must also protect and seal the underlying steel deck under heavy traffic load and severe weather conditions.
  • one layer of pavement generally cannot fulfill all or can only partially fulfill some of the above requirements due to the many different requirements. Therefore, a pavement system, consisting of several layers, is usually adopted in construction of the bridge deck pavements.
  • a pavement system consisting of several layers, is usually adopted in construction of the bridge deck pavements.
  • one of the pavement systems includes an asphalt bridge pavement system.
  • a conventional asphalt bridge pavement system includes, for example, a three-layered structure bonded to a steel bridge deck.
  • a pavement and bridge deck generally indicated by numeral 10.
  • Figure 1 shows a three-layered structure, generally indicated by numeral 20 bonded to a steel bridge deck 30.
  • the three-layered structure 20 includes for example: (1) a sealing/bonding layer (primer) 21 attached to the steel bridge deck 30, (2) a waterproofing layer 22 attached to the primer layer 21, and (3) a surface layer (e.g., asphalt) 23 attached to the waterproofing layer 22.
  • the primer layer can be eliminated from a pavement structure, and the waterproofing layer can be used as the bonding layer between the bridge deck and the top asphalt pavement.
  • a pavement and bridge deck generally indicated by numeral 40.
  • Figure 2 shows a two-layered structure, generally indicated by numeral 50 bonded to a steel bridge deck 60.
  • the two-layered structure 50 includes for example: (1) a waterproofing layer 51 attached to the steel bridge deck 60 and (2) a surface layer (e.g., asphalt) 52 attached to the waterproofing layer 51.
  • the “waterproofing layer” is the bonding layer between the primer layer and the asphalt layer, as shown in Figure 1; or between the asphalt layer and the steel bridge deck as shown in Figure 2.
  • the durability of bridges depends on the effectiveness of the bridge deck waterproofing layer.
  • the main functional requirements for the waterproofing layer includes for example: (1) water and air-tightness under all conditions; (2) adhesion between the bridge and the asphalt mixture; (3) mechanical resistance (traffic loads, thermal expansion) ; (4) resistance to de-icing agents; (5) compatibility with asphalt mixture; and (6) resistance to high temperatures during the application of hot asphalt mixture.
  • elastomeric polymer modified asphalt and epoxy asphalt which is a mixture of an epoxy formulation with highly viscous asphalt.
  • the liquid formulation is usually sprayed onto steel deck surface and cure to form a dry layer; then the melted pavements are paved on the waterproofing layer.
  • the elastomeric polymer modified asphalt’s drawback is the weak deformation stability at elevated temperature.
  • Epoxy asphalt has high viscosity, which restricts its leveling after spraying on to bridge deck.
  • U.S. Patent No. 4,162,998A discloses asphalt-epoxy resin compositions for road pavements.
  • the asphalt–epoxy resin compositions are prepared by mixing heated asphalt with a composition comprising epoxy resin and amine hardener with two active hydrogens.
  • the properties of the above example compositions are measured, including tensile strength, elongation, and softening point.
  • the example epoxy disclosed in the above patent does not include a CNSL modified epoxy.
  • liquid rubber was not introduced into the formulation for flexibility improvement at low temperature.
  • U.S. Patent Application Publication No. US20110152448A1 discloses formulated epoxy systems that exhibit a highly favorable combination of tensile strength and elongation when compared to prior art epoxy systems.
  • the elastomeric epoxy resin systems disclosed in the above publication are prepared utilizing a curing agent containing at least one mono-primary amine, and are particularly useful in applications such as, for example, castings, potting, composites, crack sealing, coatings, adhesives, and the like.
  • the epoxy resin in the formulations is EPON Resin 828, which is a diglycidyl ether of bisphenol A. CNSL modification of epoxy was not taught. Moreover, liquid rubber was not introduced into the formulation for flexibility improvement at low temperature.
  • CN104449514A discloses one formulated system of ambient-cure epoxy adhesive for application as waterproofing or bonding layer between bridge decks and upper pavements in road and bridge construction.
  • the epoxy system consists of Part A, comprising a bisphenol A based epoxy and flexible epoxy, and Part B hardener, comprising cardanol modified amine and polyol toughening additive.
  • Part A comprising a bisphenol A based epoxy and flexible epoxy
  • Part B hardener comprising cardanol modified amine and polyol toughening additive.
  • the modification of epoxy with cardanol is not taught in the above reference.
  • the elongation value at break of exemplified formulations is in the range of 100-150%, which is a range that needs to be improved by a new formulation system.
  • WO2015/085461A1 discloses a novel thermoplastic polyaminoether with application as waterproofing and bonding layer between bridge decks and upper pavements in road and bridge construction.
  • the invented liquid formulation is a two-component system, consisting of epoxy part and newly synthesized phenalkamine hardener part.
  • the novel phenalkamine was synthesized by reaction of cashew nutshell liquid with monoethanolamine.
  • the invented formulation has shortened drying time and improved pull-off strength in comparison to control formulations.
  • chemical modification of epoxy with cashew nutshell liquid was not taught in this prior art, and the elongation of cured layer was not studied.
  • One embodiment of the present invention is directed to a precursor epoxy resin composition including, for example: (a) at least one epoxy resin diluent, (b) a compound containing a cardanol moiety, including for example CNSL derivatives, and (c) at least one catalyst.
  • Another embodiment of the present invention is directed to a process for preparing the above precursor epoxy resin composition.
  • Still another embodiment of the present invention is directed to a curable epoxy resin composition including for example (A) the above precursor epoxy resin composition; and (B) a curing agent.
  • Yet another embodiment of the present invention is directed to a process for producing the above curable epoxy resin composition.
  • Even still another embodiment of the present invention is directed to a cured product prepared by curing the above curable epoxy resin composition.
  • Even yet another embodiment of the present invention is directed to a process for producing the above cured product.
  • the present invention is directed to a formulated epoxy system as a new type of design for a bonding layer for bridge pavement applications.
  • the present invention includes a curable composition including a Part A (an epoxy composition) and a Part B (ahardener composition) .
  • the Parts A and B are mixed before spraying the mixture onto a bridge deck.
  • the advantages of the formulated system of the present invention includes: (1) strong adhesion to both steel deck and epoxy asphalt pavement, for example a pull-off adhesion of greater than [>] 3.0 MPa; (2) improved elongation at low temperature, for example an elongation at break of>100 %at-10 °C; and (3) high strength at ambient temperature, for example a tensile strength of>5 MPa at 23 °C.
  • novel epoxy resins may be synthesized from the reaction of butanediol diglycidyl ether (BDDGE) and cashew nutshell liquid (CNSL) .
  • BDDGE butanediol diglycidyl ether
  • CNSL cashew nutshell liquid
  • a reactive elastomeric polymer may be introduced into the formulation to improve low-temperature flexibility (or elongation) . Due to the synergetic effect of the formulation, the formulated system of the present invention becomes a thermosetting structure after curing, and the cured thermoset possesses strong adhesion to steel plate, and high flexibility at both room temperature and low temperature (e.g., -10°C) .
  • the new epoxy resin compositions of the present invention may be illustrated by structure schemes as follows:
  • n and m can be any integer in the range of 0 to 20;
  • Figure 1 is a schematic cross-sectional view showing a part of a layered structure for a conventional type of steel bridge pavement system.
  • Figure 2 is another schematic cross-sectional view showing a part of a layered structure for another conventional type of steel bridge pavement system.
  • “Structural adhesives” herein means adhesives to provide strong bonding to a substrate such as metals including for example steel and aluminum; and other materials.
  • Waterproofing herein means impervious to water.
  • Deformation stability herein means the ability to keep the original shape or dimension under external forces.
  • the present invention includes an precursor epoxy resin diluent composition including: (a) at least one epoxy resin diluent, (b) a compound containing a cardanol moiety such as CNSL and CNSL derivatives, and (c) optionally, at least one catalyst.
  • Epoxy resin diluents, component (a) , useful in preparing the precursor epoxy resin diluent composition of the present invention can include a wide variety of epoxy resin compounds. Any epoxy diluent compound that improves the mechanical and thermal performance of the final composition is preferably used as the epoxy resin diluent composition.
  • the epoxy diluents, (or polyepoxides) useful in the present invention may include aliphatic, cycloaliphatic, aromatic, hetero-cyclic epoxy diluents, and mixtures thereof.
  • the epoxy diluent may contain, on the average, one or more reactive oxirane groups.
  • Epoxy resins useful in the embodiments described herein may include for example mono-functional epoxy resins, multi-or poly-functional epoxy resins, and combinations thereof.
  • the epoxy resins useful in the present invention and the preparation of such epoxy resins are disclosed, for example, in Lee, H. and Neville, K., Handbook of Epoxy Resins, McGraw-Hill Book Company, New York, 1967, Chapter 2, pages 2-1 to 2-27, incorporated herein by reference.
  • Suitable examples of the epoxy resin diluent, component (a) , useful in the present invention may include, but are not limited to, butyl glycidyl ether (BGE) , phenyl glycidyl ether (PGE) , cresol glycidyl ether (CGE) , benzyl glycidyl ether, p-tert-butylphenyl glycidyl ether, 2-ethyl hexyl glycidyl ether, decyl glycidyl ether, alkyl (C12-C14) glycidyl ether (AGE) , polyglycol diglycidyl ether, polypropylene diglycidyl ether, 1, 4-butanediol diglycidyl ether (BDDGE) , 1, 6-hexanediol diglycidyl ether (HDDGE) , ethylene glycol diglycidyl
  • epoxy resin diluent may include commercial resins such as D.E.R. TM 331; D.E.R. 337; D.E.R. 736; and mixtures thereof.
  • the above D.E.R. epoxy resins are commercial products available from The Dow Chemical Company.
  • One of the beneficial properties of the epoxy resin is its lower viscosity which can be, for example, less than about 5,000 mPa-s.
  • Component (b) for the precursor epoxy resin diluent composition of the present invention includes a compound containing a cardanol moiety such as for example cardol, cardanol, CNSL derivatives, and mixtures thereof.
  • a compound containing a cardanol moiety such as for example cardol, cardanol, CNSL derivatives, and mixtures thereof.
  • Exemplary of the compound containing a cardanol moiety useful in the present invention includes an epoxidized cardanol, an epoxy resin modified cardanol, phenalkamine, cashew nutshell liquid, cardanol based anhydride, and mixtures thereof.
  • the cashew nut shell liquid (CNSL) used may comprise a certain concentration of cardol, cardanol, and mixtures thereof.
  • the concentration of cardol in the CNSL may be, based on the total weight of the CNSL, 35 wt %or more in one embodiment, 40 wt %or more in another embodiment, or 45 wt %or more in still another embodiment; and at the same time, the cardol in the CNSL may be, based on the total weight of the CNSL, 60 wt %or less in one embodiment, 55 wt%or less in another embodiment, or 50 wt %or less in still another embodiment.
  • the chemical structure of cardanol is a phenol containing one hydroxyl group in the para-position, and an aliphatic side chain of from 15 carbon atoms in the meta-position.
  • the cardanol useful in the present invention is one component of CNSL, an oil isolated from the shell of the cashew nut. Cardanol can be illustrated, for example, by the following general chemical formula:
  • R can be for example C 15 H 31-n
  • n can be for example a numerical integer of 0, 2, 4, or 6.
  • Some specific side chains, R, of cardanol can include for example –C 15 H 25 , –C 15 H 27 , or –C 15 H 29 .
  • the concentration of cardanol in the CNSL may be, based on the total weight of the CNSL, 45 wt%or more, 45 wt%or more, or even 50 wt%or more, and at the same time, 70 wt%or less, 65 wt%or less, or even 60 wt%or less.
  • the concentration of cardanol in the CNSL may be, based on the total weight of the CNSL, 40 wt %or more in one embodiment, 45 wt %or more in another embodiment, or 50 wt %or more in still another embodiment; and at the same time, the cardanol in the CNSL may be, based on the total weight of the CNSL, 70 wt %or less in one embodiment, 65 wt%or less in another embodiment, or 60 wt %or less in still another embodiment.
  • the compound containing a cardanol moiety can be, for example, a cardanol-modified epoxy resin.
  • a cardanol-modified epoxy resin is the reaction product of epoxy resin and cardanol.
  • the epoxy resin used to prepare the cardanol-modified epoxy resin can be one or more of the same aforementioned epoxy resins as referenced above with regard to the epoxy resin component (i) .
  • the compound containing a cardanol moiety can be, for example, a glycidyl ether made of CNSL.
  • the glycidyl ether made of CNSL compound useful in the present invention can be one or more of the compounds described in the following publications: Gedam, P.H.; Sampathkumaran, P.S. “Cashew nut shell liquid: extraction, chemistry and applications. Progress in Organic Coatings, 1986, 14, 115-157.; and Kanehashi, S.; Yokoyama, K.; et al. “Preparation and characterization of cardanol-based epoxy resin for coating at room temperature curing. ” Journal of Applied Polymer Science, 2013, 130, 2468-2478, both which are incorporated herein by reference.
  • the compound containing a cardanol moiety can be, for example, one or more phenalkamines.
  • a phenalkamine is the condensation product of cardanol, formaldehyde, and a polyamine via the Mannich reaction (aminomethylation) well known in the art.
  • the polyamine used to produce a phenalkamine can be, for example, an aliphatic ethyleneamine, a cycloaliphatic amine, an aromatic amine, or mixtures thereof.
  • the phenalkamine can be ethylenediamine (EDA) , diethylenetriamine (DETA) , triethyenetetraamine (TETA) , tetraethylenepentaamine (TEPA) , N-aminoethylenepiperazine (AEP) , isophorone diamine (IPDA) , m-xylene diamine (MXDA) , or mixtures thereof.
  • EDA ethylenediamine
  • DETA diethylenetriamine
  • TETA triethyenetetraamine
  • TEPA tetraethylenepentaamine
  • AEP N-aminoethylenepiperazine
  • IPDA isophorone diamine
  • MXDA m-xylene diamine
  • the compound containing a cardanol moiety can be, for example, a cardanol-modified anhydride.
  • a cardanol-modified anhydride resin is the reaction product of anhydride and the cardanol.
  • the anhydride used to prepare the cardanol-modified anhydride can include, for example, phthalic acid anhydride and derivatives phthalic acid anhydride, nadic acid anhydride and derivatives of nadic acid anhydride, trimellitic acid anhydride and derivatives of trimellitic acid anhydride, pyromellitic acid anhydride and derivatives of pyromellitic acid anhydride, benzophenonetetracarboxylic acid anhydride and derivatives benzophenonetetracarboxylic acid, dodecenylsuccinic acid anhydride and derivatives of dodecenylsuccinic acid anhydride, poly (ethyloctadecanedioic acid) anhydride and derivatives of poly (ethyloctadecanedioic acid) anhydride, and the like, or mixtures thereof.
  • Each of the above cardanol-modified anhydride resins can be used alone or in an admixture
  • One of the beneficial properties of the compound containing a cardanol moiety is its low viscosity, i.e., a viscosity of lower than about 1,000 mPa-s.
  • the epoxy resins containing cardanol moiety have a lower viscosity than bisphenol A-based epoxy resins with similar EEW.
  • EP-001 has viscosity of 780 mPa. s
  • D.E.R. 664 is a solid epoxy resin at room temperature (e.g., about 25 °C) .
  • the molar ratio of epoxy groups to phenolic hydroxyl groups may be in the range of from about 10: 1 to about 1: 1 in one embodiment, from about 5: 1 to about 1: 1 in another embodiment, and from about 3: 1 to about 1: 1 in still another embodiment.
  • the optional catalyst compound useful in the precursor epoxy resin diluent composition of the present invention composition may include for example basic inorganic reagents, phosphines, quaternary ammonium compounds, phosphonium compounds, amines, imidazoles, substituted imidazoles, or mixtures thereof.
  • Some specific examples of catalysts useful in the present invention includes: NaOH, KOH, triethanolamine, triphenylphosphine.
  • Ethyltriphenylphosphonium acid acetate (ETPPAAc) ethylphenylphosphonium iodide (ETPPI)
  • DBU 1, 8-diazabicyclo [5.4.0] undec-7-ene
  • the above catalysts advantageously can be prepared into a solution of methanol or ethanol before use.
  • Preferred embodiments of the catalyst compound in the precursor epoxy resin diluent composition of the present invention composition may include for example ETPPAAc, DBU, or mixtures thereof.
  • the ETPPAAc may be prepared into a solution of methanol with a content of, for example, 70 wt %or other concentrations.
  • One of the beneficial properties of the catalyst compound is the capability of the catalyst to selectively drive the reaction of epoxy groups with phenolic OH groups rather than secondary OH groups.
  • the concentration of the catalyst compound used in the precursor epoxy resin diluent composition of the present invention may range generally from about 10 ppm to about 50,000 ppm in one embodiment, from about 100 ppm to about 5,000 ppm in another embodiment, from about 200 ppm to about 1,000 ppm in still another embodiment, and from about 200 ppm to about 500 ppm in yet another embodiment, based on the total weight of the components in the hardener composition. If the catalyst concentration is lowered below 10 ppm, the reaction may proceed slowly, and may not reach the designed conversion even when increasing reaction time and reaction temperature. If the catalyst concentration is increased to a very high level, i.e., above 50,000 ppm, the reaction may proceed at a high reaction rate, and the reaction may run away or form a gel due to accelerated release of reaction exotherm.
  • the precursor epoxy resin diluent composition of the present invention may include various other optional compounds.
  • the optional compounds that may be added to the precursor epoxy resin diluent composition may include compounds that are normally used in resin formulations known to those skilled in the art for preparing compositions and thermosets.
  • the other optional compounds that may be added to the precursor epoxy resin diluent composition of the present invention may include additives generally known to be useful for the preparation, storage, application, and curing of epoxy resin compositions.
  • additives known to those skilled in the art customarily used in diluent compositions may be added to the composition including, for example, one or more of the following compounds: pigments, fillers, leveling assistants, and the like, or mixtures thereof.
  • the optional compounds that may be added to the composition of the present invention may include for example phenolic compounds such as bisphenol A.
  • the amount of the other optional additives used in the present invention may be in the range of from 0 wt %to about 40 wt %based on the total weight of the resin forming components of the composition in one embodiment, from about 0.01 wt %to about 30 wt %in another embodiment, and from 0.1 wt %to about 20 wt %in still another embodiment.
  • too much (i.e., >40%) additives or fillers are added to the composition, the resultant products may lose specified flexibility, i.e., the elongation at break may be disadvantageously reduced.
  • the process for preparing a precursor epoxy resin diluent composition of the present invention includes admixing: (a) at least one epoxy resin diluent, (b) a compound containing a cardanol moiety such as CNSL and CNSL derivatives, and (c) optionally, at least one catalyst.
  • the precursor epoxy resin diluent composition is synthesized under conditions to form the composition.
  • the epoxy diluents, cardanol derivative and catalyst may be charged into a reaction vessel. Then, the components are admixed for a time and temperature until the theoretical value of the epoxy is reached.
  • the precursor epoxy resin diluent composition is synthesized by admixing the following components: (a) at least one epoxy resin diluent, (b) a compound containing a cardanol moiety such as CNSL and CNSL derivatives, and (c) optionally, at least one catalyst.
  • the mixture may be blending in any known mixing equipment or reactor vessels.
  • the reaction of cardanol derivatives and epoxy diluents can be conducted in the presence of a catalyst to promote the reaction of the phenolic hydroxyl groups with epoxy groups.
  • a catalyst to promote the reaction of the phenolic hydroxyl groups with epoxy groups.
  • the catalyst may be mixed with the half-ester and the polyglycidyl ether in any order.
  • the catalyst can be added to the resultant mixture.
  • the above compounds for synthesizing the precursor epoxy resin diluent composition can be mixed and dispersed at a temperature enabling the preparation of an effective advanced epoxy resin composition.
  • the temperature of mixing the components may be generally from about 20 °C to about 100 °C in one embodiment, and from about 50 °C to about 130 °C in another embodiment.
  • the time for synthesizing the precursor epoxy resin diluent composition may be from about 30 min to about 1 hour in one embodiment and from about 1 hour to about 2 hours in another embodiment.
  • the temperature may be raised to about 140 °C slowly for example at a temperature rate of from about 1 °C/minute to about 5 °C/minute.
  • the reaction temperature may be in the range of from about 100 °C to about 200 °C in one embodiment, from about 110 °C to about 170 °C in another embodiment, and from about 130 °C to about 150 °C in still another embodiment.
  • the reaction can be monitored with titration of the epoxy value of the reactant mixture.
  • the reaction may be stopped when the epoxy reaches its theoretical value.
  • the preparation of the precursor epoxy resin diluent composition useful in the present invention, and/or any of the steps thereof, may be a batch or a continuous process.
  • the mixing equipment used in the process may be any vessel and ancillary equipment well known to those skilled in the art.
  • the precursor epoxy resin diluent composition of the present invention before the composition is mixed with a curing agent, exhibits several beneficial properties including for example a lower viscosity than bisphenol A-based epoxy resins with a similar epoxy equivalent weight (EEW) .
  • EW epoxy equivalent weight
  • the precursor epoxy resin diluent composition, component (A) may be combined with a crosslinker compound, component (B) , to form a curable epoxy resin composition of the present invention which ultimately may be used in preparing a waterproofing layer of a bridge deck pavement used in the construction of bridges.
  • a crosslinker compound, component (B) may be combined with a crosslinker compound, component (B) , to form a curable epoxy resin composition of the present invention which ultimately may be used in preparing a waterproofing layer of a bridge deck pavement used in the construction of bridges.
  • component (C) such as a solvent or a curing catalyst known in the art can then be added to the curable composition.
  • the epoxy resin product prepared by reaction of butanediol diglycidyl ether and cashew nutshell liquid are examples of this component. They are EP-001, EP-002, and EP-003, which were described for their synthesis in later paragraphs.
  • Bisphenol A based epoxy like DER 331 epoxy, may be used to blend with EP-001, EP-002, EP-003.
  • Other aliphatic epoxy resins like DER 337, DER 736, may be used for blending with EP-001, EP-002, EP-003.
  • EP-003 can be used and can deliver the best properties for the formulation.
  • the precursor epoxy resin diluent composition, component (A) , useful in preparing the curable epoxy resin composition may be as described above.
  • the concentration of the precursor epoxy resin diluent composition used to form the curable epoxy resin composition of the present invention may range generally from about 30 wt %to about 60 wt %in one embodiment, from about 40 wt %to about 60 wt %in another embodiment, from about 30 wt %to about 50 wt %in still another embodiment, and from about 40 wt %to about 50 wt %in yet another embodiment, based on the total weight of the components in the curable composition. If very low concentrations are used, the curing process may be very slow, and cured product may have low hardness. If very high concentrations are used, the curing process may still be very slow, and cured product may have low hardness.
  • the curing agent compound, component (B) (also referred to as a hardener, crosslinker compound, or a crosslinking agent) , useful in preparing the curable epoxy resin composition of the present invention can include for example, amines, such as primary amines, secondary amines, or aliphatic amines, phenalkamines, polyetheramines, cycloaliphatic amines, polyamines with two, or more than two, active hydrogens, and amine terminated polymers.
  • amines such as primary amines, secondary amines, or aliphatic amines, phenalkamines, polyetheramines, cycloaliphatic amines, polyamines with two, or more than two, active hydrogens, and amine terminated polymers.
  • the curing agent, component (B) useful for preparing the curable epoxy resin composition of the present invention may include for example oleyl amine, coconut amine, aminoethylpiperazine (AEP) , amine-terminated polymers such as amine terminated butadiene-acrylonitrile (ATBN) polymer, hydroxyl-terminated polybutadiene, bisphenol A and mixtures thereof.
  • the formulations of the present invention may contain the above amines in the hardener Part B.
  • the concentration of the curing agent compound used to form the curable epoxy resin composition of the present invention may range generally from about 30 wt %to about 60 wt %in one embodiment, from about 30 wt %to about 50 wt %in another embodiment, from about 40 wt %to about 60 wt %in still another embodiment, and from about 40 wt %to about 50 wt %in yet another embodiment, based on the total weight of the components in the curable composition. If very low concentrations are used, the curing process may be very slow, and cured product may have low hardness. If very high concentrations are used, the curing process may still be very slow, and cured product may have low hardness.
  • the optional compounds that can be used in the present invention may include for example defoamers, leveling agents, fillers such as silica, and mixtures thereof.
  • optional compounds can be added to the formulation.
  • the optional compounds that may be added to the formulation of the present invention may include compounds that are normally used in curable resin formulations known to those skilled in the art.
  • the optional components used in the formulation preferably are used in a concentration sufficient to prepare the formulation with minimal impact to the thermal and mechanical properties of the formulation or to the final product made from the formulation.
  • Optional compounds that can be added to the formulation may include, for example, compounds that can be added to the formulation to enhance application properties (e.g., surface tension modifiers or flow aids) , reliability properties (e.g., adhesion promoters) the reaction rate, the selectivity of the reaction, and/or the catalyst lifetime.
  • application properties e.g., surface tension modifiers or flow aids
  • reliability properties e.g., adhesion promoters
  • optional compounds that may be added to curable epoxy composition may include, other co-curing agents; catalysts; solvents; fillers; pigments; toughening agents; flexibilizing agents, processing aides; flow modifiers; adhesion promoters; diluents; stabilizers; plasticizers; curing catalysts; catalyst de-activators; flame retardants; aromatic hydrocarbon resins, coal tar pitch; petroleum pitch; carbon nanotubes; graphene; carbon black; carbon fibers, or mixtures thereof.
  • any of the above optional compounds when used to form the curable formulated structural adhesive composition of the present invention, may be used in a concentration of, for example, in the range of from about 0 wt %to about 40 wt %, based on the total weight of the components forming the curable composition in one embodiment similar to the amount of optional components that can be used for forming the precursor epoxy resin diluent composition described above.
  • the amount of the optional compounds used in the curable composition can be in the range of from about 0.01 wt %to about 30 wt %, and from 0.1 wt %to about 20 wt %in still another embodiment.
  • adding too much (i.e., >40%) of the optional compounds to the composition may result in a resultant products that may lose specified flexibility, i.e., the elongation at break may be disadvantageously reduced.
  • the properties, such as flowability and viscosity, of the curable epoxy resin composition of the present invention, before the composition is cured, are such that the formulation can be easily handled and processed.
  • the epoxy resin formulation or composition has a viscosity in the range of from about 400 mPa-sto about 5,000 mPa-sin one embodiment, and from about 500 mPa-sto about 3,000 mPa-sin another embodiment.
  • composition does not require a solvent component
  • another advantage of using the curable coil primer composition of the present invention, before the composition is cured, is that VOCs will not be a problem when no solvent is used in the composition.
  • the curable epoxy resin composition of present invention can be cured to form a thermoset or cured composition, i.e., to adhere between two parts as the curable epoxy resin composition cures.
  • the curable epoxy resin composition or formulation of the present invention can be cured under conventional processing conditions to form a layer adhering two parts together. Curing the curable epoxy resin composition may be carried out at curing reaction conditions including a predetermined temperature and for a predetermined period of time sufficient to cure the composition.
  • the curing conditions include, for example, curing the curable epoxy resin composition at a temperature, generally in the range of from about 10 °C to about 80 °C in one embodiment; from about 10 °C to about 60 °C in another embodiment; from about 10 °C to about 50 °C in still another embodiment, and from about 10 °C to about 30 °C in yet another embodiment.
  • a curing temperature higher than 80 °C may speed up the curing process to the detriment of the process.
  • the curing may be carried out for a time sufficient to produce a cured product, for example, generally for a time of from about 2 hours to about 7 days in one embodiment, from about 6 hours to about 72 hours in another embodiment; and from about 24 hours to about 48 hours in still another embodiment.
  • the curable epoxy resin composition may be applied as a waterproofing layer in between a sealing/bonding layer (primer) and a surface layer (e.g., asphalt) , using a drawdown bar, a roller, a brush, or other conventional method practiced in the bridge industry. Then, the curable epoxy resin composition may be cured at the curing temperatures described above in a conventional manner.
  • Part A and Part B can be mixed according to a specified weight ratio in a clean, dry metal container.
  • a mechanical agitator can be used to prepare a uniform liquid mixture. During the mixing process, care should be taken so as not to entrap air in the system during mixing; 3-10 minutes of thorough mixing can be sufficient to provide a useful mixture.
  • the mixed material can be used within 30 minutes after mixing at 23 °C. Then the mixed material can be spread onto the surface of a bonding layer (or steel bridge deck) using a drawdown bar or a spray gun (or spray equipment) or other known application means.
  • the cured composition (cured thermoset product) of the present invention can exhibit a combination and a balance of advantageous properties including for example an improved adhesion to steel plate surface (>3.0 MPa) and good flexibility (elongation) at both ambient temperature (about 23 °C) and low temperature (-10 °C) .
  • low temperature (-10 °C) elongation data has not been reported in the prior art.
  • the cured composition of the present invention has a good balance of tensile strength (e.g., >about 5 MPa) ; and flexibility (e.g., elongation>about 100 %at-10 °C and elongation>about 200 %at 23 °C) .
  • the resulting cured material or thermoset exhibits several beneficial properties including for example an increased flexibility property (e.g., elongation at break greater than about 100 %at-10 °C) , a high Shore D hardness (e.g., greater than about 10) , a high tensile strength (e.g., greater than about 5 MPa) , a high elongation at break (e.g., greater than about 200 %at 23 °C ) , and a high pull-off adhesion (e.g., greater than about 3 MPa) , particularly for making a cured waterproofing layer of a bridge deck pavement.
  • an increased flexibility property e.g., elongation at break greater than about 100 %at-10 °C
  • a high Shore D hardness e.g., greater than about 10
  • a high tensile strength e.g., greater than about 5 MPa
  • a high elongation at break e.g., greater than about 200
  • the cured thermoset has a pull-off adhesion generally in the range of from about 3.0 MPa to about 10.0 MPa in one embodiment, and from about 3 MPa to about 5 MPa in another embodiment.
  • the cured thermoset has a Shore D hardness in the range of from about 10 to about 40 in one embodiment, and from about 20 to about 30 in another embodiment.
  • the cured thermoset has a tensile strength in the range of from about 3 MPa to about 20 MPa in one embodiment, and from about 5 MPa to about 10 MPa in another embodiment.
  • the cured thermoset has an elongation at break (at 23 °C) in the range of from about 100 %to about 400 %in one embodiment, and from about 200 %to about 300 %in another embodiment.
  • the cured thermoset has a flexibility property (elongation at break at-10 °C) in the range of from about 50%to about 200%in one embodiment, and from about 100%to about 200%in another embodiment.
  • the curable epoxy resin formulation or composition of the present invention is used for bridge deck pavements; and more specifically, for manufacturing a waterproofing layer of a bridge deck pavement used in the construction of bridges.
  • the curable epoxy resin composition includes a combination of compounds that advantageously imparts unique and beneficial properties to the resulting cured epoxy resin product which can be used as waterproofing layer of a bridge deck pavement.
  • the curable formulation may be used as a bonding layer to replace a conventional sealing layer on the surface of a steel bridge deck.
  • the curable epoxy resin formulation or composition of the present invention is useful in a pavement system such as an asphalt bridge pavement system wherein the asphalt bridge pavement system includes three main layers: (1) a sealing/bonding layer (primer) , (2) a waterproofing layer, and (3) a surface layer (e.g., asphalt) ; and the cured thermoset from the curable epoxy resin composition forms the waterproofing layer in between the primer layer and the asphalt layer binding the primer and asphalt layers together.
  • a sealing/bonding layer primary
  • a waterproofing layer e.g., asphalt
  • a surface layer e.g., asphalt
  • the waterproofing layer of the present invention may be used in an asphalt bridge pavement structure having any number of various layers, including the waterproofing layer.
  • one layer of the structure can be the waterproofing layer such that the waterproofing layer is disposed between the primer layer and the asphalt layer.
  • the types of layers used, the number of layers, and the thickness of the layers can be readily determined by those skilled in the art in manufacturing bridge pavement.
  • a bridge pavement structure can include a waterproofing layer directly applied to a primer layer and the asphalt layer is applied to the waterproofing layer.
  • the waterproofing layer may be applied to the steel bridge deck surface directly, without the application of primer layer, and the asphalt layer is applied to the waterproofing layer.
  • Viscosity is measured using Brookfield CAP-2000+with #6 spindle according to the method of ASTM D445 (2010) .
  • EEW is determined by using Mettler Toledo T70 Titrator according to the test method of ASTM D1652 (2004) .
  • Shore D hardness is measured using a durometer according to the test method of ASTM D2240 (2010) .
  • Tensile strength and elongation at break were measured using an Instron model 4505 Materials Testing System according to the test method of ASTM D638 (2010) at two temperatures: 23 °C and-10 °C.
  • Pull-off adhesion was measured using adhesion testing form according to the testing method of ASTM D4541 (2002) .
  • the commercial epoxy overlay system Mark 165 was coated to square concrete substrate, and cured at room temperature. Then the epoxy formulation system to be tested was cast on the surface of Mark 165 layer, attached by steel panel. The epoxy formulation was cured at 160 °C for 2 hours before testing.
  • the reaction was held at 180 °C for another 2 hours before discharging of a final product.
  • the synthesized epoxy resin has an EEW of 588 (eq. ) and a viscosity of 235 mPa-sat 23 °C.
  • Part A comprises a commercial epoxy resin (D.E.R. 337, D.E.R. 331, or D.E.R. 736) or one of the synthesized flexible epoxy (EP-001, EP-002, and EP-003) for the above Synthesis Examples 1, 2 and 3, respectively.
  • Part B comprises Oleyl amine as a basic hardener component, a liquid rubber to improve flexibility of the cured layer, and other components. To compare the effect on performance of the cured layers, three new epoxy resins were formulated into different formulation and their content were modified.
  • HTPB hydroxyl-terminated polybutadiene
  • ATBN amine-terminated butadiene-acrylonitrile
  • Part A and Part B Viscosity of Part A and Part B were measured (Table III) .
  • Part A has viscosity of ⁇ 10,000 mPa-s (except for Formulation F-1 with viscosity of 18750 cP)
  • Part B has viscosity of ⁇ 1,000 mPa-s.
  • formulations were prepared by mixing Part A with Part B (described in Table II) using a high speed mixer.
  • Membrane samples were prepared by casting the formulation to Teflon plate and curing at 80 °C for 2 days before measurements.
  • the measured properties of cured formulation are summarized in Table IV.
  • Most of the formulations have a hardness property close to or greater than 20, except for the F-3 sample which has a hardness of 12D.
  • Most of the formulations have a tensile strength at 23 °C of greater than 5 MPa, and a tensile strength at-10 °C of greater than 20 MPa. Elongation is the property related to material flexibility.

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

Abstract

La présente invention concerne une composition de diluant à base de résine époxyde précurseur comprenant : a) au moins un diluant de résine époxy, (b) un composé contenant une fraction de cardanol, et (c) optionnellement, au moins un catalyseur ; une composition de résine époxy durcissable comprenant (A) la composition de diluant à base de résine époxy précurseur ci-dessus et (B) un composé de réticulation ; et une couche d'étanchéité comprenant un produit réactionnel de (i) la composition de diluant à base de résine époxy précurseur ci-dessus et (ii) d'un composé de réticulation.
PCT/CN2015/090692 2015-09-25 2015-09-25 Composition de résine époxy WO2017049578A1 (fr)

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CN110229617A (zh) * 2019-07-16 2019-09-13 正邦(广州)新材料有限公司 一种蠕变型环氧沥青及其制备方法
CN111234181A (zh) * 2020-04-01 2020-06-05 全球能源互联网研究院有限公司 一种高韧性绝缘环氧树脂固化物及其制备方法和应用
CN113025155A (zh) * 2021-02-07 2021-06-25 南京工业大学 一种高防腐特性生物基涂料的制备方法
CN109734922B (zh) * 2018-12-27 2021-09-17 常熟耐素生物材料科技有限公司 一种非离子反应型环氧树脂乳化剂及其制备方法
CN113683752A (zh) * 2021-10-14 2021-11-23 山东天茂新材料科技股份有限公司 一种高韧性环氧树脂的制备方法
CN114539796A (zh) * 2022-03-07 2022-05-27 鄂尔多斯市路泰公路工程有限责任公司 一种耐高温的路用环氧沥青及其制备方法
CN116285689A (zh) * 2023-03-30 2023-06-23 湖北古城建筑防水工程有限公司 一种可低温熔化的非固化沥青防水涂料及其制备方法

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CN104693966A (zh) * 2015-02-09 2015-06-10 中国船舶重工集团公司第七二五研究所 一种水下施工无溶剂防腐涂料的制备方法

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US20150051317A1 (en) * 2012-03-20 2015-02-19 Yan Wu Modified epoxy resin composition used in high solids coating
CN104693966A (zh) * 2015-02-09 2015-06-10 中国船舶重工集团公司第七二五研究所 一种水下施工无溶剂防腐涂料的制备方法

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109734922B (zh) * 2018-12-27 2021-09-17 常熟耐素生物材料科技有限公司 一种非离子反应型环氧树脂乳化剂及其制备方法
CN110229617A (zh) * 2019-07-16 2019-09-13 正邦(广州)新材料有限公司 一种蠕变型环氧沥青及其制备方法
CN110229617B (zh) * 2019-07-16 2021-07-30 正邦(广州)新材料有限公司 一种蠕变型环氧沥青及其制备方法
CN111234181A (zh) * 2020-04-01 2020-06-05 全球能源互联网研究院有限公司 一种高韧性绝缘环氧树脂固化物及其制备方法和应用
CN111234181B (zh) * 2020-04-01 2023-03-28 全球能源互联网研究院有限公司 一种高韧性绝缘环氧树脂固化物及其制备方法和应用
CN113025155A (zh) * 2021-02-07 2021-06-25 南京工业大学 一种高防腐特性生物基涂料的制备方法
CN113683752A (zh) * 2021-10-14 2021-11-23 山东天茂新材料科技股份有限公司 一种高韧性环氧树脂的制备方法
CN114539796A (zh) * 2022-03-07 2022-05-27 鄂尔多斯市路泰公路工程有限责任公司 一种耐高温的路用环氧沥青及其制备方法
CN114539796B (zh) * 2022-03-07 2023-02-28 鄂尔多斯市路泰公路工程有限责任公司 一种耐高温的路用环氧沥青及其制备方法
CN116285689A (zh) * 2023-03-30 2023-06-23 湖北古城建筑防水工程有限公司 一种可低温熔化的非固化沥青防水涂料及其制备方法
CN116285689B (zh) * 2023-03-30 2024-06-07 湖北古城建筑防水工程有限公司 一种可低温熔化的非固化沥青防水涂料及其制备方法

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