WO2019051885A1 - 一种环氧树脂材料及其制备方法和应用 - Google Patents

一种环氧树脂材料及其制备方法和应用 Download PDF

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WO2019051885A1
WO2019051885A1 PCT/CN2017/103949 CN2017103949W WO2019051885A1 WO 2019051885 A1 WO2019051885 A1 WO 2019051885A1 CN 2017103949 W CN2017103949 W CN 2017103949W WO 2019051885 A1 WO2019051885 A1 WO 2019051885A1
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epoxy resin
resin material
material according
acrylonitrile
compound
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English (en)
French (fr)
Inventor
周萌
刘赵兴
杜秀才
孙晓丽
初长坤
张聪颖
李鑫
姜庆梅
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Wanhua Chemical Group Co Ltd
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Wanhua Chemical Group Co Ltd
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Priority to EP17925438.8A priority Critical patent/EP3683249A4/en
Priority to US16/644,798 priority patent/US11248085B2/en
Publication of WO2019051885A1 publication Critical patent/WO2019051885A1/zh
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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
    • C08G59/20—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
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic 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
    • C08G59/20—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5026—Amines cycloaliphatic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5006—Amines aliphatic
    • 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
    • C08G59/56—Amines together with other curing agents
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the invention relates to an epoxy resin material and a preparation method and application thereof, and further relates to an epoxy resin material which can be applied to the preparation of large composite materials such as wind power blades.
  • Wind power is a renewable and clean energy source that is mature and widely used.
  • Large-scale composite wind turbine blades as an important part of wind turbines, play a role in converting wind energy into electrical energy.
  • the design and material selection of wind turbine blades determines the performance and power of the wind turbine. Due to its excellent mechanical properties, heat resistance, chemical resistance and good fatigue resistance, epoxy resin has been continuously expanded in wind turbine blades. It is understood that the mainstream wind power blades on the market are generally processed by epoxy composite materials.
  • the common amine curing agent used has a high activity and a short operation time after mixing with the resin, and cannot be sufficiently flowed in the mold during the process of preparing the composite material. If a latent curing agent having low reactivity is used, the cured product has poor mechanical properties due to its high post-aging temperature and cannot be used for the preparation of large-scale wind turbine blades.
  • methods for reducing the activity of the curing agent in the epoxy resin composition mainly include epoxy compound modification, silicone modification, and microcapsule coating.
  • the epoxy compound is modified mainly by reacting a low-viscosity epoxy diluent with a polyamine to reduce the concentration of free amine in the curing agent; and the increase of steric hindrance after accessing multiple groups on the polyamine Thereby reducing the reaction activity Sex.
  • the viscosity of the curing agent after the modification of the epoxy compound is large, and the degree of activity reduction is small, and the operation time of the mixed system cannot meet the requirements of the molding process of the large wind power blade.
  • the silicone-modified curing agent adjusts the curing agent activity mainly by changing the kind and number of reactive groups on the curing agent or adjusting the length of the siloxane segment.
  • the microcapsule coating is a polysulfone plastic as a wall material, and an imidazole latent curing agent is used as a core, and a low-activity epoxy curing agent is prepared by an emulsification-solvent evaporation method.
  • the curing agent is not easy to release at normal temperature, and can be quickly cured by heating to a specified temperature during use.
  • the microcapsule coating curing agent has poor compatibility with the epoxy resin, requires a high post-maturing temperature, and the cured product has low mechanical properties and heat resistance, and is difficult to industrialize.
  • the epoxy resin material currently widely used in wind power blades is bisphenol A type epoxy resin which is diluted by a diluent and then cured by an amine curing agent.
  • a large amount of diluent is added to improve the processing property, the volume shrinkage of the product after curing is large, the mechanical properties of the cured resin are deteriorated, and the glass transition temperature Tg is lowered, resulting in adverse effects on the blade life.
  • the commonly used curing procedure is to simply mix and cure the curing agent and the epoxy resin main agent at room temperature, and the epoxy resin composite material thus obtained is easy to be mechanically, solvent-resistant and vitrified. There are defects in temperature and the like.
  • a vacuum infusion epoxy resin system for a wind power blade is provided in Chinese Patent Application Publication No. CN 106380785 A, which uses a bisphenol A type epoxy resin with an epoxy diluent as an epoxy resin main agent, and a polyether amine and The isophorone diamine is combined with a modified amine as a curing agent, and an epoxy resin material for a wind power blade is prepared by mixing an epoxy resin main agent and a curing agent; according to reports, the epoxy resin system can improve the maximum heat release Temperature and operable time. According to the disclosed test data, the characteristics of the glass transition temperature Tg of the obtained product are not satisfactory.
  • the invention provides an epoxy resin material and a preparation method and application thereof, in order to make up for the deficiencies of the prior art, and the epoxy resin material of the invention has the characteristics of low mixing viscosity, long operation time and low heat release during preparation. .
  • a first aspect of the present invention provides a method for preparing an epoxy resin material, comprising the steps of: reacting a mixture of an epoxy resin main agent and a curing agent placed at room temperature to 40-85 ° C for reaction curing, wherein the curing agent contains An adduct of an acrylonitrile compound and an amine compound.
  • the active hydrogen in the amino group undergoes a ring-opening addition reaction with the epoxy group to form an N-hydrocarbyl nitrile group, and the mixture is placed at room temperature. Thereafter, the temperature is raised to 40-85 ° C, and the cyano group further undergoes an addition reaction with a hydroxyl group to form an amide bond structure, thereby improving heat resistance, solvent resistance and mechanical properties of the cured product.
  • the mixture is warmed to 50-80 ° C for reaction curing.
  • the epoxy resin material is prepared by the preferred embodiment, the obtained product has better performance and exhibits superior solvent resistance, mechanical properties and Tg value.
  • the reaction after heating is 3-7 h, and more preferably 4-7 h.
  • the mixture is heated to 50-80 ° C for 4-7 h, and the performance of the product prepared by the preferred embodiment is further improved.
  • the mixture is allowed to stand at room temperature for more than 24 hours before the mixture is heated to carry out reaction curing, thereby facilitating the production of a better performance product, and the standing time at room temperature may be 24 hours. It can be any length of time greater than 24 hours, and the extension of the placement time has little effect on the performance of the product, usually taking into account the production efficiency without selecting a longer placement time.
  • the adduct of the acrylonitrile compound and the amine compound comprises one or more of the following compounds of the formula (I):
  • n is an integer from 1 to 6;
  • R 2 is selected from one of the following formulas:
  • R 3 is selected from H or one selected from the group consisting of the following structural formulas:
  • a preferred adduct of an acrylonitrile compound and an amine compound provides a longer operating time, a lower mixing viscosity, and a lower exotherm in the preparation of the epoxy resin material. It is more conducive to obtaining epoxy resin materials which are more excellent in mechanical properties, heat resistance and solvent resistance.
  • the acrylonitrile compound may specifically be one or more of acrylonitrile, 3-butenenitrile, 2-pentenenitrile, 3-pentenenitrile and 4-pentenenitrile. It is preferably acrylonitrile.
  • the amine compound may specifically be diethylenetriamine, triethylenetetramine, polyetheramine, 1,3-cyclohexyldimethylamine, isophoronediamine, 4,4.
  • the adduct is obtained by adding an amine compound and an acrylonitrile compound in a molar ratio of 1: (1-4).
  • the adduct of the acrylonitrile compound and the amine compound is obtained by a method comprising the steps of: an amine compound and an acrylonitrile compound are subjected to an addition reaction at 45 to 85 ° C, preferably The addition reaction was carried out at 55-75 °C. Further preferably, after heating the amine compound to 45 to 85 ° C, the acrylonitrile compound is added dropwise.
  • the adduct of the acrylonitrile compound and the amine compound is simple in preparation, practical, and the obtained adduct of the acrylonitrile compound and the amine compound has a low viscosity.
  • the amine compound and the acrylonitrile compound are subjected to an addition reaction in a molar ratio of 1: (1-4).
  • the addition reaction is carried out for a period of from 5 to 10 h, preferably from 6 to 7 h.
  • the addition reaction is carried out under the action of a basic catalyst, and the amount of the basic catalyst is from 0.01% to 0.3% by mass based on the mass of the amine compound, and more preferably from 0.05% to 0.2%.
  • the basic catalyst is preferably one or more of triethylamine, hexahydropyridine, sodium hydroxide, potassium hydroxide, sodium ethoxide, potassium tert-butoxide, sodium amide, and a quaternary amine base. It is preferably triethylamine.
  • the acrylonitrile compound has a purity of 50% by weight or more, preferably a purity of 50 to 80% by weight, more preferably a purity of 65 to 75% by weight.
  • the acrylonitrile compound which achieves the above purity requirements can be obtained commercially.
  • the acrylonitrile compound which achieves the above purity requirement can be obtained by purifying by a method comprising the steps of: the acrylonitrile compound has a degree of vacuum of -0.5 to -0.05 MPa, and the temperature is 20 to 60 ° C. Distillation under the conditions; more preferably, the degree of vacuum is -0.2 to -0.09 MPa, and the temperature is 35 to 50 °C.
  • the mass ratio of the epoxy resin main agent to the curing agent is (3-8):1, preferably (3.5-7):1.
  • the epoxy resin main agent comprises the following components by mass percentage: based on the mass of the epoxy resin main agent, 60-80 wt% of the epoxy resin, 2-20 wt% of the diluent,
  • the foaming agent is 1-20% by weight.
  • the epoxy resin is preferably one or more of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin. Further preferably, the epoxy resin has an epoxy value of from 0.1 to 0.65 and is liquid at room temperature. More preferably, the epoxy resin is a bisphenol A type epoxy resin having an epoxy value of 0.1 to 0.65 and being liquid at room temperature. As an example, the epoxy resin may be one or more of E-44, E-51, E-54, and the like.
  • the diluent is preferably selected from the group consisting of butyl glycidyl ether, benzyl glycidyl ether, butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,2-cyclohexane Alcohol diglycidyl ether, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycidyl ether containing a C12-C14 alkyl group in the main chain, benzyl alcohol, phenylethyl alcohol, nonylphenol, carbonic acid One or more of propylene ester, trimethylolpropane triacrylate, diisopropanol methyl ether, toluene and xylene.
  • the antifoaming agent is preferably selected from at least one of a polyacrylate and a modified silicone.
  • the antifoaming agent may specifically be one or more of BYK066N, BYKA530, BYK141, and BYK354 produced by BYK Chemical.
  • the curing agent contains 55 to 75 wt% of an adduct of an acrylonitrile compound and an amine compound, based on the total mass of the curing agent.
  • the The curing agent includes the following components by mass percentage: based on the total mass of the curing agent, the adduct of the acrylonitrile compound and the amine compound is 55-75 wt%, and the polyether amine is 25-45 wt%.
  • the polyetheramine may be one or more of D230, D400, D2000, T403, and T5000, preferably D230.
  • the following includes an adduct of acrylonitrile and isophorone diamine in the curing agent, and an example of the main epoxy resin E-51 in the epoxy resin main agent.
  • the main reaction process for the preparation of epoxy resin materials is only an example and is not intended to limit the invention.
  • the first step in the following example is the main reaction of the epoxy resin main agent and curing agent at room temperature, and the second step is the main reaction when the temperature is raised to 40-85 °C:
  • a second aspect of the present invention provides an epoxy resin material which is obtained by the above-described preparation method.
  • a third aspect of the invention provides the use of the epoxy resin material described above, which is applied to the preparation of large composite materials, for example, for the preparation of large composite materials used or possibly used in the following fields: : wind power blades, flue gas desulfurization towers, power transmission and transformation equipment, High-pressure gas cylinders, automobile bodies, rail transit bodies, passenger aircraft wing, nose covers, yachts, fishing boats, house reinforcement materials, tunnel engineering, large-scale warehousing and sporting goods. More preferably applied to the preparation of wind turbine blades.
  • Large-scale composite material refers to a part in which the epoxy resin composition is used in an amount of more than 1 ton during the one-time curing process of the material.
  • the epoxy resin material of the present invention introduces -CN into the curing agent, and the electron cloud density on the amino group is lowered due to the strong electron-withdrawing effect of the CN, and the reaction between the amino group and the epoxy group is suppressed during the curing reaction, thereby Increasing the pot life of the hybrid system, and reducing the maximum exothermic peak temperature, the extension of the exothermic peak time can meet the construction process requirements of large composite materials such as wind turbine blades. The sensitivity to moisture and carbon dioxide in the air is reduced and it can flow more fully in the mold.
  • the pot life can reach 3-6h (100g, 25 ° C), the highest exothermic peak temperature can be as low as 35-50 ° C, and the highest exothermic peak can be extended to 430- 600min.
  • the temperature rise reaction is carried out after being left at room temperature, and the heat resistance, solvent resistance and mechanical properties of the cured product can be effectively improved.
  • the epoxy resin material prepared by the invention can have a Tg of 90-120 ° C, and in a preferred embodiment, can reach more than 114 ° C; no significant change in immersion in a concentration of 5% hydrochloric acid for 60-90 days, in a preferred scheme In the middle, it can achieve no significant change after soaking for more than 85 days; the tensile strength can reach 60-80 MPa, and in the preferred scheme, it can reach 76 MPa or more.
  • the epoxy resin material prepared by the epoxy resin composition of the present invention is particularly suitable for the preparation of large wind turbine blades of 70-90 meters.
  • IPDA Isophorone diamine
  • Diethylenetriamine (DETA) Japan Tosoh Corporation Diphenylmethanediamine (MDA) Wanhua Chemical Group Co., Ltd.
  • Polyetheramine (D-230) Huntsman Chemical Acrylonitrile Sinopharm Chemical Reagent Co., Ltd 3-butenenitrile Sinopharm Chemical Reagent Co., Ltd 3-pentenenitrile Sinopharm Chemical Reagent Co., Ltd 4-pentenenitrile Sinopharm Chemical Reagent Co., Ltd DER 331 Dow Chemical XY622 Anhui Xinyuan Chemical Co., Ltd.
  • the viscosity that may be involved in the following examples is measured by the following test conditions: Boehler viscometer, temperature 25 ° C, 18 # rotor;
  • acrylonitrile is purified by a rotary evaporator, the pump is vacuumed, the degree of vacuum is -0.2 MPa, the temperature is 45 ° C, and the fraction having an acrylonitrile content of about 65 wt% is collected;
  • IPDA 170g IPDA was added to the reaction vessel, replaced with nitrogen, and heated at 55 ° C. Under the action of 0.085 g of triethylamine, the fraction obtained in 106 g of 1 was added dropwise to the reaction vessel. After the completion of the dropwise addition, the reaction was allowed to cool for 6 hours. An adduct of the acrylonitrile compound and an amine compound is obtained.
  • the obtained epoxy resin main agent and curing agent were uniformly mixed at a mass ratio of 4:1, defoamed, poured into a mold, and left at room temperature for 24 hours to obtain an epoxy resin material.
  • 100g of epoxy resin material prepared in Comparative Example 1 has a pot life of 3h at 25 ° C, the highest exotherm The peak temperature was 50 ° C, the highest exothermic peak appeared at 430 min, the cured product Tg was 90 ° C, and there was no significant change in 5% HCl for 60 d, and the tensile strength was 60 MPa.
  • acrylonitrile is purified by a rotary evaporator, the pump is vacuumed, the degree of vacuum is -0.2 MPa, the temperature is 45 ° C, and the fraction having an acrylonitrile content of about 65 wt% is collected;
  • IPDA 170g of IPDA was added to the reaction vessel, replaced with nitrogen, and the temperature was raised to 55 ° C. Under the action of 0.085 g of triethylamine, the fraction obtained in 106 g of 1 was added dropwise to the reaction vessel, and after the completion of the dropwise addition, the reaction was carried out for 6 hours, and the temperature was lowered to room temperature. The adduct is obtained.
  • the obtained epoxy resin main agent and curing agent were uniformly mixed at a mass ratio of 4:1, defoamed, poured into a mold, left at room temperature for 24 hours, and then heated to 40 ° C for 3 hours to obtain an epoxy resin material.
  • 100g of the epoxy resin material prepared in Example 1 has a pot life of 3 h at 25 ° C, a maximum exothermic peak temperature of 50 ° C, a maximum exothermic peak appearance time of 430 min, a cured product Tg of 102 ° C, and immersion in 5% HCl. There was no significant change in 70d and the tensile strength was 71 MPa.
  • the obtained epoxy resin main agent and curing agent were uniformly mixed at a mass ratio of 4:1, defoamed, poured into a mold, left at room temperature for 24 hours, and then heated to 85 ° C for 7 hours to obtain an epoxy resin material.
  • 100g of the epoxy resin material prepared in Example 2 has a pot life of 3h at 25 ° C, a maximum exothermic peak temperature of 50 ° C, a maximum exothermic peak appearance time of 430 min, a cured product Tg of 93 ° C, soaked in 5% HCl There was no significant change in 62d and the tensile strength was 65 MPa.
  • the 13-butenenitrile was purified by a rotary evaporator, the pump was evacuated, the degree of vacuum was -0.2 MPa, the temperature was 45 ° C, and a fraction of 3-butenenitrile content of about 65 wt% was collected;
  • the obtained epoxy resin main agent and curing agent were uniformly mixed at a mass ratio of 7:1, defoamed, poured into a mold, left at room temperature for 24 hours, heated to 50 ° C, and reacted for 4 hours to obtain an epoxy resin material.
  • 100g of the epoxy resin material prepared in Example 3 has a pot life of 6h at 25 ° C, a maximum exothermic peak temperature of 35 ° C, a maximum exothermic peak appearance time of 600 min, a cured product Tg of 120 ° C, and immersion in 5% HCl. There was no significant change in 90d and the tensile strength was 80 MPa.
  • the 14-pentenenitrile is purified by a rotary evaporator, the pump is evacuated, the degree of vacuum is -0.2 MPa, the temperature is 45 ° C, and the fraction having a 4-pentenenitrile content of about 65 wt% is collected;
  • the obtained epoxy resin main agent and curing agent were uniformly mixed at a mass ratio of 5:1, defoamed, poured into a mold, left at room temperature for 24 hours, heated to 80 ° C, and reacted for 7 hours to obtain an epoxy resin material.
  • 100 g of the epoxy resin material prepared in Example 4 has a pot life of 4.7 h at 25 ° C, a maximum exothermic peak temperature of 43 ° C, a maximum exothermic peak appearance time of 520 min, and a cured product Tg of 114 ° C in 5% HCl. There was no significant change after soaking for 85 days, and the tensile strength was 76 MPa.
  • the adducts of the acrylonitrile compound and the amine compound used may also be prepared without using the method of the examples, and the existing raw materials meeting the same requirements may be directly used, and may also be commercially available.
  • Comparative Example 1 In the preparation of the epoxy resin material, it was only placed at room temperature without a step of raising the temperature, and the epoxy resin obtained in Comparative Example 1 was compared to the subsequent example in which the temperature was raised to 40-85 ° C for the reaction.
  • the Tg value of the material is low, and the solvent resistance and the tensile strength are not as good as other examples.
  • the temperature rise reaction temperature was 40 ° C and 85 ° C, respectively, and the solvent resistance, Tg value and tensile strength of the products prepared were compared with those of Examples 3-4 at a temperature rise reaction temperature of 50-80 ° C. Inferior to Examples 4-5.
  • Examples 3-4 have a longer pot life, the exothermic temperature is also higher, and the maximum exothermic peak appearance time is also greatly extended.

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Abstract

本发明提供一种环氧树脂材料及其制备方法和应用，本发明提供的环氧树脂材料的制备方法，将室温放置的环氧树脂主剂和固化剂的混合物升温至40-85℃反应固化，所述固化剂中含有烯腈化合物和胺类化合物的加合物。本发明制备环氧树脂材料的方法，在制备时具有混合粘度低、较长的操作时间和低放热等特点。

Description

一种环氧树脂材料及其制备方法和应用 技术领域
本发明涉及一种环氧树脂材料及其制备方法和应用，进一步涉及一种可应用于大型复合材料例如风电叶片的制备的环氧树脂材料。
背景技术
风力发电是一种技术成熟且应用广的可再生清洁能源。而大型复合材料风电叶片作为风电机组的重要组成部分，起着将风能转化为电能的作用。风电叶片的设计和材料的选择决定了风力发电装置的性能和功率。环氧树脂由于具有优异的力学性能、耐热性能、耐化学介质和良好的耐疲劳性能，在风电叶片中的应用也得到了不断拓展。据了解，目前市场上的主流风电叶片一般都采用环氧复合材料加工而成。
近几年来，随着我国风电行业的迅速发展，陆上优质风场的日益减少，为了进一步提高风能的利用效率，很多低风速的风场和海上风场成为未来风电行业发展的重点。因此，风电企业对大功率单机装机容量的风电机组提出了新的要求。这也就意味着风电叶片的叶片长度将进一步增加。因此，制备风电叶片的材料的性能要求也提升到了新的高度。如何开发一种具有放热少、黏度低、适用期长，耐热性高、力学性能好、与纤维的相容性好等优点的环氧树脂材料已成为风电行业较为迫切的需求点之一。
目前应用于风电叶片的环氧树脂材料中，所使用的普通胺类固化剂由于活性较高，与树脂混合后的操作时间较短，在制备复合材料的过程中无法充分的在模具中流动。若使用具有低反应活性的潜伏型固化剂，由于其后熟化温度较高，固化物力学性能差，也无法用于大型风电叶片的制备。目前降低环氧树脂组合物中的固化剂活性的方法主要有环氧化合物改性、有机硅改性和微胶囊包覆。其中环氧化合物改性主要是通过低黏度的环氧稀释剂与多元胺进行反应，降低固化剂中游离胺的浓度；并且由于在多元胺上接入多个基团后空间位阻的增大从而降低反应活 性。但是环氧化合物改性后的固化剂黏度较大，活性降低程度较小，混合体系操作时间无法满足大型风电叶片成型工艺的要求。有机硅改性的固化剂则主要是通过改变固化剂上活性基团的种类和数目或调节硅氧烷链段的长度来调节固化剂活性。但是，有机硅改性的固化剂中存在的大量烷氧基链段，其耐热性以及材料弯曲模量受到限制。微胶囊包覆则是以聚砜类塑料为壁材原料，以咪唑类潜伏型固化剂为囊芯，通过乳化-溶剂蒸发法制备低活性环氧固化剂。该固化剂在常温下不易释放，使用时加热到指定温度即可达到快速固化目的。微胶囊包覆固化剂与环氧树脂的相容性差，需要较高的后熟化温度，且固化物的力学性能和耐热性较低，难以工业化应用。
当前广泛应用于风电叶片的环氧树脂材料为双酚A型环氧树脂通过稀释剂稀释后，采用胺类固化剂固化得到。但由于其中需加入大量的稀释剂以提高其加工性能，导致固化后产品体积收缩率大，固化后的树脂力学性能变差，玻璃化温度Tg降低，造成对叶片寿命的不良影响。另外，目前在制备环氧复合材料时，常用的固化程序是将固化剂和环氧树脂主剂室温简单混合固化，这样做出来的环氧树脂复合材料容易在力学性能、耐溶剂性和玻璃化温度等方面存在缺陷。
公开号为CN 106380785A的中国专利申请中提供了一种风电叶片用真空灌注环氧树脂系统，其以双酚A型环氧树脂搭配环氧稀释剂为环氧树脂主剂，以聚醚胺和异弗尔酮二胺搭配改性胺为固化剂，通过将环氧树脂主剂和固化剂混合制得一种风电叶片用环氧树脂材料；据介绍，该环氧树脂体系可改善最高放热温度和可操作时间。而其披露的检测数据来看，其制得的产品玻璃化温度Tg等方面的特性还不够理想。
发明内容
本发明为弥补现有技术的不足，提供一种环氧树脂材料及其制备方法和应用，本发明的环氧树脂材料在制备时具有混合粘度低、较长的操作时间和低放热等特点。
本发明为达到目的，采用的技术方案如下：
本发明第一方面提供一种环氧树脂材料的制备方法，包括如下步骤：将室温放置的含有环氧树脂主剂和固化剂的混合物升温至40-85℃反应固化，所述固化剂中含有烯腈化合物和胺类化合物的加合物。
本发明中，制备环氧树脂材料时，在固化剂和环氧树脂主剂混合后，氨基中的活性氢与环氧基发生开环加成反应，形成N-烃基腈基胍，混合物室温放置后，升温至40-85℃，体系中氰基进一步与羟基发生加成反应，形成酰胺键结构，提高固化物的耐热性、耐溶剂性和机械性能。
在本发明的优选方案中，将所述混合物升温至50-80℃反应固化。采用该优选方案制备环氧树脂材料时，所制得的产品性能更佳，表现出更优异的耐溶剂性、机械性能和Tg值。
更为优选的方案中，升温后反应3-7h，进一步优选为4-7h。
进一步优选的方案中，所述混合物升温至50-80℃反应4-7h，该优选方案制备的产品性能有更进一步的提升。
作为一种优选的具体实施方式，在将所述混合物升温进行反应固化之前，将所述混合物室温放置24h以上，从而利于制得性能更佳的产品，在室温放置的时长可以是24小时，也可以是大于24小时的任意时长，放置时长的延长对产品的性能几乎不产生影响，通常考虑到生产效率而不会选择更久的放置时长。
本发明优选的，所述烯腈化合物和胺类化合物的加合物包含具有如下结构式(Ⅰ)的化合物中的一种或多种：
Figure PCTCN2017103949-appb-000001
其中，式(Ⅰ)中R1的结构式选自下式中的一种：
Figure PCTCN2017103949-appb-000002
其中的n值为1～6的整数；
R2的结构式选自下式中的一种：
Figure PCTCN2017103949-appb-000003
Figure PCTCN2017103949-appb-000004
R3选自H或者选自如下结构式中的一种：
Figure PCTCN2017103949-appb-000005
Figure PCTCN2017103949-appb-000006
采用优选的烯腈化合物和胺类化合物的加合物，在制备环氧树脂材料时可获得较长的操作时间，较低的混合粘度，且低放热。更有助于获得机械性能、耐热性和耐溶剂性更为优异的环氧树脂材料。
在本发明的优选方案中，所述烯腈化合物具体可以为丙烯腈、3-丁烯腈、2-戊烯腈、3-戊烯腈和4-戊烯腈中的一种或几种，优选为丙烯腈。
在本发明的优选方案中，所述胺类化合物具体可以为二乙烯三胺、三乙烯四胺、聚醚胺、1,3-环己基二甲胺、异弗尔酮二胺、4,4’-二氨基二环己基甲烷、二氨甲基环已基甲烷和二苯基甲烷二胺中的一种或多种，优选为异弗尔酮二胺。
在本发明的优选方案中，所述加合物为胺类化合物和烯腈化合物按照摩尔比为1：(1-4)加成制得。
作为本发明的一种优选实施方式，所述烯腈化合物和胺类化合物的加合物按照包括如下步骤的方法制得：胺类化合物和烯腈化合物在45-85℃进行加成反应，优选为在55-75℃进行加成反应。进一步优选的，将胺类化合物加热至45-85℃后，再将烯腈化合物以滴加的方式加入。上述优选实施方式中，烯腈化合物和胺类化合物的加合物的制备工艺简单，实用性强，制得的烯腈化合物和胺类化合物的加合物粘度低。作为一种优选的实施方式中，胺类化合物和烯腈化合物按照摩尔比为1：(1-4)进行加成反应。
在优选实施方式中，进行加成反应的时间为5-10h，优选为6-7h。
本发明的优选实施方式中，所述加成反应在碱性催化剂作用下进行，碱性催化剂的用量为胺类化合物质量的0.01％-0.3％，进一步优选为0.05％-0.2％。所述碱性催化剂优选为三乙胺、六氢吡啶、氢氧化钠、氢氧化钾、乙醇钠、三级丁醇钾、氨基钠和四级胺碱中的一种或多种，更 优选为三乙胺。
在本发明的部分优选实施方式中，所述烯腈化合物为纯度达到50wt％以上，优选纯度达到50-80wt％，更优选为纯度达到65-75wt％。达到上述纯度要求的烯腈化合物可以通过商业渠道获得。在本发明的部分优选方案中，达到上述纯度要求的烯腈化合物可通过采用包括如下步骤的方法提纯制得：将烯腈化合物在真空度为-0.5～-0.05MPa，温度为20～60℃的条件下蒸馏；更为优选，真空度为-0.2～-0.09MPa，温度为35～50℃。
作为本发明的优选方案，所述环氧树脂主剂和固化剂的质量比为(3-8):1，优选为(3.5-7):1。
在本发明的优选实施方式中，所述环氧树脂主剂包括如下质量百分比的各组分：基于环氧树脂主剂的质量，环氧树脂60-80wt％，稀释剂2-20wt％，消泡剂1-20wt％。
本发明中，所述环氧树脂优选为双酚A型环氧树脂和双酚F型环氧树脂中的一种或多种。进一步优选的，所述环氧树脂的环氧值为0.1-0.65，室温下为液体。更为优选的，所述环氧树脂为环氧值0.1-0.65、室温下为液体的双酚A型环氧树脂。作为一种示例，所述环氧树脂可以为E-44、E-51和E-54等中的一种或多种。
本发明中，所述稀释剂优选选自丁基缩水甘油醚、苄基缩水甘油醚、丁二醇二缩水甘油醚、1,6-己二醇二缩水甘油醚、1,2-环己二醇二缩水甘油醚、聚乙二醇二缩水甘油醚、三羟甲基丙烷三缩水甘油醚、分子主链含有C12-C14烷基的缩水甘油醚、苯甲醇、苯乙醇、壬基酚、碳酸丙烯酯、三羟甲基丙烷三丙烯酸酯、二异丙醇甲醚、甲苯和二甲苯中的一种或多种。
本发明中，所述消泡剂优选选自聚丙烯酸酯和改性有机硅中的至少一种。作为一种示例，所述消泡剂具体可以为毕克化学生产的BYK066N、BYKA530、BYK141和BYK354中的一种或多种。
在本发明的优选方案中，基于固化剂的总质量，所述固化剂中含有55-75wt％的烯腈化合物和胺类化合物的加合物。更优选的方案中，所述 固化剂包括如下质量百分比的各组分：基于固化剂的总质量，烯腈化合物和胺类化合物的加合物55-75wt％，聚醚胺25-45wt％。作为一种示例，所述聚醚胺可以为D230、D400、D2000、T403和T5000中的一种或多种，优选为D230。
为了便于理解本发明环氧树脂材料的制备原理，下面以固化剂中含有丙烯腈、异弗尔酮二胺的加合物，环氧树脂主剂中主要为环氧树脂E-51的例子说明环氧树脂材料制备的主要反应过程。以下反应过程仅是一个示例，并非对本发明的限制。以下示例中第一步为环氧树脂主剂和固化剂在室温放置时的主要反应，第二步为升温至40-85℃时的主要反应：
Figure PCTCN2017103949-appb-000007
本发明第二方面提供一种环氧树脂材料，采用上文所述的制备方法制得。
本发明第三方面提供上文所述的环氧树脂材料的应用，所述环氧树脂材料应用于大型复合材料的制备，例如可应用于如下领域使用到或可能使用到的大型复合材料的制备：风电叶片、烟气脱硫塔、输变电设备、 高压气瓶、汽车车身、轨道交通车体、民航客机机翼、机头罩、游艇、渔船、房屋补强材料、隧道工程、大型仓储和体育用品等领域。更优选应用于风电叶片的制备。
大型复合材料是指在材料一次性固化成型过程中，环氧树脂组合物的使用量超过1吨的制件。
本发明提供的技术方案具有如下有益效果：
本发明的环氧树脂材料，在固化剂中引入-CN，由于CN的强吸电子效应，降低了氨基上的电子云密度，在进行固化反应时，抑制了氨基与环氧基的反应，从而增长混合体系适用期，并降低最高放热峰温度，出现放热峰的时间延长，可满足风电叶片等大型复合材料的施工工艺要求。对空气中的水分和二氧化碳的敏感度下降，可以更充分的在模具中流动。
利用本发明的方案制备环氧树脂材料时，适用期可达到3-6h(100g，25℃)，最高放热峰温度可低至35-50℃，最高放热峰出现时间可延长至430-600min。本发明制备环氧树脂材料时，在室温放置后进行升温反应，可有效改善固化物的耐热性、耐溶剂性和机械性能。本发明所制备的环氧树脂材料的Tg可达到90-120℃，在优选方案中，更可达到114℃以上；在浓度为5％的盐酸中浸泡60-90天无明显变化，在优选方案中，更可达到浸泡85天以上无明显变化；拉伸强度可达到60-80MPa，在优选方案中，更可达到76MPa以上。
本发明的环氧树脂组合物制备的环氧树脂材料特别适用于70-90米大型风电叶片的制备。
具体实施方式
为了更好的理解本发明的技术方案，下面结合实施例进一步阐述本发明的内容，但本发明的内容并不仅仅局限于以下实施例。
以下实施例中所用的原料及来源详见表1。
表1原料及来源
化学名称 厂家
异弗尔酮二胺(IPDA) 万华化学集团股份有限公司
二乙烯三胺(DETA) 日本东曹株式会社
二苯基甲烷二胺(MDA) 万华化学集团股份有限公司
聚醚胺(D-230) Huntsman化工
丙烯腈 国药化学试剂有限公司
3-丁烯腈 国药化学试剂有限公司
3-戊烯腈 国药化学试剂有限公司
4-戊烯腈 国药化学试剂有限公司
DER 331 美国陶氏化学
XY622 安徽新远化工有限公司
以下实施例中可能涉及到的黏度均为如下测试条件测得：博勒飞黏度计，温度25℃，18#转子；
对比例1
(1)烯腈化合物和胺类化合物的加合物(以下简称加合物)的制备
①丙烯腈采用旋转蒸发仪提纯，水泵抽真空，真空度为-0.2MPa，温度为45℃，收集丙烯腈含量约65wt％的馏分；
②将170g IPDA加入到反应釜中，氮气置换，升温55℃，在0.085g三乙胺的作用下，将106g①中所得馏分逐滴加入到反应釜中，滴加完成后反应6h，降温至室温，得所述烯腈化合物和胺类化合物的加合物。
(2)环氧树脂材料的制备
环氧树脂主剂的制备：将70g DER 331加入到混合设备中，升温至55℃并保持恒温；加入15g XY622和15g BYKA530(毕克化学生产)，70℃持续搅拌2.5小时，混合均匀，静置；
固化剂的制备：将45g D-230和55g(1)中制备的加合物加入反应釜中，使反应釜的温度保持在35℃，充分搅拌1.5小时，混合均匀，静置1小时，将混合好地固化剂装入产品容器中，密封室温保存；
将所得的环氧树脂主剂和固化剂按照质量比为4:1混合均匀，脱泡后倒入模具中，在室温下放置24h，得到环氧树脂材料。
100g对比例1制备的环氧树脂材料在25℃的适用期为3h，最高放热 峰温度为50℃，最高放热峰出现时间为430min，固化物Tg为90℃，在5％HCl中浸泡60d无明显变化，拉伸强度为60MPa。
实施例1
(1)烯腈化合物和胺类化合物的加合物的制备(以下简称加合物)
①丙烯腈采用旋转蒸发仪提纯，水泵抽真空，真空度为-0.2MPa，温度为45℃，收集丙烯腈含量约65wt％的馏分；
②将170gIPDA加入到反应釜中，氮气置换，升温55℃，在0.085g三乙胺的作用下，将106g①中所得馏分逐滴加入到反应釜中，滴加完成后反应6h，降温至室温，得所述加合物。
(2)环氧树脂材料的制备
环氧树脂主剂的制备：将70gDER 331加入到混合设备中，升温至55℃并保持恒温；加入15gXY622和15gBYKA530，70℃持续搅拌2.5小时，混合均匀，静置；
固化剂的制备：将45g D-230和55g(1)中制备的加合物加入反应釜中，使反应釜的温度保持在35℃，充分搅拌1.5小时，混合均匀，静置1小时，将混合好地固化剂装入产品容器中，密封室温保存；
将所得的环氧树脂主剂和固化剂按照质量比为4:1混合均匀，脱泡后倒入模具中，在室温下放置24h，然后升温至40℃，反应3h，得到环氧树脂材料。
100g实施例1制备的环氧树脂材料在25℃的适用期为3h，最高放热峰温度为50℃，最高放热峰出现时间为430min，固化物Tg为102℃，在5％HCl中浸泡70d无明显变化，拉伸强度为71MPa。
实施例2
(1)烯腈化合物和胺类化合物的加合物的制备(以下简称加合物)
①丙烯腈采用旋转蒸发仪提纯，水泵抽真空，真空度为-0.2MPa，温度为45℃，收集中间含量约65wt％的馏分；
②将170gIPDA加入到反应釜中，氮气置换，升温55℃，在0.085g三 乙胺的作用下，将106g①中所得馏分逐滴加入到反应釜中，滴加完成后反应6h，降温至室温，得所述加合物。
(2)环氧树脂材料的制备
环氧树脂主剂的制备：将70gDER 331加入到混合设备中，升温至55℃并保持恒温；加入15gXY622和15gBYKA530，70℃持续搅拌2.5小时，混合均匀，静置；
固化剂的制备：将45g D-230和55g(1)中制备的加合物加入反应釜中，使反应釜的温度保持在35℃，充分搅拌1.5小时，混合均匀，静置1小时，将混合好地固化剂部分装入产品容器中，密封室温保存；
将所得的环氧树脂主剂和固化剂按照质量比为4:1混合均匀，脱泡后倒入模具中，在室温下放置24h，然后升温至85℃，反应7h，得到环氧树脂材料。
100g实施例2制备的环氧树脂材料在25℃的适用期为3h，最高放热峰温度为50℃，最高放热峰出现时间为430min，固化物Tg为93℃，在5％HCl中浸泡62d无明显变化，拉伸强度为65MPa。
实施例3
(1)烯腈化合物和胺类化合物的加合物的制备(以下简称加合物)
①3-丁烯腈采用旋转蒸发仪提纯，水泵抽真空，真空度为-0.2MPa，温度为45℃，收集3-丁烯腈含量约65wt％的馏分；
②将103gDETA(二乙烯三胺)加入到反应釜中，氮气置换，升温55℃，在0.26gKOH的催化下，将201g①中所得馏分逐滴加入到反应釜中，滴加完成后反应6h，降温至室温，得所述加合物。
(2)环氧树脂材料的制备
环氧树脂主剂的制备：将70gDER 331加入到混合设备中，升温至55℃并保持恒温；加入15gXY622和15gBYKA530，70℃持续搅拌2.5小时，混合均匀，静置；
固化剂的制备：将25g D-230和75g(1)中制备的加合物加入反应釜中，使反应釜的温度保持在35℃，充分搅拌1.5小时，混合均匀，静 置1小时，将混合好的固化剂装入产品容器中，密封室温保存；
将所得的环氧树脂主剂和固化剂按照质量比为7:1混合均匀，脱泡后倒入模具中，在室温下放置24h，升温至50℃，反应4h得到环氧树脂材料。
100g实施例3制备的环氧树脂材料在25℃的适用期为6h，最高放热峰温度为35℃，最高放热峰出现时间为600min，固化物Tg为120℃，在5％HCl中浸泡90d无明显变化，拉伸强度为80MPa。
实施例4
(1)烯腈化合物和胺类化合物的加合物的制备(以下简称加合物)
①4-戊烯腈采用旋转蒸发仪提纯，水泵抽真空，真空度为-0.2MPa，温度为45℃，收集4-戊烯腈含量约65wt％的馏分；
②将230gD-230(聚醚胺)加入到反应釜中，氮气置换，升温55℃，在0.23g六氢吡啶的催化下，将243g①中所得馏分逐滴加入到反应釜中，滴加完成后反应6h，降温至室温，得所述加合物。
(2)环氧树脂材料的制备
环氧树脂主剂的制备：将70gDER 331加入到混合设备中，升温至55℃并保持恒温；加入15gXY622和15gBYKA530，70℃持续搅拌2.5小时，混合均匀，静置；
固化剂的制备：将25g D-230和75g(1)中制备的加合物加入反应釜中，使反应釜的温度保持在35℃，充分搅拌1.5小时，混合均匀，静置1小时，将混合好地固化剂装入产品容器中，密封室温保存；
将所得的环氧树脂主剂和固化剂按照质量比为5:1混合均匀，脱泡后倒入模具中，在室温下放置24h，升温至80℃，反应7h，得到环氧树脂材料。
100g实施例4制备的环氧树脂材料在25℃的适用期为4.7h，最高放热峰温度为43℃，最高放热峰出现时间为520min，固化物Tg为114℃，在5％HCl中浸泡85d无明显变化，拉伸强度为76MPa。
以上实施例1-4中，所用的烯腈化合物和胺类化合物的加合物也可不采用实施例中的方法制备，而直接采用现有的符合同等要求的原料，也可通过商业渠道购买。
对比例1在制备环氧树脂材料时，仅是室温放置，而没有升温反应的步骤，相比于后续将温度升至40-85℃进行反应的实施例，对比例1制得的环氧树脂材料的Tg值较低，且耐溶剂性、拉升强度均不如其他实施例。实施例1-2，其升温反应温度分别为40℃、85℃，相比于升温反应温度50-80℃的实施例3-4，其制备的产品耐溶剂性、Tg值、拉升强度均逊色于实施例4-5。此外，实施例3-4具有更长的适用期，放热温度也更高，最高放热峰出现时间也得到较大幅度的延长。
本领域技术人员可以理解，在本说明书的教导之下，可对本发明做出一些修改或调整。这些修改或调整也应当在本发明权利要求所限定的范围之内。

Claims (17)

  1. 一种环氧树脂材料的制备方法，其特征在于，包括如下步骤：将经室温放置的含有环氧树脂主剂和固化剂的混合物升温至40-85℃反应固化，优选的，将所述混合物升温至50-80℃反应固化；所述固化剂中含有烯腈化合物和胺类化合物的加合物。
  2. 根据权利要求1所述的环氧树脂材料的制备方法，其特征在于，升温后反应3-7h，优选为4-7h。
  3. 根据权利要求1-2任一项所述的环氧树脂材料的制备方法，其特征在于，在将所述混合物升温进行反应固化之前，将所述混合物室温放置24h以上。
  4. 根据权利要求1-3任一项所述的环氧树脂材料的制备方法，其特征在于，所述烯腈化合物和胺类化合物的加合物包含具有如下结构式(Ⅰ)的化合物中的一种或多种：
    Figure PCTCN2017103949-appb-100001
    其中，式(Ⅰ)中R1的结构式选自下式中的一种：
    Figure PCTCN2017103949-appb-100002
    其中的n值为1-6的整数；
    R2的结构式选自下式中的一种：
    Figure PCTCN2017103949-appb-100003
    Figure PCTCN2017103949-appb-100004
    R3选自H或者选自如下结构式中的一种：
    Figure PCTCN2017103949-appb-100005
    Figure PCTCN2017103949-appb-100006
  5. 根据权利要求1-3任一项所述的环氧树脂材料的制备方法，其特征在于，所述烯腈化合物为丙烯腈、3-丁烯腈、2-戊烯腈、3-戊烯腈和4-戊烯腈中的一种或几种，优选为丙烯腈；
    所述胺类化合物为二乙烯三胺、三乙烯四胺、聚醚胺、1,3-环己基二甲胺、异弗尔酮二胺、4,4’-二氨基二环己基甲烷、二氨甲基环已基甲烷和二苯基甲烷二胺中的一种或多种，优选为异弗尔酮二胺。
  6. 根据权利要求1-5任一项所述的环氧树脂材料的制备方法，其特征在于，所述加合物为胺类化合物和烯腈化合物按照摩尔比为1：(1-4)加成制得。
  7. 根据权利要求1-6任一项所述的环氧树脂材料的制备方法，其特征在于，所述烯腈化合物和胺类化合物的加合物按照包括如下步骤的方法制得：胺类化合物和烯腈化合物在45-85℃进行加成反应，优选为在55-75℃进行加成反应；
    优选的，将胺类化合物加热至45-85℃后，更优选为加热至55-75℃后，再将烯腈化合物以滴加的方式加入。
  8. 根据权利要求7所述的环氧树脂材料的制备方法，其特征在于，加成反应的时间为5-10h，优选为6-7h。
  9. 根据权利要求7-8任一项所述的环氧树脂材料的制备方法，其特征在于，在碱性催化剂作用下进行所述加成反应，碱性催化剂的用量为胺类化合物质量的0.01％-0.3％。
  10. 根据权利要求7-9任一项所述的环氧树脂材料的制备方法，其特征在于，所述烯腈化合物的纯度为50wt％以上；
    优选的，所述烯腈化合物采用包括如下步骤的方法提纯制得：将烯腈化合物在真空度为-0.5～-0.05MPa，温度为20～60℃的条件下蒸馏。
  11. 根据权利要求1-10任一项所述的环氧树脂材料的制备方法，其特征在于，所述环氧树脂主剂和固化剂的质量比为(3-8):1，优选为(3.5-7):1。
  12. 根据权利要求1-11任一项所述的环氧树脂材料的制备方法，其特征在于，所述环氧树脂主剂包括如下质量百分比的各组分：基于环氧树脂主剂的质量，环氧树脂60-80wt％，稀释剂2-20wt％，消泡剂1-20wt％。
  13. 根据权利要求12所述的环氧树脂材料的制备方法，其特征在于，所述环氧树脂为双酚A型环氧树脂和双酚F型环氧树脂中的一种或多种；
    优选的，所述环氧树脂的环氧值为0.1-0.65，室温下为液体；更优选环氧值为0.1-0.65、室温下为液体的双酚A型环氧树脂。
  14. 根据权利要求12所述的环氧树脂材料的制备方法，其特征在于，所述稀释剂选自丁基缩水甘油醚、苄基缩水甘油醚、丁二醇二缩水甘油醚、1,6-己二醇二缩水甘油醚、1,2-环己二醇二缩水甘油醚、聚乙二醇二缩水甘油醚、三羟甲基丙烷三缩水甘油醚、分子主链含有C12-C14烷基的缩水甘油醚、苯甲醇、苯乙醇、壬基酚、碳酸丙烯酯、三羟甲基丙烷三丙烯酸酯、二异丙醇甲醚、甲苯和二甲苯中的一种或多种；
    所述消泡剂选自聚丙烯酸酯和改性有机硅中的至少一种；
  15. 根据权利要求1-14任一项所述的环氧树脂材料的制备方法，其特征在于，基于固化剂的总质量，所述固化剂中含有55-75wt％的烯腈化合物和胺类化合物的加合物；
    优选的，基于固化剂的总质量，所述固化剂中还含有25-45wt％的聚醚胺。
  16. 一种环氧树脂材料，其特征在于，采用权利要求1-15任一项所述的制备方法制得。
  17. 权利要求16所述的环氧树脂材料的应用，其特征在于，所述环氧树脂材料应用于大型复合材料的制备，优选用于风电叶片的制备。
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