CN111087761A - Epoxy resin and preparation method thereof - Google Patents

Epoxy resin and preparation method thereof Download PDF

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Publication number
CN111087761A
CN111087761A CN201911423017.7A CN201911423017A CN111087761A CN 111087761 A CN111087761 A CN 111087761A CN 201911423017 A CN201911423017 A CN 201911423017A CN 111087761 A CN111087761 A CN 111087761A
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China
Prior art keywords
epoxy resin
resin
curing agent
parts
epoxy
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Inventor
冯云龙
施佳盛
王浩
黄锐
缪鹏程
付建辉
李恒
刘坐镇
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Huachang Polymer Co Ltd East China University Of Science & Technology
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Huachang Polymer Co Ltd East China University Of Science & Technology
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Priority to CN201911423017.7A priority Critical patent/CN111087761A/en
Publication of CN111087761A publication Critical patent/CN111087761A/en
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    • 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
    • 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
    • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C1/00—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge
    • F17C1/16—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge constructed of plastics materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/01—Reinforcing or suspension means
    • F17C2203/011—Reinforcing means
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/0634—Materials for walls or layers thereof
    • F17C2203/0658—Synthetics
    • F17C2203/0663—Synthetics in form of fibers or filaments
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/0634—Materials for walls or layers thereof
    • F17C2203/0658—Synthetics
    • F17C2203/0663—Synthetics in form of fibers or filaments
    • F17C2203/0673—Polymers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/0634—Materials for walls or layers thereof
    • F17C2203/0658—Synthetics
    • F17C2203/0675—Synthetics with details of composition
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2221/00—Handled fluid, in particular type of fluid
    • F17C2221/01—Pure fluids
    • F17C2221/012—Hydrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2270/00—Applications
    • F17C2270/01—Applications for fluid transport or storage
    • F17C2270/0165—Applications for fluid transport or storage on the road
    • F17C2270/0184—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage

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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)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Epoxy Resins (AREA)

Abstract

The invention provides an epoxy resin. The raw materials for preparing the epoxy resin comprise a resin A and a curing agent B, and the mass ratio of the resin A to the curing agent B is 100: 35-50; the resin A comprises, by weight, 40-80 parts of bisphenol A type epoxy resin, 0-45 parts of bisphenol F type epoxy resin, 5-20 parts of polyfunctional group epoxy resin and 5-10 parts of epoxy resin diluent; the curing agent B comprises 20-60 parts by weight of epoxy curing agent, wherein the epoxy curing agent is an amine curing agent and 0-6 parts by weight of epoxy curing accelerator. The invention also provides a preparation method of the epoxy resin. The epoxy resin provided by the invention has lower initial viscosity, long viscosity doubling time at room temperature, long working life of more than 12 hours at room temperature and long operable time; the preparation method provided by the invention has short curing reaction time and is beneficial to improving the preparation efficiency of the epoxy resin.

Description

Epoxy resin and preparation method thereof
Technical Field
The invention relates to a resin and a preparation method thereof, in particular to an epoxy resin and a preparation method thereof.
Background
The carbon fiber as a novel high-performance fiber has the characteristics of high strength, high modulus, high temperature resistance, corrosion resistance, fatigue resistance, creep resistance, electric conduction and heat transfer and the like, is gradually applied to various fields of military and civil industries, and aims at the high-quality and high-strength reinforcing material in the market and the vigorous development of the technology in the field of wind power.
The carbon fiber wound gas cylinder has been widely used in the fields of fire fighting, medical treatment, new energy automobiles and the like due to its light weight, high strength and good fatigue performance. The hydrogen cylinder is the main part of the hydrogen supply system of the hydrogen fuel cell automobile. The hydrogen storage tank has the performance characteristics of high pressure for bearing compressed hydrogen, light gas cylinder weight and high hydrogen storage density, is fixed on a road vehicle, is used for storing hydrogen fuel and can be repeatedly filled. Considering that the cylinders may be involved in high temperature working environments, some standards have been described, such as the DOT-CFFC (2007) standard of the U.S. department of transportation, which specifically requires that the cylinders be subjected to a thermal cycle test at 50-90 ℃, and a high temperature creep test if the glass transition temperature of the resin system is below 102 ℃. In view of the above, it is generally desirable to select epoxy resins having a relatively high glass transition temperature (Tg > 102 ℃). The carbon fiber hydrogen storage cylinder resin matrix not only needs to meet the requirement of the cylinder on temperature resistance, but also needs a high-strength, high-toughness and fatigue-resistant resin system to guarantee the service life of the cylinder because the matrix is easy to generate fatigue damage in the use environment of long-term inflation and deflation. The resin matrix used in wet entangling (forming after impregnating the fibers in a resin) requires a low initial viscosity at the working temperature and a long pot life at that temperature.
Therefore, the development of the epoxy resin system for winding the carbon fiber on the gas cylinder becomes an important development direction. There are some prior patent inventions, such as patent literature publication name "an epoxy resin composition for filament winding and a method for preparing the same" (application publication No. CN 107641292A; application publication No. 2018.01.30) which discloses an epoxy resin composition for filament winding, the resin composition has high reactivity at room temperature, the phenomenon that the viscosity of the epoxy resin is doubled at room temperature of 2-4 hours in a tank is shown, the wettability of the resin and the fiber is influenced, and the operation time for soaking the fiber in the resin is shortened; and the curing reaction time is long in the process of preparing the resin composition, so that the production efficiency of the resin composition is influenced.
Disclosure of Invention
The invention provides an epoxy resin, which adopts resin and a curing agent with specific components, has the advantages of long viscosity doubling time at room temperature, room-temperature pot life of more than 12 hours, high toughness, good heat resistance and high mechanical strength.
The invention also provides a preparation method of the epoxy resin, which has short curing reaction time and is beneficial to improving the preparation efficiency of the epoxy resin.
The invention also provides application of the epoxy resin in soaking the fiber for winding the gas cylinder.
The invention also provides a fiber-wound gas cylinder, wherein the winding layer of the gas cylinder is made of the epoxy resin and the fibers.
The epoxy resin provided by the invention comprises the following raw materials of a resin A and a curing agent B, wherein the mass ratio of the resin A to the curing agent B is 100: 35-50;
the resin A comprises, by weight, 40-80 parts of bisphenol A type epoxy resin, 0-45 parts of bisphenol F type epoxy resin, 5-20 parts of polyfunctional group epoxy resin and 5-10 parts of epoxy resin diluent;
the curing agent B comprises 20-60 parts by weight of epoxy curing agent, wherein the epoxy curing agent is an amine curing agent and 0-6 parts by weight of epoxy curing accelerator.
In the aspect of the present invention, the multifunctional epoxy resin may have an epoxy value of 0.8 to 0.95. Or the multifunctional epoxy resin is multifunctional epoxy resin with the functionality of 3-4. For example, the multifunctional epoxy resin may be one or more of multifunctional epoxy resins AG-80, AG-80H, AFG-90, AFG-90H and AG-70.
In the scheme of the invention, the amine curing agent can be one or more of aliphatic amine (such as EC201 and EC210), phenolic amine (such as 2003D and 2003), phenolic amide, polyether amine (such as EC301), dicyandiamide (such as UR300 and UR100), alicyclic amine and aromatic amine (such as diethyl toluene diamine and dimethyl sulfur toluene diamine).
In an embodiment of the present invention, the bisphenol a-type epoxy resin has the following characteristics: the epoxy value is 0.51-0.56, and the viscosity is 8000-11000cp at 25 ℃. For example, the bisphenol A type epoxy resin may be one or more of NPEL-128, NPEL-127 and NPEL-128R.
In an aspect of the present invention, the bisphenol F epoxy resin has the following features: the epoxy value is 0.56-0.62, and the viscosity is 2000-5000cp at 25 ℃. For example, the bisphenol F type epoxy resin is one or more of NPEF-175, NPEF-170, NPEF-180 and NPEF-185.
In an aspect of the present invention, the epoxy resin diluent is a reactive diluent, such as: the epoxy resin diluent may be one or more of phenyl glycidyl ether, o-tolyl glycidyl ether, butyl glycidyl ether, benzyl glycidyl ether, carboxydodecyl to tetradecyl glycidyl ether, 1, 4-butanediol diglycidyl ether, and ethylene glycol diglycidyl ether.
The epoxy curing accelerator is one or more of substituted urea, tertiary amine and salts thereof, imidazole and salts thereof, acetylacetone metal salt, phenols and the like. For example, the epoxy curing accelerator may be one or more of N-methylimidazole and benzyltriethylammonium chloride.
The epoxy resin provided by the invention is a product obtained by curing and reacting the resin A and the curing agent B at 100-140 ℃ for 2-4 hours.
In one embodiment of the present invention, the present invention provides a method for preparing the epoxy resin, comprising the steps of:
1) mixing the components in the resin A at normal pressure to obtain resin A;
2) mixing the components in the curing agent B at normal pressure to obtain a curing agent B; and
3) when in use, the resin A and the curing agent B are mixed, defoamed, and then cured for 2 to 4 hours at the temperature of 100 to 140 ℃ to prepare the epoxy resin.
In the aspect of the present invention, the epoxy resin may be one in which the resin a and the curing agent B are separately packaged. In use, the resin a is mixed with a curing agent B. When the fiber is used for soaking, the fiber soaking step is further included after the resin A and the curing agent B are mixed, and then the fiber is cured for 2 to 4 hours at the temperature of between 100 and 140 ℃ to prepare the fiber for winding the gas cylinder.
Further, the normal pressure in the steps 1) and 2) means 1 atmosphere, or in the case that the reaction vessel does not need pressurization. The mixing temperature in the steps 1) and 2) can be controlled to be a temperature at which the components have good dispersibility, the feeding is convenient or the mixing is uniform. The temperature of the mixing in steps 1) and 2) may be normal temperature, for example 20-35 ℃, or 80-100 ℃. If the ingredients contained in step 2) are solid, the ingredients need to be heated to liquid state for uniform mixing, and the mixing temperature can be determined as required by those skilled in the art knowing the types of the ingredients.
Further, after defoaming in the step 3), curing at 100 ℃ for 1-2 hours and curing at 140 ℃ for 1-2 hours to obtain the epoxy resin.
The invention also provides application of the epoxy resin in soaking the fiber for winding the gas cylinder.
The invention also provides a wound gas cylinder, and a winding layer of the gas cylinder is made of the epoxy resin and the fibers.
The scheme of the invention has the following advantages:
1) the epoxy resin provided by the invention has lower initial viscosity (500-700mPa.s), long viscosity doubling time at room temperature and pot life of more than 12 hours at room temperature (2-4 hours in the prior art).
2) According to the method for preparing the epoxy resin for winding, the curing reaction in the prior art needs to be carried out for 12-18 hours, but the scheme of the application only needs 2-4 hours, so that the preparation efficiency of the epoxy resin is improved.
3) The epoxy resin provided by the invention has improved heat resistance, the glass transition temperature Tg is above 130 ℃, and the epoxy resin also has the advantages of high toughness, good heat resistance and high mechanical strength.
Detailed Description
The present invention is further illustrated by the following examples, which are commercially available from south Asia epoxy resin works as the bisphenol A type epoxy resins NPEL-128, NPEL-127, NPEL-128R, and bisphenol F type epoxy resins NPEF-175, NPEF-170, NPEF-180, NPEF-185 described below. Multifunctional epoxy resins AG-80, AG-80H, AFG-90, and AFG-90H, AG-70 were all available from Shanghai Huayi resin Co., Ltd. Epoxy resin diluents phenyl glycidyl ether, o-tolyl glycidyl ether, butyl glycidyl ether, benzyl glycidyl ether, C-dodecyl to C-tetradecyl glycidyl ether, 1, 4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether were all purchased from New technology, Inc., Anhui, Inc. Diethyltoluenediamine and dimethylthiotoluenediamine were purchased from Yarui chemical Co., Ltd, Kyoho. EC201, EC210, EC301 were procured from the New materials science and technology company, Jia Di Da, Shenzhen. 2003D, 2003 phenolic amine curing agents were purchased from Kadeli. Dicyandiamide UR300, UR100 was purchased from shanghai massecuite industries ltd.
Example 1
1) Preparation of resin A: sequentially adding bisphenol A epoxy resin NPEL-12880 parts, polyfunctional epoxy resin AG-7010 parts and epoxy resin diluent butyl glycidyl ether 5 parts into a reaction kettle, and heating to 80 ℃ at normal pressure; stirring for 1 hour until the mixture is uniform, and cooling the resin mixture to room temperature to obtain resin A;
2) preparation of curing agent B: sequentially adding EC 21020 parts and polyether amine curing agent EC 30110 parts into a reaction kettle, and stirring at normal temperature and normal pressure for 1 hour until the mixture is uniform to obtain curing agent B;
3) and (3) curing: and uniformly mixing the resin A and the curing agent B according to the mass ratio of 100:35, defoaming in vacuum, injecting into a mold, curing at 100 ℃ for 1 hour, and curing at 140 ℃ for 2 hours to obtain the epoxy resin.
The initial viscosity of the epoxy resin was 600cps, the viscosity doubling time was 12 hours, the Tg was 130 ℃, the tensile strength was 78MPa, the tensile modulus was 2940MPa, and the elongation at break was 5.2%. The flexural strength was 120MPa and the flexural modulus was 2860 MPa. Fracture toughness K1C3.5MPa.m1/2。
Example 2:
1) sequentially adding bisphenol A type epoxy resin NPEL-12745 parts, bisphenol F type epoxy resin NPEF-17545 parts, polyfunctional group epoxy resin AG-7015 parts and epoxy resin diluent benzyl glycidyl ether 5 parts into a reaction kettle, heating to 80 ℃ under normal pressure, stirring for 1 hour until the mixture is uniform, and cooling the resin mixture to room temperature to obtain resin A;
2) sequentially adding 40 parts of diethyl toluenediamine and 3 parts of accelerant N-methylimidazole into a reaction kettle, and stirring at normal temperature and normal pressure for 1 hour until the mixture is uniform to obtain a curing agent B;
3) and uniformly mixing the resin A and the curing agent B according to the mass ratio of 100:43, defoaming in vacuum, injecting into a mold, curing at 100 ℃ for 1 hour, and curing at 140 ℃ for 1 hour to obtain the epoxy resin.
The initial viscosity of the epoxy resin was 600cps, the viscosity doubling time was 16 hours, the Tg was 140 ℃, the tensile strength was 83MPa, the tensile modulus was 3000MPa, and the elongation at break was 6% were measured. The flexural strength was 128MPa and the flexural modulus was 2950 MPa. Fracture toughnessK1C4.2MPa.m1/2。
Example 3:
1) sequentially adding 50 parts of bisphenol A epoxy resin NPEL-128R, 50 parts of bisphenol F epoxy resin NPEF-17045 parts, multifunctional epoxy AG-8012 parts and 10 parts of epoxy resin diluent ethylene glycol diglycidyl ether into a reaction kettle, heating to 80 ℃ under normal pressure, stirring for 1 hour until the mixture is uniform, and cooling the resin mixture to room temperature to obtain resin A;
2) sequentially adding 45 parts of dimethyl-sulfur-based toluene diamine and 3 parts of promoter benzyltriethylammonium chloride into a reaction kettle, heating to 100 ℃ under normal pressure, and stirring for 1 hour until the mixture is uniform to obtain a curing agent B;
3) and uniformly mixing the resin A and the curing agent B according to the mass ratio of 100:48, defoaming in vacuum, injecting into a mold, curing at 100 ℃ for 2 hours, and curing at 140 ℃ for 1 hour to obtain the epoxy resin.
The initial viscosity of the epoxy resin was measured to be 650cps, the viscosity doubling time was 15 hours, the Tg was 145 ℃, the tensile strength was 88MPa, the tensile modulus was 3180MPa, and the elongation at break was 6.2%. The flexural strength was 130MPa and the flexural modulus was 3150 MPa. Fracture toughness K1C4.3MPa.m1/2。
Example 4:
1) sequentially adding bisphenol A type epoxy resin NPEL-12880 parts, bisphenol F type epoxy resin NPEF-17010 parts, polyfunctional group epoxy resin AG-90H 10 parts and epoxy resin diluent ethylene glycol diglycidyl ether 7 parts into a reaction kettle, heating to 80 ℃ under normal pressure, stirring for 1 hour until the mixture is uniform, and cooling the resin mixture to room temperature to obtain resin A;
2) sequentially adding polyether amine curing agent EC 30125 parts, phenolic aldehyde amine 200310 parts and accelerator N-methylimidazole 1 part into a reaction kettle, and stirring at normal temperature and normal pressure for 1 hour until the mixture is uniform to obtain curing agent B;
3) and uniformly mixing the resin A and the curing agent B according to the mass ratio of 100:36, defoaming in vacuum, injecting into a mold, curing at 100 ℃ for 1 hour, and curing at 140 ℃ for 1 hour to obtain the epoxy resin.
The initial viscosity of the epoxy resin was measured to be 650cps, and the viscosity doubling time was measured to be 12The tensile strength was 90MPa, the tensile modulus was 3280MPa, and the elongation at break was 4.2% at 138 ℃ in hours. The flexural strength was 146MPa, and the flexural modulus was 3350 MPa. Fracture toughness K1C3.3MPa.m1/2。
Comparative example 1:
1) sequentially adding NPEL-12890 parts of bisphenol A epoxy resin and NPEF-17010 parts of bisphenol F epoxy resin into a reaction kettle, heating to 80 ℃ under normal pressure, stirring for 1 hour until the mixture is uniform, and cooling the resin mixture to room temperature to obtain resin A;
2) sequentially adding the alicyclic amine curing agent EC 20130 parts and the promoter benzyltriethylammonium chloride 1 part into a reaction kettle, heating to 100 ℃ under normal pressure, and stirring for 1 hour until the mixture is uniform to obtain a curing agent B;
3) and uniformly mixing the resin A and the curing agent B according to the mass ratio of 100:39, defoaming in vacuum, injecting into a mold, heating to 100 ℃ for 1 hour, and heating to 140 ℃ for 1 hour to obtain the epoxy resin.
It was found that the epoxy resin had an initial viscosity of 750cps, a doubling time of 4 hours, a Tg of 115 ℃, a tensile strength of 72MPa, a tensile modulus of 2880MPa, and an elongation at break of 3.6%. The flexural strength was 122MPa and the flexural modulus was 2850 MPa. Fracture toughness K1C1.6MPa.m1/2。
Comparative example 2:
1) sequentially adding NPEL-12860 parts of bisphenol A epoxy resin, NPEF-17030 parts of bisphenol F epoxy resin and AG-8010 parts of polyfunctional epoxy resin into a reaction kettle, heating to 80 ℃ under normal pressure, stirring for 1 hour until the mixture is uniform, and cooling the resin mixture to room temperature to obtain resin A;
2) adding 85 parts of anhydride curing agent methyl tetrahydrophthalic anhydride and 3 parts of promoter benzyl triethyl ammonium chloride into a reaction kettle in sequence, heating to 100 ℃ under normal pressure, and stirring for 1 hour until the mixture is uniform to obtain a curing agent B;
3) and uniformly mixing the resin A and the curing agent B according to the mass ratio of 100:95, defoaming in vacuum, injecting into a mold, heating to 100 ℃ for 4 hours, and heating to 140 ℃ for 4 hours to obtain the epoxy resin.
The initial viscosity of the epoxy resin was measured to be 960cps, the viscosity doubling time was 2.5 hours, the Tg was 134 ℃, the tensile strength was 71MPa, the tensile modulus was 2980MPa, and the elongation at break was 3.3%. The flexural strength was 121MPa and the flexural modulus was 3060 MPa. Fracture toughness K1C1.8MPa.m1/2。
The performance index test method and test standard specification of the epoxy resin system are as follows:
1: mixing viscosity test over time
The epoxy resin A and the curing agent B are mixed by 200g according to the proportion, placed in a thermostat at 25 ℃, the viscosity is tested every 1 hour, and the viscosity doubling time is recorded. The test instrument was a Brookfield viscometer, Standard ASTM D-2983.
2: mechanical property test of resin casting body
Tensile properties were tested according to ISO527 and flexural properties were tested according to ISO 178. The fracture toughness was tested according to GB/T2567-.
3: tg test of resin casting
The test was performed according to the DSC midpoint method.
4. Table 1 shows the results of the performance parameter tests of the examples of the present invention and the comparative examples.
TABLE 1
Figure BDA0002352802580000071
Figure BDA0002352802580000081
The epoxy resin provided by the invention has the advantages of low initial viscosity, long viscosity doubling time at room temperature, long service life of more than 12 hours at room temperature, long operable time, high toughness, good heat resistance and high mechanical strength.

Claims (10)

1. The epoxy resin is characterized in that raw materials for preparing the epoxy resin comprise a resin A and a curing agent B, and the mass ratio of the resin A to the curing agent B is 100: 35-50;
the resin A comprises, by weight, 40-80 parts of bisphenol A type epoxy resin, 0-45 parts of bisphenol F type epoxy resin, 5-20 parts of polyfunctional group epoxy resin and 5-10 parts of epoxy resin diluent;
the curing agent B comprises 20-60 parts by weight of epoxy curing agent, wherein the epoxy curing agent is an amine curing agent and 0-6 parts by weight of epoxy curing accelerator.
2. The epoxy resin of claim 1, wherein the multifunctional epoxy resin is a multifunctional epoxy resin having a functionality of 3 to 4.
3. The epoxy resin of claim 1, wherein the amine curing agent is one or more of aliphatic amine, phenolic amide, polyetheramine, dicyandiamide, alicyclic amine, and aromatic amine.
4. The epoxy resin according to claim 1, wherein the bisphenol A epoxy resin has the following characteristics: the epoxy value is 0.51-0.56, and the viscosity is 8000-11000cp at 25 ℃.
5. The epoxy resin of claim 1, wherein the bisphenol F epoxy resin has the following characteristics: the epoxy value is 0.56-0.62, and the viscosity is 2000-5000cp at 25 ℃.
6. The epoxy resin according to claim 1, wherein the epoxy resin is a product obtained by curing reaction of resin A and curing agent B at 100 ℃ to 140 ℃ for 2 to 4 hours.
7. A process for preparing the epoxy resin according to any one of claims 1 to 6,
1) mixing the components in the resin A at normal pressure to obtain resin A;
2) mixing the components in the curing agent B at normal pressure to obtain a curing agent B; and
3) and mixing the resin A and the curing agent B, defoaming, and curing at 100-140 ℃ for 2-4 hours to obtain the epoxy resin.
8. The epoxy resin method according to claim 7, wherein the epoxy resin is prepared by curing at 100 ℃ for 1 to 2 hours and at 140 ℃ for 1 to 2 hours after the defoaming in the step 3).
9. Use of an epoxy resin according to any one of claims 1 to 6 for impregnating fibres for winding gas cylinders.
10. A filament wound cylinder wherein the wound layers of the cylinder are made of the epoxy resin and the filament according to any one of claims 1 to 6.
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CN113861490B (en) * 2021-11-16 2022-12-23 西北工业大学 Method for preparing epoxy microporous foam material based on liquid epoxy resin

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