CN115058099A - Epoxy resin composition with two-phase sea-island structure, composite material and preparation method thereof - Google Patents
Epoxy resin composition with two-phase sea-island structure, composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides an epoxy resin composition with a two-phase sea-island structure, a composite material and a preparation method thereof. The epoxy resin composition with the two-phase sea-island structure comprises the following components in parts by mass: 50-120 parts of bisphenol type glycidyl ether epoxy resin, 5-30 parts of low-viscosity aliphatic glycidyl ether epoxy resin, 50-120 parts of anhydride curing agent, 5-30 parts of polyether toughening agent and 0-5 parts of accelerator. The epoxy resin composition and the epoxy resin-based composite material have a typical two-phase sea-island structure, the toughening effect is obvious, the impact toughness of the prepared composite material is greatly improved, the bending strength and the bending modulus are improved, and after the epoxy resin is toughened by the two-phase sea-island structure, the toughening agent has less influence on the tensile strength and the tensile modulus of the material, and hardly has influence on the glass transition temperature.
Description
Technical Field
The invention belongs to the technical field of epoxy resin-based composite materials, and particularly relates to an epoxy resin composition with a two-phase sea-island structure, a composite material and a preparation method thereof.
Background
Epoxy resin is an advanced composite material resin matrix, and has excellent performance, particularly in wear resistance, mechanical property, adhesion property, chemical stability, electrical insulation property, adhesion property to a base material and the like, so that the figure of the epoxy resin can be seen in the fields of machinery, chemical engineering, buildings, railway traffic, aerospace and the like. However, the epoxy resin forms a three-dimensional network structure after being crosslinked and cured, the crosslinking density is increased, the internal stress is increased, and a cured product is hard and brittle, has poor toughness and is easy to crack, so that the application of the cured product in high-strength and high-toughness composite materials is limited, and therefore, the epoxy resin needs to be modified to achieve the purposes of reinforcement and toughening.
At present, the common modification method is to add epoxy resin with flexible molecular chain, curing agent with flexible molecular chain or modifying agent with active terminal group into epoxy resin/acid anhydride system, which are dispersed at molecular level and embedded into the cross-linked network of epoxy resin through chemical bonding to soften the whole epoxy cross-linked network. For example, chinese patent publication No. CN108892776A discloses an organosilicon-modified epoxy resin and a method for preparing the same, in which the toughness of the modified epoxy resin can be improved by the good flexibility of polysiloxane through a Q-type POSS-terminated polymethylphenylsiloxane-modified bisphenol a-type epoxy resin, but this modification inevitably sacrifices the rigidity and heat resistance of the material although the brittleness of the epoxy resin is reduced to some extent.
Therefore, it is desirable to provide a modified epoxy resin material, which has greatly improved toughness and small influence on the tensile strength, tensile modulus and heat resistance of the material when used as a matrix material of a composite material.
Disclosure of Invention
The invention solves the technical problem of providing an epoxy resin composition with a two-phase sea-island structure, a composite material and a preparation method thereof, wherein the epoxy resin composition and the epoxy resin-based composite material have a typical two-phase sea-island structure, the toughening effect is obvious, the impact toughness of the prepared composite material is greatly improved, the bending strength and the bending modulus are improved, and after the epoxy resin is toughened by the two-phase sea-island structure, the toughening agent has less influence on the tensile strength and the tensile modulus of the material and hardly has influence on the vitrification temperature.
In order to solve the above problems, an aspect of the present invention provides an epoxy resin composition having a two-phase sea-island structure, comprising the following components in parts by mass:
50-120 parts of bisphenol type glycidyl ether epoxy resin, 5-30 parts of low-viscosity aliphatic glycidyl ether epoxy resin, 50-120 parts of anhydride curing agent, 5-30 parts of polyether toughening agent and 0-5 parts of accelerator.
Preferably, the epoxy resin composition with the two-phase sea-island structure comprises the following components in parts by mass:
80-90 parts of bisphenol type glycidyl ether epoxy resin, 10-20 parts of low-viscosity aliphatic glycidyl ether epoxy resin, 80-90 parts of anhydride curing agent, 10-20 parts of polyether toughening agent and 0-2 parts of accelerator.
Preferably, the polyether toughening agent is one or more of polypropylene oxide glycol with the molecular weight of 200-4000 and polytetrahydrofuran glycol with the molecular weight of 200-4000.
Preferably, the bisphenol type glycidyl ether epoxy resin is one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin and bisphenol S type epoxy resin;
preferably, the low-viscosity aliphatic glycidyl ether epoxy resin is one or more of n-butyl glycidyl ether, C12-C14 polyalkyl glycidyl ether, polyethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, 1, 2-propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, and neopentyl glycol diglycidyl ether;
preferably, the anhydride curing agent is one or a combination of more of tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, trimellitic anhydride, tung oil anhydride, methyl nadic anhydride and maleic anhydride.
Another aspect of the present invention provides a method for preparing the above epoxy resin composition having a two-phase sea-island structure, comprising the steps of:
mixing and stirring the bisphenol type glycidyl ether epoxy resin, the low-viscosity aliphatic glycidyl ether epoxy resin, the anhydride curing agent, the polyether toughening agent and the accelerator to obtain the epoxy resin composition with the two-phase sea-island structure.
Preferably, the method specifically comprises the following steps:
s1, mixing the bisphenol type glycidyl ether epoxy resin with the low-viscosity aliphatic glycidyl ether epoxy resin, and performing first ultrasonic emulsification to obtain a modified epoxy resin component;
s2, mixing the anhydride curing agent, the polyether toughening agent and the accelerator, and performing second ultrasonic emulsification to obtain a modified curing agent component;
and S3, mixing the modified epoxy resin component with the modified curing agent component to obtain the epoxy resin composition with the two-phase sea-island structure.
Preferably, the ultrasonic frequency of the first ultrasonic emulsification and/or the second ultrasonic emulsification is 25-60KHz, and the ultrasonic power is 600-6000W.
In another aspect, the present invention provides an epoxy resin-based composite material, which is obtained by compounding a resin matrix material and a fiber-reinforced material, wherein the resin matrix material is the epoxy resin composition having a two-phase sea-island structure or the epoxy resin composition having a two-phase sea-island structure prepared by the above-mentioned preparation method.
Preferably, in the epoxy resin-based composite material, the mass fraction of the fiber reinforced material is 20-40%.
The invention further provides a preparation method of the epoxy resin-based composite material, which comprises the following steps:
A1. preparing the epoxy resin composition having a two-phase sea-island structure;
A2. the epoxy resin composition with the two-phase sea-island structure is adopted to impregnate a fiber reinforced material, and the epoxy resin-based composite material is prepared by a pultrusion process.
Compared with the prior art, the invention has the following beneficial effects:
the epoxy resin composition and the epoxy resin-based composite material have a typical two-phase sea-island structure and an obvious toughening effect. The impact toughness of the epoxy resin-based composite material is greatly improved, the bending strength and the bending modulus are improved, and after the epoxy resin is toughened by forming the two-phase sea island structure, the toughening agent has little influence on the tensile strength and the tensile modulus of the material, and hardly has influence on the vitrification temperature.
According to the preparation method of the epoxy resin composition, bisphenol type glycidyl ether epoxy resin and low-viscosity aliphatic glycidyl ether epoxy resin are mixed and then subjected to ultrasonic emulsification, and the viscosity of the bisphenol type glycidyl ether epoxy resin is reduced through the cavitation effect of the ultrasonic emulsification, so that the operability of the epoxy resin is improved, and the fiber impregnation effect in the production process can be improved. The anhydride curing agent, the polyether toughening agent and the accelerator are mixed and then subjected to ultrasonic emulsification, and the toughening agent is uniformly dispersed in the curing agent at a nano-scale level through the cavitation effect of the ultrasonic emulsification, so that necessary micro-environment conditions are provided for the curing reaction of the epoxy resin and the formation of a uniformly distributed two-phase island structure, and an obvious toughening effect is generated.
Drawings
FIG. 1 is a scanning electron microscope image of an epoxy resin-based composite material of example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first aspect of the embodiments of the present application provides an epoxy resin composition having a two-phase sea-island structure, which comprises the following components in parts by mass:
50-120 parts of bisphenol type glycidyl ether epoxy resin, 5-30 parts of low-viscosity aliphatic glycidyl ether epoxy resin, 50-120 parts of anhydride curing agent, 5-30 parts of polyether toughening agent and 0-5 parts of accelerator.
According to the epoxy resin composition with the two-phase sea-island structure, the polyether toughening agent is added, the polyether toughening agent is aggregated into spherical particles to form a disperse phase in a continuous phase formed by an epoxy resin cross-linked network, the diameter of the disperse phase particles is usually less than several micrometers, and a cured epoxy resin homogeneous phase system is changed into a multiphase system, namely, the 'sea-island structure' is formed, once the 'sea-island structure' is formed, the cracking resistance of the material is mutated, the fracture toughness of the material is greatly (several times and dozens of times) improved, the loss of the inherent mechanical property and heat resistance of the material is small, and the flexibility modification of the epoxy resin cannot be compared.
In some embodiments, the epoxy resin composition having a two-phase sea-island structure comprises the following components in parts by mass:
80-90 parts of bisphenol type glycidyl ether epoxy resin, 10-20 parts of low-viscosity aliphatic glycidyl ether epoxy resin, 80-90 parts of anhydride curing agent, 10-20 parts of polyether toughening agent and 0-2 parts of accelerator.
In some embodiments, the polyether toughening agent is one or more of polyoxypropylene glycol with a molecular weight of 200-4000 and polytetrahydrofuran glycol with a molecular weight of 200-4000.
The specific polyether toughening agent selected in the embodiment of the application, polyoxypropylene glycol is an alcoholic hydroxyl-terminated polypropylene oxide compound, the molecular structure of the polyoxypropylene glycol is a polymer with a long-chain linear molecular structure, two ends of the polyoxypropylene glycol are terminated by hydroxyl groups, ether bonds in the molecular chain exist to greatly increase the flexibility of the molecular chain in the network structure, polyether polyol is precipitated in the curing process due to incompatibility of a polypropylene oxide chain segment and an epoxy curing network structure to form a dispersed phase structure, epoxy resin is cured to form a continuous phase structure, and finally a two-phase 'sea-island structure' is formed. Therefore, the sea-island structure can prevent crack propagation and effectively play a toughening role. Polytetrahydrofuran diol is used as polyether toughening agent, and its toughening mechanism is similar to that of polypropylene oxide diol.
In some embodiments, the bisphenol-type glycidyl ether epoxy resin may be a combination of one or more of bisphenol a-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin.
In some embodiments, the low viscosity aliphatic glycidyl ether epoxy can be a combination of one or more of n-butyl glycidyl ether, C12-C14 polyalkyl glycidyl ether, polyethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, 1, 2-propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether.
The specific low-viscosity aliphatic glycidyl ether epoxy resin selected in the embodiment of the application is a long straight-chain polymer, has excellent flexibility, and can improve the toughness of a cured product; because of low relative molecular weight, low viscosity and good manufacturability, the application life of the glue solution can be prolonged when the glue solution is used as an active diluent.
In some embodiments, the anhydride curing agent may be one or a combination of tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, trimellitic anhydride, eleostearic anhydride, methyl nadic anhydride, and maleic anhydride.
The specific anhydride curing agent selected in the embodiment of the application has the advantages that the epoxy resin cured material cured by the anhydride is excellent in performance, excellent in heat resistance and chemical resistance, small in volatility and toxicity, small in skin irritation, large in mixing amount with the epoxy resin, small in viscosity, capable of being modified by adding the filler, beneficial to reducing cost, long in service life and convenient to construct, and compared with an amine curing agent, the anhydride curing agent is small in mixing amount with the epoxy resin.
In some embodiments, the promoter is a nucleophilic promoter. Further, the nucleophilic accelerator may be triethylamine, Benzyldimethylamine (BDMA), dimethylaminomethylphenol (DMP-10), tris (dimethylaminomethyl) phenol (DMP-30), 2-ethylhexanoate, 2-methylimidazole, 2-ethyl-4-methylimidazole, N-dimethylaniline, triethanolamine, naphthenate, octanoate, or the like.
The specific nucleophilic promoter selected in the embodiment of the application has dual catalysis effects on the anhydride curing agent, namely, the catalyst not only for the anhydride but also for the epoxy resin. The nucleophilic promoter catalyzes the epoxy/anhydride curing system by first generating an alkoxy anion to react with the anhydride to generate a new carboxyl anion, which reacts with the epoxy group to generate a new alkoxy anion. The reaction is alternately carried out to form a polyester type cross-linked structure, and the catalytic polymerization reaction of epoxy groups can be initiated to obtain a polyether cross-linked network structure. The nucleophilic promoter mostly belongs to Lewis base, the stronger Lewis basicity is, the smaller steric hindrance of substituent groups is, the higher catalytic activity is, and the larger influence of the structure and performance of the promoter on the crosslinking curing reaction rate and the performance of a cured product is. The promoter such as DMP-30 selected by the invention is in a stable state at room temperature, so that the service life of the glue solution is greatly prolonged, and the glue solution is rapidly decomposed to generate tertiary amine when heated to about 100 ℃ to generate a catalytic effect.
In some embodiments, the epoxy resin composition having a two-phase sea-island structure further comprises 1 to 3 parts of a release agent.
In some embodiments, the release agent may be a metal stearate such as barium stearate, calcium stearate, magnesium stearate, cadmium stearate, zinc stearate, lead stearate, and the like.
The second aspect of the embodiments of the present application provides a method for preparing the above epoxy resin composition having a two-phase sea-island structure, comprising the steps of:
bisphenol type glycidyl ether epoxy resin, low-viscosity aliphatic glycidyl ether epoxy resin, an anhydride curing agent, a polyether toughening agent and an accelerator are mixed and stirred to obtain the epoxy resin composition with the two-phase sea-island structure.
In some embodiments, the method of preparing the epoxy resin composition having a two-phase sea-island structure may further include the steps of:
s1, mixing bisphenol type glycidyl ether epoxy resin with low-viscosity aliphatic glycidyl ether epoxy resin, and performing first ultrasonic emulsification to obtain a modified epoxy resin component;
s2, mixing an anhydride curing agent, a polyether toughening agent and an accelerator, and performing second ultrasonic emulsification to obtain a modified curing agent component;
and S3, mixing the modified epoxy resin component with the modified curing agent component to obtain the epoxy resin composition with the two-phase sea-island structure.
In the embodiment of the application, bisphenol type glycidyl ether epoxy resin and low-viscosity aliphatic glycidyl ether epoxy resin are mixed and then subjected to ultrasonic emulsification, and the bisphenol type glycidyl ether epoxy resin is modified through the cavitation effect of the ultrasonic emulsification.
In the embodiment of the application, the anhydride curing agent, the polyether toughening agent and the accelerator are mixed and then subjected to ultrasonic emulsification, the curing agent is modified through the cavitation effect of the ultrasonic emulsification, and the modified toughening agent is uniformly dispersed in the curing agent at a nanoscale level, so that necessary micro-environment conditions are provided for the curing reaction of the epoxy resin and the formation of a uniformly distributed two-phase sea-island structure, and an obvious toughening effect is generated.
In some embodiments, the first phacoemulsification and/or the second phacoemulsification is performed in a high power phacoemulsification machine.
In some embodiments, the ultrasonic frequency of the first ultrasonic emulsification and/or the second ultrasonic emulsification is 25-60KHz, and the ultrasonic power is 600-6000W.
In some embodiments, the first phacoemulsification and/or the second phacoemulsification are performed at room temperature.
In some embodiments, a release agent may also be added and mixed in step S2 to facilitate smooth release of the product.
In a third aspect of the present invention, there is provided an epoxy resin-based composite material, which is obtained by compounding a resin matrix material and a fiber-reinforced material, wherein the resin matrix material is the above epoxy resin composition having a two-phase sea-island structure or the epoxy resin composition having a two-phase sea-island structure prepared by the above preparation method.
In the embodiment of the application, the epoxy resin composition with the two-phase sea-island structure is used as a resin base material, the epoxy resin composition has a typical two-phase sea-island structure, the toughening effect is obvious, the impact toughness of the prepared composite material is greatly improved, the bending strength and the bending modulus are improved, and after the epoxy resin is toughened by the two-phase sea-island structure, the toughening agent has less influence on the tensile strength and the tensile modulus of the material, and hardly has influence on the vitrification temperature.
In some embodiments, the mass fraction of the fiber reinforced material in the epoxy resin-based composite material can be 20% -40%, which can further ensure the toughness, rigidity and heat resistance of the composite material.
A fourth aspect of the embodiments of the present application provides a method for preparing the epoxy resin-based composite material, including the following steps:
A1. preparing an epoxy resin composition having a two-phase sea-island structure;
A2. the epoxy resin composite with the two-phase sea-island structure is adopted to impregnate the fiber reinforced material, and the epoxy resin matrix composite is prepared by a pultrusion process.
In some embodiments, step a2 may further include the steps of:
A21. arranging the fiber reinforced material according to a threading drawing;
A22. impregnating a fiber reinforcement with an epoxy resin composition having a two-phase sea-island structure;
A23. and (3) performing preforming, extrusion molding, curing, traction, cutting and preparing the product of the impregnated fiber reinforced material to obtain the epoxy resin-based composite material.
Examples
The present disclosure is more particularly described in the following examples that are intended as illustrative only, since various modifications and changes within the scope of the present disclosure will be apparent to those skilled in the art. All parts, percentages, and ratios reported in the following examples are on a weight basis, all reagents used in the examples are commercially available or synthesized according to conventional methods and can be used directly without further treatment, and the equipment used in the examples is commercially available, unless otherwise specified.
Example 1
The preparation method of the epoxy resin-based composite material comprises the following steps:
1. preparation of epoxy resin composition having two-phase sea-island Structure:
101. mixing 85 parts of bisphenol F type epoxy resin and 15 parts of 1, 4-butanediol diglycidyl ether, and performing ultrasonic emulsification at normal temperature by using a high-power ultrasonic emulsifier, wherein the ultrasonic frequency is 40KHz, and the ultrasonic power is 2000W to obtain a modified epoxy resin component;
102. mixing 60 parts of methyl tetrahydrophthalic anhydride, 20 parts of maleic anhydride, 10 parts of polyoxypropylene glycol with the molecular weight of 2000, 1 part of tris (dimethylaminomethyl) phenol (DMP-30 accelerator and 2 parts of magnesium stearate serving as a release agent, and carrying out ultrasonic emulsification at normal temperature by using a high-power ultrasonic emulsifier, wherein the ultrasonic frequency is 45KHz and the ultrasonic power is 2500W to obtain a modified curing agent component;
103. mixing the modified epoxy resin component and the modified curing agent component, and mechanically stirring to obtain a uniformly dispersed epoxy resin composition with a two-phase sea-island structure;
2. preparing an epoxy resin-based composite material:
201. the glass fiber and the glass fiber stitch-bonding felt are used as fiber reinforced materials, the total usage amount of the glass fiber and the stitch-bonding felt accounts for 22 percent of the total mass of the composite material, and the fiber reinforced materials are arranged according to a threading diagram;
202. impregnating a fiber reinforcement with an epoxy resin composition having a two-phase sea-island structure;
203. and (3) performing preforming, extrusion molding, curing, traction, cutting and preparing the product of the impregnated fiber reinforced material to obtain the epoxy resin-based composite material.
The microstructure of the prepared epoxy resin-based composite material is observed by a scanning electron microscope, as shown in fig. 1, it can be seen that an obvious two-phase sea-island structure (as shown in the marked square frame) is formed in the epoxy resin-based composite material.
Example 2
The preparation method of the epoxy resin-based composite material comprises the following steps:
1. preparation of epoxy resin composition having two-phase sea-island Structure:
101. mixing 80 parts of bisphenol A type epoxy resin and 20 parts of C12-C14 polyalkyl glycidyl ether, and performing ultrasonic emulsification at normal temperature by using a high-power ultrasonic emulsifier, wherein the ultrasonic frequency is 35KHz, and the ultrasonic power is 3000W to obtain a modified epoxy resin component;
102. mixing 55 parts of methyl hexahydrophthalic anhydride, 25 parts of methyl tetrahydrophthalic anhydride, 20 parts of polyoxypropylene glycol with the molecular weight of 800, 1 part of triethylamine accelerator and 2 parts of zinc stearate serving as a release agent, and carrying out ultrasonic emulsification at normal temperature by using a high-power ultrasonic emulsifier, wherein the ultrasonic frequency is 35KHz, and the ultrasonic power is 3000W to obtain a modified curing agent component;
103. mixing the modified epoxy resin component and the modified curing agent component, and mechanically stirring to obtain a uniformly dispersed epoxy resin composition with a two-phase sea-island structure;
2. preparing an epoxy resin-based composite material:
201. taking glass fiber and glass fiber stitch-bonded felt as fiber reinforced materials, wherein the total usage amount of the glass fiber and the stitch-bonded felt accounts for 24% of the total mass of the composite material, and arranging the fiber reinforced materials according to a threading diagram;
202. impregnating a fiber reinforcement with an epoxy resin composition having a two-phase sea-island structure;
203. and (3) performing preforming, extrusion molding, curing, traction, cutting and preparing the product of the impregnated fiber reinforced material to obtain the epoxy resin matrix composite material.
Example 3
The preparation method of the epoxy resin-based composite material comprises the following steps:
1. preparation of epoxy resin composition having two-phase sea-island Structure:
101. mixing 90 parts of bisphenol A epoxy resin and 10 parts of 1, 2-propylene glycol diglycidyl ether, and performing ultrasonic emulsification at normal temperature by using a high-power ultrasonic emulsification machine, wherein the ultrasonic frequency is 50KHz, and the ultrasonic power is 3500W, so as to obtain a modified epoxy resin component;
102. mixing 35 parts of methyl tetrahydrophthalic anhydride, 45 parts of trimellitic anhydride, 15 parts of polytetrahydrofuran glycol with the molecular weight of 2000, 1 part of 2-methylimidazole promoter and 2 parts of release agent lead stearate, and performing ultrasonic emulsification at normal temperature by using a high-power ultrasonic emulsification machine, wherein the ultrasonic frequency is 35KHz and the ultrasonic power is 3000W to obtain a modified curing agent component;
103. mixing the modified epoxy resin component and the modified curing agent component, and mechanically stirring to obtain a uniformly dispersed epoxy resin composition with a two-phase sea-island structure;
2. preparing an epoxy resin-based composite material:
201. the glass fiber and the glass fiber stitch-bonding felt are used as fiber reinforced materials, the total usage amount of the glass fiber and the stitch-bonding felt accounts for 21 percent of the total mass of the composite material, and the fiber reinforced materials are arranged according to a threading diagram;
202. impregnating a fiber reinforcement with an epoxy resin composition having a two-phase sea-island structure;
203. and (3) performing preforming, extrusion molding, curing, traction, cutting and preparing the product of the impregnated fiber reinforced material to obtain the epoxy resin-based composite material.
Example 4
The preparation method of the epoxy resin-based composite material comprises the following steps:
1. preparation of epoxy resin composition having two-phase sea-island structure:
101. mixing 90 parts of bisphenol A epoxy resin and 10 parts of ethylene glycol diglycidyl ether, and performing ultrasonic emulsification at normal temperature by using a high-power ultrasonic emulsifier, wherein the ultrasonic frequency is 55KHz, and the ultrasonic power is 4000W to obtain a modified epoxy resin component;
102. mixing 80 parts of methyl tetrahydrophthalic anhydride, 10 parts of methyl nadic anhydride, 20 parts of polytetrahydrofuran glycol with the molecular weight of 3000, 1 part of 2-ethyl-4-methylimidazole promoter and 2 parts of zinc stearate serving as a release agent, and performing ultrasonic emulsification at normal temperature by using a high-power ultrasonic emulsifier, wherein the ultrasonic frequency is 30KHz, and the ultrasonic power is 4500W to obtain a modified curing agent component;
103. mixing the modified epoxy resin component and the modified curing agent component, and mechanically stirring to obtain a uniformly dispersed epoxy resin composition with a two-phase sea-island structure;
2. preparing an epoxy resin-based composite material:
201. taking glass fiber and glass fiber stitch-bonded felt as fiber reinforced materials, wherein the total usage amount of the glass fiber and the stitch-bonded felt accounts for 23.5 percent of the total mass of the composite material, and arranging the fiber reinforced materials according to a threading diagram;
202. impregnating a fiber reinforcement with an epoxy resin composition having a two-phase sea-island structure;
203. and (3) performing preforming, extrusion molding, curing, traction, cutting and preparing the product of the impregnated fiber reinforced material to obtain the epoxy resin-based composite material.
Comparative example 1
The preparation method of the epoxy resin-based composite material of the comparative example is the same as that of example 1, except that the preparation method of the epoxy resin composition comprises the following steps:
101. mixing 90 parts of bisphenol A epoxy resin and 10 parts of ethylene glycol diglycidyl ether, and uniformly stirring to obtain an epoxy resin component;
102. mixing 80 parts of methyl tetrahydrophthalic anhydride, 10 parts of methyl nadic anhydride, 1 part of 2-ethyl-4-methylimidazole accelerator and 2 parts of release agent zinc stearate, and uniformly stirring to obtain a curing agent component;
103. the epoxy resin component and the curing agent component are mixed and mechanically stirred to obtain the epoxy resin composition.
Comparative example 2
In the preparation method of the epoxy resin-based composite material of the comparative example, the kinds and the parts by mass of the respective preparation raw materials were the same as those in example 1, except that the ultrasonic emulsification was not performed in step 101.
The epoxy resin composition prepared by the comparative example has short pot life, the surface of the composite material prepared by the composition has certain color difference, the obvious die sticking phenomenon can occur after a period of production, and the mechanical property is reduced to a certain degree.
Comparative example 3
In the method for preparing the epoxy resin-based composite material of the present comparative example, the kinds and the parts by mass of the respective preparation raw materials were the same as those in example 1, except that the ultrasonic emulsification was not performed in step 102.
The epoxy resin composition prepared by the comparative example has a remarkably shorter pot life, the composite material prepared by the composition has low surface gloss, after the composite material is produced for a period of time, the surface of the product is whitish and appears intermittently, and the Tg value of the product is remarkably reduced. The analysis may be that the curative ingredients are not well mixed and not well contacted at the molecular level.
Static mechanical property and glass transition temperature test of epoxy resin-based composite material
The glass transition temperature and the static mechanical properties of the epoxy resin-based composite materials obtained in the above examples and comparative examples were measured according to the following test methods, and the test results are shown in table 1.
And DMA test: the test specimens were tested using a DMA1 tester from METTLER TOLEDO instruments, Switzerland. Test parameters are as follows: the heating rate is 20 ℃/min, and the temperature range is 30-150 ℃.
The testing processes of the mechanical properties of the epoxy resin-based composite material, such as tensile property, bending property, impact property and the like, refer to national standards GB/T1447-.
TABLE 1
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. An epoxy resin composition with a two-phase sea-island structure is characterized by comprising the following components in parts by mass:
50-120 parts of bisphenol type glycidyl ether epoxy resin, 5-30 parts of low-viscosity aliphatic glycidyl ether epoxy resin, 50-120 parts of anhydride curing agent, 5-30 parts of polyether toughening agent and 0-5 parts of accelerator.
2. The epoxy resin composition with two-phase sea-island structure according to claim 1, comprising the following components in parts by mass:
80-90 parts of bisphenol type glycidyl ether epoxy resin, 10-20 parts of low-viscosity aliphatic glycidyl ether epoxy resin, 80-90 parts of anhydride curing agent, 10-20 parts of polyether toughening agent and 0-2 parts of accelerator.
3. The epoxy resin composition having a two-phase sea-island structure according to claim 1, wherein:
the polyether toughening agent is one or more of polyoxypropylene glycol with the molecular weight of 200-4000 and polytetrahydrofuran glycol with the molecular weight of 200-4000.
4. The epoxy resin composition having a two-phase sea-island structure according to claim 1, wherein:
the bisphenol type glycidyl ether epoxy resin is one or a combination of bisphenol A type epoxy resin, bisphenol F type epoxy resin and bisphenol S type epoxy resin;
the low-viscosity aliphatic glycidyl ether epoxy resin is one or a combination of more of n-butyl glycidyl ether, C12-C14 polyalkyl glycidyl ether, polyethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, 1, 2-propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, diglycidyl ether and neopentyl glycol diglycidyl ether;
the anhydride curing agent is one or a combination of more of tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, trimellitic anhydride, tung oil anhydride, methyl nadic anhydride and maleic anhydride.
5. A method for preparing the epoxy resin composition having two-phase sea-island structure according to any one of claims 1 to 4, comprising the steps of:
mixing and stirring the bisphenol type glycidyl ether epoxy resin, the low-viscosity aliphatic glycidyl ether epoxy resin, the anhydride curing agent, the polyether toughening agent and the accelerator to obtain the epoxy resin composition with the two-phase sea-island structure.
6. The preparation method according to claim 5, characterized by comprising the following steps:
s1, mixing the bisphenol type glycidyl ether epoxy resin with the low-viscosity aliphatic glycidyl ether epoxy resin, and performing first ultrasonic emulsification to obtain a modified epoxy resin component;
s2, mixing the anhydride curing agent, the polyether toughening agent and the accelerator, and performing second ultrasonic emulsification to obtain a modified curing agent component;
and S3, mixing the modified epoxy resin component with the modified curing agent component to obtain the epoxy resin composition with the two-phase sea-island structure.
7. The method of claim 6, wherein:
the ultrasonic frequency of the first ultrasonic emulsification and/or the second ultrasonic emulsification is 25-60KHz, and the ultrasonic power is 600-6000W.
8. An epoxy resin-based composite material, which is obtained by compounding a resin matrix material and a fiber-reinforced material, wherein the resin matrix material is the epoxy resin composition having a two-phase sea-island structure according to any one of claims 1 to 4 or the epoxy resin composition having a two-phase sea-island structure obtained by the preparation method according to any one of claims 5 to 7.
9. The epoxy-based composite material according to claim 8, characterized in that:
in the epoxy resin-based composite material, the mass fraction of the fiber reinforced material is 20-40%.
10. A method for preparing an epoxy resin based composite material according to claim 8 or 9, comprising the steps of:
A1. preparing the epoxy resin composition having a two-phase sea-island structure;
A2. the epoxy resin composition with the two-phase sea-island structure is adopted to impregnate a fiber reinforced material, and the epoxy resin-based composite material is prepared by a pultrusion process.
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| CN202210990323.4A CN115058099B (en) | 2022-08-18 | 2022-08-18 | Epoxy resin composition with two-phase sea-island structure, composite material and preparation method of epoxy resin composition |
| PCT/CN2023/103005 WO2024037194A1 (en) | 2022-08-18 | 2023-06-28 | Epoxy resin composition having two-phase sea-island structure, composite material, and preparation methods therefor |
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| CN117343487A (en) * | 2023-10-26 | 2024-01-05 | 苏州浦泰汽配有限公司 | Wear-resistant impact-resistant automobile bottom guard plate and forming method thereof |
| WO2024037194A1 (en) * | 2022-08-18 | 2024-02-22 | 北京玻钢院复合材料有限公司 | Epoxy resin composition having two-phase sea-island structure, composite material, and preparation methods therefor |
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| Publication number | Publication date |
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| CN115058099B (en) | 2022-11-11 |
| WO2024037194A1 (en) | 2024-02-22 |
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