CN114085359A - High-modulus epoxy resin matrix with controllable reaction activity and preparation method thereof - Google Patents

High-modulus epoxy resin matrix with controllable reaction activity and preparation method thereof Download PDF

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CN114085359A
CN114085359A CN202111274693.XA CN202111274693A CN114085359A CN 114085359 A CN114085359 A CN 114085359A CN 202111274693 A CN202111274693 A CN 202111274693A CN 114085359 A CN114085359 A CN 114085359A
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epoxy resin
curing agent
resin matrix
substituent
controllable
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李龙
杨云华
冯志海
朱世鹏
张犇
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Aerospace Research Institute of Materials and Processing Technology
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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
    • C08G59/40—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
    • C08G59/20—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
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3218—Carbocyclic compounds
    • 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
    • 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
    • C08G59/54—Amino amides>

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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)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)

Abstract

The invention discloses a high-modulus epoxy resin matrix with controllable reaction activity, which is a combination of multifunctional epoxy resin and aromatic amine curing agents, wherein the aromatic amine curing agents are compounds obtained by substituting aromatic ring structures such as benzene rings, biphenyl, diphenyl and condensed rings with amino groups and electron-withdrawing groups or electron-donating groups. The invention also discloses a preparation method of the high-modulus epoxy resin matrix with controllable reaction activity.

Description

High-modulus epoxy resin matrix with controllable reaction activity and preparation method thereof
Technical Field
The invention belongs to the technical field of resin matrix composite materials, and relates to a high-modulus epoxy resin matrix with controllable reaction activity.
Background
Epoxy resin is the most common resin matrix of resin-based composite materials, has wide sources and various varieties, and the molecular structure, the crosslinking density and the like of the epoxy resin and a curing agent determine the mechanical properties of a resin cured product; common epoxy resin curing agents comprise amines, acid anhydrides, imidazoles and the like, wherein the amine curing agent has the advantages of cheap raw materials, high performance of reaction cured products and wide application. The amine curing agent can be divided into aliphatic amine and aromatic amine, and the aromatic amine has a benzene ring structure, so that the molecular chain rigidity is higher, and the modulus of the obtained cured product is higher.
There are many methods for forming epoxy resin-based composite materials, but in any process, the forming process can be summarized as that the resin soaks the reinforcing fiber and the curing reaction occurs under the pressure/temperature condition to obtain the composite material product. Whether the formulation of the molding process parameters of the composite material is reasonable or not is determined to determine the molding quality of the composite material, and the optimal molding process parameters must be formulated by combining the characteristics of the molding process, such as the size, the shape characteristic, the rheological property of resin, the curing property of resin and the like. The formulation of molding process parameters is closely related to the curing reactivity of the resin, the resin gel time reflecting the resin reactivity determines the process window time of the resin, and the resin matrix has to have a certain process window to meet the preparation requirement of the composite material.
For a given combination of resin and curing agent, the method for adjusting the reactivity and the process window is usually to add an accelerator or an inhibitor, and the method has two problems, namely, the additive is a third phase which may significantly affect the physical properties of the epoxy cured product, such as the activity adjustment is realized, but significantly affects the properties of the cured product, such as strength, modulus and the like; on the other hand, most amine curing agents have relatively high reaction activity, and the method of adding the inhibitor has no obvious effect on adjusting the reaction activity of the amine curing agents, so that the actual requirements of the composite material forming process are difficult to meet.
Disclosure of Invention
The invention aims to overcome the defects and provide a high-modulus epoxy resin matrix with controllable reaction activity, the high-modulus epoxy resin matrix is a combination of multifunctional epoxy resin and aromatic amine curing agents, and the aromatic amine curing agents are compounds obtained by substituting structures such as amino groups and electron-withdrawing groups or electron-donating groups for benzene rings and the like. The invention also provides a preparation method of the high-modulus epoxy resin matrix with controllable reactivity.
In order to achieve the above purpose, the invention provides the following technical scheme:
a high-modulus epoxy resin matrix with controllable reaction activity comprises the following components in parts by weight:
100 parts of polyfunctional epoxy resin;
10-50 parts of an activity-controllable aromatic amine curing agent;
the functionality of the multifunctional epoxy resin is more than or equal to 3;
the activity controllable aromatic amine curing agent is an accelerating curing agent or an inhibiting curing agent;
the accelerating curing agent is a combination of one or more compounds obtained by substituting an X1 substituent and an X2 substituent on a main body structure, wherein in each compound, the main body structure is one of a benzene ring structure, a diphenyl structure, a biphenyl structure, a heterocyclic structure or a condensed ring structure, the X1 substituent is an electron-donating group, and the X2 substituent is an amino group;
the inhibition type curing agent is a combination of one or more compounds obtained by substituting an X1 substituent and an X2 substituent on a main body structure, wherein in each compound, the main body structure is one of a benzene ring structure, a diphenyl structure, a biphenyl structure, a heterocyclic structure or a condensed ring structure, the X1 substituent is an electron withdrawing group, and the X2 substituent is amino.
Furthermore, in each compound of the activity-controllable aromatic amine curing agent, the number of amino groups is more than or equal to 1 and less than or equal to 3.
Further, in each compound of the accelerated curing agent, the electron donating group includes-OH, - (CH)2)nCH3，-O(CH2)nCH3，-(CH2)nNH2or-NH2One or more than one of them.
Further, the method comprisesWherein each of the compounds of the inhibiting curing agent has an electron-withdrawing group comprising Y, -CY3，-NO2，-SO3H, -CONH-or-CN, wherein Y represents halogen element.
Further, the multifunctional epoxy resin is one or a mixture of more than one of trifunctional or tetrafunctional glycidyl amine, trifunctional or tetrafunctional glycidyl ether, trifunctional or tetrafunctional alicyclic epoxy and trifunctional or tetrafunctional heterocyclic epoxy.
Furthermore, the accelerating curing agent is one or a mixture of more than one of 2, 4-diaminotoluene, 1,3, 5-tri (4-aminophenyl) benzene, m-xylylenediamine or diaminodiphenylmethane, and the like, the molar ratio of active hydrogen of amino groups in the accelerating curing agent to epoxy groups in the multifunctional epoxy resin is 0.8-1.2, and compared with the main structure of the aromatic amine, the gel time of a resin matrix can be shortened to less than half of the original gel time compared with the unsubstituted curing agent of X1 after the accelerating curing agent substituted by X1 is applied.
Furthermore, the inhibiting type curing agent is one or a mixture of more than one of 4-fluoro-1, 2-phenylenediamine, 3, 5-diaminobenzotrifluoride, sulfoaniline, 1, 5-naphthalene diamine, 1, 8-naphthalene diamine, diaminodiphenyl amide or diaminodiphenyl sulfone, and the like, and the molar ratio of active hydrogen of amino in the inhibiting type curing agent to epoxy groups in the multifunctional epoxy resin is 0.8-1.2. Compared with the main structure of aromatic amine, after the inhibiting curing agent substituted by X1 is applied, the gel time of the resin matrix can be prolonged to more than 2 times compared with the unsubstituted curing agent X1.
The preparation method of the high-modulus epoxy resin matrix with controllable reactivity is characterized by comprising the following steps:
(1) uniformly mixing the polyfunctional epoxy resin and the active controllable aromatic amine type curing agent at room temperature;
(2) homogenizing the mixture obtained in the step (1) to obtain a resin composition;
(3) and casting and defoaming the resin composition to obtain the high-modulus epoxy resin matrix with controllable reactivity.
Further, in the step (2), the mixture obtained in the step (1) is homogenized by a specific method, namely, the mixture obtained in the step (1) is placed in a dispersion homogenizer and stirred at a high speed of 300-18000 r/min for 5-30 min;
in the step (3), the resin composition is poured into a mold preheated to 40-100 ℃, and is placed in a vacuum oven for deaeration for 5-20 min.
Compared with the prior art, the invention has the following beneficial effects:
(1) the high-modulus epoxy resin matrix with controllable reaction activity is a combination of multifunctional epoxy resin and aromatic amine curing agents, ensures that the resin modulus can be maintained at a higher level (more than 4.3 GPa), and is beneficial to improving performances of compression, shearing and the like of a composite material closely related to the resin when the high-modulus epoxy resin matrix is used as the matrix;
(2) compared with an aromatic amine main body structure, the accelerating curing agent enables the gel time of the resin matrix to be shortened to be less than half of the original gel time, and the inhibiting curing agent enables the gel time of the resin matrix to be prolonged to be more than 2 times of the original gel time;
(3) aiming at the adjustment of the curing activity of the widely applied aromatic amine curing agent, the high-modulus epoxy resin matrix with controllable reactivity realizes the adjustment of the amino reactivity by virtue of electrophilic and nucleophilic effects of a substituent group from the perspective of molecular structure design; the reaction activity of the aromatic amine group is changed by adjusting the type, the number and the position of the substituent groups, so that the aim of controllable reaction activity is fulfilled; from the perspective of molecular structure modification, the reaction activity of the curing agent is adjusted in a larger range, but the performance of the original curing agent is changed as much as possible; when the epoxy resin matrix with controllable reaction activity and high modulus is used as a composite material matrix, different process time windows are provided according to curing activity performance, and the requirements of different molding processes are met;
(4) according to the high-modulus epoxy resin matrix with controllable reactivity, the curing activity is changed through the molecular structure design, a third phase of reaction inhibitor or accelerator is not required to be added while the curing activity is adjusted, the influence on the viscosity of the resin matrix and the mechanical property of a cured product of the resin matrix is small, and the mechanical property and the process property can be considered at the same time.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
The invention aims to provide a high-modulus epoxy resin matrix with controllable reaction activity and a preparation method thereof aiming at the requirement of a composite material forming process on a high-modulus resin process window, and on the basis of ensuring the mechanical properties of epoxy resin such as high modulus and the like, the resin curing activity is regulated and controlled in a larger range, so that the actual requirements of different composite material forming processes are met.
The invention relates to a high-modulus epoxy resin matrix with controllable reaction activity, which comprises polyfunctional epoxy resin and an activity-controllable aromatic amine curing agent shown in a formula (1); the epoxy resin and the curing agent respectively comprise the following components in parts by weight: 100 parts of epoxy resin and 10-50 parts of curing agent.
Figure BDA0003329754480000051
The activity-controllable aromatic amine curing agent can be a single compound or a mixture of a plurality of single compounds; the main structure of the single compound can be a benzene ring structure, or can be a diphenyl structure, a biphenyl structure, a heterocyclic structure or a condensed ring structure obtained by substituting R1 in the formula (1); the main structure of the aromatic ring is provided with one or more amino groups, wherein-NH in the amino group2The number of n is n, n is more than or equal to 1 and less than or equal to 3; in addition to the amine group, there are other substituents X1.
The activity-controllable aromatic amine curing agent can be used as a low-activity inhibition curing agent according to different substituent groups X1, namely compared with a curing agent which is not substituted by X1, the room-temperature gel time is prolonged to more than 2 times of the original room-temperature gel time; or as a highly active accelerating curing agent, i.e., the room temperature gel time is reduced to within half of the original room temperature gel time compared to a curing agent not substituted with X1.
The substituent X1 of the compound contained in the low-activity inhibition type curing agent comprises one or more of halogen elements, nitryl, sulfo, amido, cyano or trihalomethyl, namely X1 represents-Y, -CY3(Y is a halogen element), -NO2、-SO3H. One or more of-CONH-, -CN and the like.
The substituent X1 in the compound contained in the high-activity accelerating type curing agent comprises one or more of hydroxyl, alkyl, alkoxy, alkylamino or amino, namely X1 represents-OH, - (CH2)nCH3、-O(CH2)nCH3、-(CH2)nNH2、-NH2And the like.
The multifunctional epoxy resin is one or more of trifunctional or tetrafunctional glycidyl amine, glycidyl ether, alicyclic epoxy or heterocyclic epoxy.
The invention relates to a preparation method of a high-modulus epoxy resin matrix with controllable reaction activity, which comprises the following steps,
(1) uniformly mixing the polyfunctional epoxy resin and the active controllable aromatic amine type curing agent according to the mass ratio at room temperature;
(2) placing the obtained mixture in a high-speed dispersion homogenizer, and stirring at a high speed of 300-18000 r/min for 5-30 min to obtain a homogeneous resin composition;
(3) and pouring the resin composition into a mold preheated to 40-100 ℃, placing the mold into a vacuum oven, defoaming for 5-20 min, and then preparing a resin casting body or a subsequent composite material molding process.
The principle of the technical scheme of the invention is as follows: on one hand, by designing a multifunctional epoxy resin structure and a multifunctional active controllable aromatic amine type curing agent, the crosslinking density and the molecular chain rigidity of a resin cured material are improved, and the high modulus performance of the epoxy resin is realized; on the other hand, based on the principle of reaction of amino and epoxy groups, electron withdrawing groups or electron donating groups are introduced into the molecules of the curing agent to change the electron cloud density of the amino, so that the reaction activity of the amino is inhibited or promoted, and the manufacturability of the resin composition is adjusted; the molecular structure design does not need to introduce a third phase, and the influence on other properties of resin curing is avoided as much as possible while the manufacturability is adjusted.
Example 1:
the epoxy resin is 4, 5-epoxy cyclohexane-1, 2-dicarboxylic acid diglycidyl ester, namely TDE-85 epoxy resin; the curing agent is a mixture of 2, 4-diaminotoluene and 1,3, 5-tri (4-aminophenyl) benzene. Mixing 100 parts by mass of epoxy resin, 10 parts by mass of 2, 4-diaminotoluene and 30 parts by mass of 1,3, 5-tris (4-aminophenyl) benzene curing agent, placing the mixture in a high-speed dispersion homogenizer, carrying out high-speed homogenization for 5min, and taking a part of sample for measuring the gel time at room temperature; and pouring the other part of the sample into a mold preheated to 60 ℃, placing the mold into a vacuum oven, defoaming for 5min, and then using the sample for resin casting body preparation or cooling and then using the sample for composite material preparation.
Example 2:
mixing 100 parts by mass of epoxy resin and 27 parts by mass of curing agent, placing the mixture in a high-speed dispersion homogenizer for high-speed homogenization for 30min, and taking a part of sample for measuring the gel time at room temperature; and pouring the other part of the sample into a mold preheated to 60 ℃, placing the mold into a vacuum oven, defoaming for 10min, and then preparing the resin casting body or cooling the resin casting body for preparing the composite material.
Example 3:
mixing 100 parts (by mass) of epoxy resin and 38 parts (by mass) of curing agent, placing the mixture in a high-speed dispersion homogenizer, homogenizing at a high speed for 10min, and taking a part of sample to measure the gel time at room temperature; and pouring the other part of the sample into a mold preheated to 80 ℃, placing the mold into a vacuum oven, defoaming for 10min, and then preparing the resin casting body or cooling the resin casting body for preparing the composite material.
Example 4:
mixing 100 parts of epoxy resin, 25 parts (by mass) of diaminodiphenylamide and 12 parts (by mass) of 1, 8-diaminonaphthalene curing agent, placing the mixture in a high-speed dispersion homogenizer, homogenizing at a high speed for 20min, and taking a part of sample for measuring the gel time at room temperature; and pouring the other part of the sample into a mold preheated to 80 ℃, placing the mold into a vacuum oven, defoaming for 10min, and then preparing the resin casting body or cooling the resin casting body for preparing the composite material.
Example 5:
mixing 100 parts of epoxy resin and 26 parts (mass parts) of curing agent, placing the mixture in a high-speed dispersion homogenizer, homogenizing at a high speed for 30min, and taking a part of samples to measure the gel time at room temperature; and pouring the other part of the sample into a mold preheated to 100 ℃, placing the mold into a vacuum oven, defoaming for 10min, and then preparing the resin casting body or cooling the resin casting body for preparing the composite material.
Comparative example 1
Through the query of literature, a common high-modulus epoxy resin composition is selected for comparison, namely TDE-85 epoxy resin and m-phenylenediamine curing agent. Compared with the comparative example 1, the resin modulus of the examples 1 to 5 of the invention is kept higher, more than 4.3GPa, on the premise of keeping the similarity of the main molecular structure, and the mechanical property is not obviously sacrificed when the curing activity of the resin matrix is adjusted.
Compared with the m-phenylenediamine curing agent in the comparative example 1, on the main structure of the common aromatic amine, the design of the example 1 introduces electron donating groups on methyl and amino, and the electron donating groups are mixed, so that the activity of the amino is improved, and the curing agent is used as an accelerating curing agent; examples 2 and 3 designed to introduce an electron withdrawing group of halogen, reduced the amino activity, and used as an inhibitory curing agent; example 4 an electron withdrawing group incorporating a fused ring structure and diphenylamide was designed and mixed to reduce the amino activity and used as an inhibitory curing agent; example 5 an electron withdrawing group with a sulfonate group was designed to reduce the amino activity and used as an inhibiting curing agent. Compared with the 22h gel time measured in the comparative example 1, the gel time of the resin composition is prolonged or shortened by several times by designing different substituents on the curing agent molecules in the examples 1 to 5, the gel time is shortened to 4.5h at the minimum and is prolonged to more than 168h (one week) at the maximum at room temperature, and the reaction activity of the resin composition is greatly adjusted.
TABLE 1 comparison of the Properties of the examples and comparative examples
Figure BDA0003329754480000081
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Those skilled in the art will appreciate that those matters not described in detail in the present specification are well known in the art.

Claims (9)

1. The high-modulus epoxy resin matrix with controllable reactivity is characterized by comprising the following components in parts by mass:
100 parts of polyfunctional epoxy resin;
10-50 parts of an activity-controllable aromatic amine curing agent;
the functionality of the multifunctional epoxy resin is more than or equal to 3;
the activity controllable aromatic amine curing agent is an accelerating curing agent or an inhibiting curing agent;
the accelerating curing agent is a combination of one or more compounds obtained by substituting an X1 substituent and an X2 substituent on a main body structure, wherein in each compound, the main body structure is one of a benzene ring structure, a diphenyl structure, a biphenyl structure, a heterocyclic structure or a condensed ring structure, the X1 substituent is an electron-donating group, and the X2 substituent is an amino group;
the inhibition type curing agent is a combination of one or more compounds obtained by substituting an X1 substituent and an X2 substituent on a main body structure, wherein in each compound, the main body structure is one of a benzene ring structure, a diphenyl structure, a biphenyl structure, a heterocyclic structure or a condensed ring structure, the X1 substituent is an electron withdrawing group, and the X2 substituent is amino.
2. The reactive controlled high modulus epoxy resin matrix according to claim 1, wherein said reactive controlled aromatic amine type curing agent has 1 or less amino groups and 3 or less amino groups per compound.
3. The reactive controlled high modulus epoxy resin matrix of claim 1, wherein said accelerating curative comprises-OH, - (CH) for each compound of said accelerating curative2)nCH3，-O(CH2)nCH3，-(CH2)nNH2or-NH2One or more than one of them.
4. The reactive controlled high modulus epoxy resin matrix of claim 1, wherein said inhibiting curing agent comprises Y, -CY for each electron withdrawing group3，-NO2，-SO3H, -CONH-or-CN, wherein Y represents halogen element.
5. The reactive controlled high modulus epoxy matrix of claim 1, wherein said multifunctional epoxy resin is one or a mixture of more than one of trifunctional or tetrafunctional glycidyl amine, trifunctional or tetrafunctional glycidyl ether, trifunctional or tetrafunctional alicyclic epoxy, and trifunctional or tetrafunctional heterocyclic epoxy.
6. The reactive high modulus epoxy resin matrix according to claim 1, wherein said accelerating curing agent is one or more of 2,4 diaminotoluene, 1,3, 5-tris (4-aminophenyl) benzene, m-xylylenediamine or diaminodiphenylmethane, and the molar ratio of the amino active hydrogen in said accelerating curing agent to the epoxy group in the multifunctional epoxy resin is 0.8-1.2.
7. The reactive high modulus epoxy resin matrix according to claim 1, wherein the inhibiting curing agent is one or more of 4-fluoro-1, 2-phenylenediamine, 3, 5-diaminobenzotrifluoride, sulfoaniline, 1, 5-naphthalene diamine, 1, 8-naphthalene diamine, diaminodiphenyl amide or diaminodiphenyl sulfone, and the molar ratio of the active hydrogen of the amino group in the inhibiting curing agent to the epoxy group in the multifunctional epoxy resin is 0.8-1.2.
8. The process for the preparation of a controlled reactivity high modulus epoxy resin matrix according to any one of claims 1 to 7 comprising the steps of:
(1) uniformly mixing the polyfunctional epoxy resin and the active controllable aromatic amine type curing agent at room temperature;
(2) homogenizing the mixture obtained in the step (1) to obtain a resin composition;
(3) and casting and defoaming the resin composition to obtain the high-modulus epoxy resin matrix with controllable reactivity.
9. The method for preparing a high modulus epoxy resin matrix with controllable reactivity according to claim 8, wherein in the step (2), the mixture obtained in the step (1) is homogenized by placing the mixture obtained in the step (1) in a dispersion homogenizer, and stirring at a high speed of 300-18000 rpm for 5-30 min;
in the step (3), the resin composition is poured into a mold preheated to 40-100 ℃, and is placed in a vacuum oven for deaeration for 5-20 min.
CN202111274693.XA 2021-10-29 2021-10-29 High-modulus epoxy resin matrix with controllable reaction activity and preparation method thereof Pending CN114085359A (en)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN116162225A (en) * 2023-01-09 2023-05-26 华东理工大学 Epoxy resin material and preparation method and application thereof

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CN1740207A (en) * 2005-09-14 2006-03-01 中国科学院广州化学研究所 A kind of epoxy resin roughening and curing agent
JP2008255217A (en) * 2007-04-04 2008-10-23 Yokohama Rubber Co Ltd:The Curable resin composition
CN110283300A (en) * 2019-07-15 2019-09-27 上海华谊树脂有限公司 One kind being suitable for molding epoxy composite of composite liquid and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1740207A (en) * 2005-09-14 2006-03-01 中国科学院广州化学研究所 A kind of epoxy resin roughening and curing agent
JP2008255217A (en) * 2007-04-04 2008-10-23 Yokohama Rubber Co Ltd:The Curable resin composition
CN110283300A (en) * 2019-07-15 2019-09-27 上海华谊树脂有限公司 One kind being suitable for molding epoxy composite of composite liquid and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116162225A (en) * 2023-01-09 2023-05-26 华东理工大学 Epoxy resin material and preparation method and application thereof
CN116162225B (en) * 2023-01-09 2024-04-02 华东理工大学 Epoxy resin material and preparation method and application thereof

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