CN109385045B - Medium-temperature cured high-toughness epoxy resin and preparation method thereof - Google Patents
Medium-temperature cured high-toughness epoxy resin and preparation method thereof Download PDFInfo
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- CN109385045B CN109385045B CN201810938261.6A CN201810938261A CN109385045B CN 109385045 B CN109385045 B CN 109385045B CN 201810938261 A CN201810938261 A CN 201810938261A CN 109385045 B CN109385045 B CN 109385045B
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
Abstract
The invention relates to a medium-temperature curing high-toughness epoxy resin and a preparation method thereof, which are characterized in that: the resin is prepared fromThe adhesive comprises, by mass, 1-15 parts of hydroxyl hyperbranched polysiloxane containing tertiary amine, 85-100 parts of bisphenol A epoxy resin and 65-80 parts of anhydride curing agent. The resin has the characteristics of low curing temperature, good manufacturability, good toughness and the like, is used as a resin matrix of electronic packaging materials, structural composite materials and the like in the fields of electronic appliances, vehicles and the like, and has wide application prospect. The curing process of the casting body is 100 ℃/2h +130 ℃/3h +150 ℃/2h, and the impact strength is more than 38.0KJ/m2The bending strength is more than 140MPa, and the thermal stability is good.
Description
Technical Field
The invention belongs to the technical field of advanced polymer material science, and relates to a medium-temperature cured high-toughness epoxy resin and a preparation method thereof.
Background
Epoxy resin is used as the most common industrial resin matrix material, and is widely applied in the fields of aerospace, electronic industry, automobile manufacturing and the like due to the advantages of excellent mechanical property, good processability, higher dimensional stability, solvent resistance and the like. However, with the development of science and technology, the technical requirements of emerging fields on products are higher and higher, the performance of the traditional epoxy resin cured product cannot meet the requirements, the problems of high brittleness, insufficient toughness, reduced thermal stability after modification and the like exist, and a new method needs to be found for modifying the products.
At present, the methods for modifying epoxy resin at home and abroad mainly comprise rubber elastomer modification, thermoplastic resin modification, core-shell polymer modification, nanoparticle modification and the like. However, the above methods also have significant disadvantages in toughening epoxy resins. The rubber elastomer toughening epoxy resin utilizes phase separation of rubber particles in an epoxy resin continuous phase; on the other hand, the active end group of the rubber is used for participating in the curing reaction of the epoxy resin so as to improve the interface bonding strength between the epoxy resin and the resin matrix. When an external force is applied, the two-phase interface can generate plastic deformation to prevent cracks from expanding, and the toughening effect is achieved. Various rubbers such as hydroxyl-terminated polybutadiene, carboxyl-terminated polybutadiene, hydroxyl-terminated nitrile rubber, carboxyl-terminated nitrile rubber and epoxy-terminated nitrile rubber are used for toughening modification of epoxy resin. However, rubber, while improving the toughness of cured epoxy resins, often results in a significant decrease in the thermal stability and modulus of the cured epoxy resins and a deterioration in the processing of the resins.
Compared with rubber elastomers, the thermoplastic resin has higher modulus and heat resistance, and the addition of the thermoplastic resin into the epoxy resin can improve the toughness of the material and maintain or improve the modulus and the heat stability of the material. When the epoxy resin is subjected to external force, the thermoplastic resin can generate large deformation to absorb fracture energy, so that the expansion of cracks is hindered, and the toughness of the epoxy resin is improved. Polysulfone, polyethersulfone, polyetherimide, polyetherketone, polyetheretherketone and polycarbonate can be used for toughening and modifying epoxy resin. However, in the thermoplastic resin modified epoxy resin system, the phase separation process and control of the phase structure are critical for the modification. In the molding process, the thermoplastic resin can not generate phase inversion to form a continuous phase structure, and the toughening effect can be directly influenced; whether the solubility parameter of the epoxy resin is matched with that of the epoxy resin or not and whether the phase splitting process of the selected curing agent can be controlled or not are the prerequisites for obtaining the high-toughness epoxy resin. Meanwhile, the thermoplastic resin modified epoxy resin has problems that the viscosity of the epoxy resin is increased, the process is complicated, and the control is difficult.
When the core-shell polymer is used as a toughening agent, the core-shell polymer is usually in a soft core-hard shell structure, the core layer is a rubber body with a toughening effect, and the shell layer is a polymer which can be compatible and reacted with epoxy resin and usually has a functional group capable of reacting with an epoxy resin matrix. The core-shell polymer toughened epoxy has the biggest characteristic that the particle form is basically kept unchanged before and after curing, and the particles can be uniformly dispersed in a resin matrix, so that the toughening effect is obvious, but the friction coefficient of the epoxy resin is increased, and the wear resistance is reduced.
The inorganic nano particle toughened epoxy resin has high surface activity and can be tightly connected with a resin matrix because the epoxy resin has a very large specific surface area and the surface contains special structures such as unsaturated bonds or dangling bonds. The mechanism of the inorganic nano particle toughening epoxy resin is as follows: (1) the nano particles are easy to cause stress concentration under the action of external force, so that surrounding resin is yielded and energy is absorbed; (2) the inorganic particles have different deformation rates from the matrix resin, and when they are impacted, they form voids, preventing crack propagation. However, the dispersion of the nanoparticles in the resin matrix directly determines the toughening effect. When the content is slightly higher, agglomeration occurs among particles, and defects are formed after curing, so that the mechanical properties of the product are reduced. Thus, nanoparticle toughened epoxy resins are greatly limited.
Hyperbranched polymer toughened epoxy resins are also a focus of recent research. The hyperbranched polymer has the advantages of low viscosity, high functionality, less chain entanglement, good solubility and the like due to the unique branched structure, and can obviously improve the toughness and the manufacturability of the epoxy resin. The toughening agent is added into epoxy resin, and has different compatibility with the epoxy resin according to the addition amount, and the toughening effect and mechanism are also obviously different. The epoxy resin toughened by the hyperbranched polymer has the following two advantages: (1) the spherical structure of the epoxy resin can reduce the contractibility of epoxy cured products; (2) the terminal groups are various in types and quantity. Based on the above advantages, the research reports of toughening epoxy resin with hyperbranched polymer are increasing in recent years. However, the existing method for preparing the hyperbranched polymer has strict preparation requirement and complex steps, uses a large amount of organic solvent and catalyst, and is not suitable for commercial large-scale popularization and production.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a medium-temperature curing high-toughness epoxy resin and a preparation method thereof.
Technical scheme
The medium-temperature curing high-toughness epoxy resin is characterized by comprising 1-15 parts by mass of hydroxyl hyperbranched polysiloxane containing tertiary amine, 85-100 parts by mass of bisphenol A epoxy resin and 65-80 parts by mass of anhydride curing agent;
the structural formula of the tertiary amine-containing hydroxyl hyperbranched polysiloxane is as follows:
the structural formula of the bisphenol A type epoxy resin is as follows:
the hydroxyl hyperbranched polysiloxane containing the tertiary amine is ethyl orthosilicate, N-methyldiethanolamine and triethanolamine in a molar ratio of 3:5: 3.
The anhydride curing agent comprises phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride or methyl hexahydrophthalic anhydride.
The method for preparing the medium-temperature curing high-toughness epoxy resin is characterized by comprising the following steps:
step 1: stirring 85-100 parts of bisphenol A epoxy resin and 65-80 parts of anhydride curing agent at 60-90 ℃ for 10-40 min to obtain a resin prepolymer;
step 2: adding 1-15 parts of hydroxyl hyperbranched polysiloxane containing tertiary amine into the resin prepolymer, stirring for 10-40 min, pouring into a mold, vacuumizing in a vacuum box at 70-90 ℃ to remove bubbles, putting into a forced air drying box for staged heating and curing, wherein the curing process is 80-100 ℃/2h + 120-140 ℃/3h, cooling, demolding, and post-treating at 150-170 ℃ for 2h to obtain the intermediate-temperature cured high-toughness epoxy resin.
The tertiary amine-containing hydroxyl hyperbranched polysiloxane is: the catalyst is prepared by removing ethanol from ethyl orthosilicate, N-methyldiethanolamine and triethanolamine in a molar ratio of 3:5:3 under the reaction conditions of no solvent, no catalyst and a heating temperature of 80-160 ℃ and carrying out polycondensation.
The die is preheated at 70-90 ℃.
Advantageous effects
The invention provides a medium-temperature curing high-toughness epoxy resin and a preparation method thereof, the medium-temperature curing high-toughness epoxy resin uses hyperbranched polysiloxane containing aliphatic tertiary amine and the end group of which is hydroxyl to modify bisphenol A type epoxy resin, and uses acid anhydride as a curing agent, under the condition of lower heating, the tertiary amine attacks the acid anhydride to generate carboxylate anions, then the carboxylate anions open the ring of an epoxy group to generate oxyanions, and the oxyanions open the ring of the acid anhydride which does not participate in the reaction, and the reaction is alternately carried out to form a polyester type cross-linking structure to form a three-dimensional structure; the addition of the hyperbranched polysiloxane not only improves the curing reaction rate, but also ensures that the mixed resin has lower viscosity in a wider temperature range, thereby being beneficial to casting and molding.
In addition, the hydroxyl hyperbranched polysiloxane uses novel hydroxyl-terminated hyperbranched polysiloxane which is prepared by a one-pot method through ester exchange polycondensation and contains aliphatic tertiary amine to toughen and modify epoxy resin. Besides the characteristics of common hyperbranched polymer toughened epoxy resin, the resin toughness is further improved by utilizing a hydrogen bond formed by terminal hydroxyl and hydroxyl generated in the curing process of the epoxy resin, and the contained aliphatic tertiary amine can promote the curing reaction rate, reduce the curing temperature, endow the modified resin with the characteristics of high toughness, good thermal stability and the like, improve the preparation process of the modified resin, is easy for industrial large-scale production, and has wide application prospect as a resin matrix of electronic packaging materials, structural composite materials and the like in the fields of electronic appliances, vehicles and the like. The curing process of the casting body is 100 ℃/2h +130 ℃/3h +150 ℃/2h, and the impact strength is more than 38.0KJ/m2The bending strength is more than 140MPa, and the thermal stability is good.
Detailed Description
The invention will now be further described with reference to the examples:
the bisphenol A epoxy resin is modified by using the hyperbranched polysiloxane containing the aliphatic tertiary amine and the hydroxyl group as the end group, so that the curing temperature of the epoxy resin can be reduced while the epoxy resin is endowed with high toughness, and medium-temperature curing is realized; meanwhile, the thermal stability of the system is almost kept unchanged while the processing technology is not influenced. Namely, the resin is composed of 1-15 parts by mass of hydroxyl hyperbranched polysiloxane containing tertiary amine, 85-100 parts by mass of bisphenol A type epoxy resin and 65-80 parts by mass of anhydride curing agent.
The structural formula of main chemical substances in the composite material is as follows:
hydroxy hyperbranched polysiloxanes
Bisphenol a type epoxy resin:
the hydroxyl hyperbranched polysiloxane is prepared by performing ester exchange polycondensation on tetraethoxysilane, N-methyldiethanolamine and triethanolamine.
The traditional hyperbranched polymer preparation method has strict requirements on conditions, redundant steps and needs to use a large amount of organic solvent and catalyst, so the preparation cost is high and large-scale commercial preparation is difficult to realize; bisphenol A epoxy resin has high crosslinking density and insufficient toughness, and the preparation process is reduced and the thermal stability is poor after modification. Therefore, in order to improve the toughness of the epoxy resin without affecting the processing technology thereof and endow the epoxy resin with good thermal stability, the key is to select and synthesize the hyperbranched polysiloxane, to perform toughening modification on the epoxy resin matrix and optimize the processing technology thereof without affecting the thermal stability thereof. The epoxy resin is modified by utilizing the characteristics of low viscosity, large number of end groups, large free volume and aliphatic tertiary amine of the hyperbranched polysiloxane, and simultaneously the epoxy resin is mixed, copolymerized and cured with the bisphenol A type epoxy resin and the anhydride curing agent according to a certain proportion to improve the curing process, improve the toughness and keep good thermal stability of the epoxy resin, so that the prepared epoxy resin modified system has good manufacturability, excellent mechanical property and thermal stability.
The specific method comprises the following steps:
mixing 85-100 parts of bisphenol A epoxy resin and 65-80 parts of anhydride curing agent, and stirring at 60-90 ℃ for 10-40 min to prepare a resin prepolymer. Then, adding 1-15 parts of hyperbranched polysiloxane into the prepolymer, stirring for 10-40 min, pouring into a mold preheated at 70-90 ℃, vacuumizing in a vacuum box at 70-90 ℃ to remove bubbles, putting into a forced air drying box for staged heating and curing, wherein the curing process is 80-100 ℃/2h + 120-140 ℃/3h, cooling, demolding, and post-treating for 2h at 150-170 ℃ to obtain the hyperbranched polysiloxane.
Example 1 was carried out:
85 parts of bisphenol A epoxy resin and 65 parts of an acid anhydride curing agent were mixed and stirred at 60 ℃ for 20 minutes to prepare a resin prepolymer. Then, adding 15 parts of hyperbranched polysiloxane into the prepolymer, stirring for 10min, pouring into a mold preheated at 70 ℃, vacuumizing in a vacuum box at 70 ℃ to remove bubbles, putting into a forced air drying box for staged heating and curing, wherein the curing process is 80 ℃/2h +120 ℃/3h, cooling, demolding, and performing post-treatment at 150 ℃ for 2h to obtain the hyperbranched polysiloxane.
Example 2 was carried out:
90 parts of bisphenol A epoxy resin and 70 parts of an acid anhydride curing agent were mixed and stirred at 60 ℃ for 20 minutes to prepare a resin prepolymer. Then, adding 10 parts of hyperbranched polysiloxane into the prepolymer, stirring for 10min, pouring into a mold preheated at 70 ℃, vacuumizing in a vacuum box at 70 ℃ to remove bubbles, putting into a forced air drying box for staged heating and curing, wherein the curing process is 80 ℃/2h +120 ℃/3h, cooling, demolding, and performing post-treatment at 150 ℃ for 2h to obtain the hyperbranched polysiloxane.
Example 3 of implementation:
95 parts of bisphenol A epoxy resin and 75 parts of an acid anhydride curing agent were mixed and stirred at 60 ℃ for 20 minutes to prepare a resin prepolymer. Then, 5 parts of hyperbranched polysiloxane is added into the prepolymer, stirred for 10min, poured into a mold preheated at 70 ℃, vacuumized to remove bubbles in a vacuum box at 70 ℃, put into a forced air drying box for staged temperature rise curing, cooled, demoulded, and post-treated for 2h at 150 ℃ to obtain the hyperbranched polysiloxane prepolymer.
Example 4 of implementation:
100 parts of bisphenol A epoxy resin and 80 parts of an acid anhydride curing agent were mixed and stirred at 60 ℃ for 20 minutes to prepare a resin prepolymer. Then, adding 1 part of hyperbranched polysiloxane into the prepolymer, stirring for 10min, pouring into a mold preheated at 70 ℃, vacuumizing in a vacuum box at 70 ℃ to remove bubbles, putting into a forced air drying box for staged heating and curing, wherein the curing process is 80 ℃/2h +120 ℃/3h, cooling, demolding, and performing post-treatment at 150 ℃ for 2h to obtain the hyperbranched polysiloxane.
Example 5 was carried out:
90 parts of bisphenol A epoxy resin and 70 parts of an acid anhydride curing agent were mixed and stirred at 60 ℃ for 20 minutes to prepare a resin prepolymer. Then, adding 10 parts of hyperbranched polysiloxane into the prepolymer, stirring for 10min, pouring into a mold preheated at 70 ℃, vacuumizing in a vacuum box at 70 ℃ to remove bubbles, putting into a forced air drying box for staged heating and curing, wherein the curing process is 90 ℃/2h +130 ℃/3h, cooling, demolding, and performing post-treatment at 150 ℃ for 2h to obtain the hyperbranched polysiloxane.
Example 6 of implementation:
95 parts of bisphenol A epoxy resin and 75 parts of an acid anhydride curing agent were mixed and stirred at 60 ℃ for 20 minutes to prepare a resin prepolymer. Then, 5 parts of hyperbranched polysiloxane is added into the prepolymer, stirred for 10min, poured into a mold preheated at 70 ℃, vacuumized to remove bubbles in a vacuum box at 70 ℃, put into a forced air drying box for staged temperature rise curing, cooled, demoulded, and post-treated for 2h at 150 ℃ to obtain the hyperbranched polysiloxane prepolymer.
Example 7 was carried out:
100 parts of bisphenol A epoxy resin and 80 parts of an acid anhydride curing agent were mixed and stirred at 60 ℃ for 20 minutes to prepare a resin prepolymer. Then, adding 1 part of hyperbranched polysiloxane into the prepolymer, stirring for 10min, pouring into a mold preheated at 70 ℃, vacuumizing in a vacuum box at 70 ℃ to remove bubbles, putting into a forced air drying box for staged heating and curing, wherein the curing process is 90 ℃/2h +130 ℃/3h, cooling, demolding, and performing post-treatment at 150 ℃ for 2h to obtain the hyperbranched polysiloxane.
Example 8 was carried out:
100 parts of bisphenol A epoxy resin and 80 parts of an acid anhydride curing agent were mixed and stirred at 80 ℃ for 20 minutes to prepare a resin prepolymer. Then, adding 1 part of hyperbranched polysiloxane into the prepolymer, stirring for 10min, pouring into a mold preheated at 80 ℃, vacuumizing in a vacuum box at 80 ℃ to remove bubbles, putting into a forced air drying box for staged heating and curing, wherein the curing process is 100 ℃/2h +130 ℃/3h, cooling, demolding, and performing post-treatment at 150 ℃ for 2h to obtain the hyperbranched polysiloxane.
Claims (5)
1. The medium-temperature curing high-toughness epoxy resin is characterized by comprising 1-15 parts by mass of hydroxyl hyperbranched polysiloxane containing tertiary amine, 85-100 parts by mass of bisphenol A epoxy resin and 65-80 parts by mass of anhydride curing agent; the structural formula of the tertiary amine-containing hydroxyl hyperbranched polysiloxane is as follows:
the structural formula of the bisphenol A type epoxy resin is as follows:
the hydroxyl hyperbranched polysiloxane containing the tertiary amine is prepared by performing ester exchange polycondensation on tetraethoxysilane, N-methyldiethanolamine and triethanolamine in a molar ratio of 3:5: 3.
2. The medium-temperature-curing high-toughness epoxy resin as claimed in claim 1, wherein: the anhydride curing agent comprises phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride or methyl hexahydrophthalic anhydride.
3. A method for preparing the medium-temperature curing high-toughness epoxy resin as described in any one of claims 1-2, which is characterized by comprising the following steps:
step 1: stirring 85-100 parts of bisphenol A epoxy resin and 65-80 parts of anhydride curing agent at 60-90 ℃ for 10-40 min to obtain a resin prepolymer;
step 2: adding 1-15 parts of hydroxyl hyperbranched polysiloxane containing tertiary amine into the resin prepolymer, stirring for 10-40 min, pouring into a mold, vacuumizing in a vacuum box at 70-90 ℃ to remove bubbles, putting into a forced air drying box for staged heating and curing, wherein the curing process is 80-100 ℃/2h + 120-140 ℃/3h, cooling, demolding, and post-treating at 150-170 ℃ for 2h to obtain the intermediate-temperature cured high-toughness epoxy resin.
4. The method of claim 3, further comprising: the tertiary amine-containing hydroxyl hyperbranched polysiloxane is: the catalyst is prepared by removing ethanol from ethyl orthosilicate, N-methyldiethanolamine and triethanolamine in a molar ratio of 3:5:3 under the reaction conditions of no solvent, no catalyst and a heating temperature of 80-160 ℃ and carrying out polycondensation.
5. The method of claim 3, further comprising: the die is preheated at 70-90 ℃.
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| CN101792574A (en) * | 2010-03-30 | 2010-08-04 | 中科院广州化学有限公司 | Modified epoxy resin composite material of prereacted material of epoxy-terminated silicone oil and preparation method and application thereof |
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