CN114456410B - High-performance epoxy resin toughening agent for winding and forming composite material and preparation method thereof - Google Patents
High-performance epoxy resin toughening agent for winding and forming composite material and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
Abstract
The application relates to a high-performance epoxy resin toughening agent for winding and forming a composite material and a preparation method thereof, wherein the toughening agent is composed of hollow or solid polymer nanoparticles and silicon dioxide, the silicon dioxide is deposited on the outer surface of the polymer nanoparticles, the polymer nanoparticles are composed of amphiphilic block polymers, hydrophilic chain segments of the amphiphilic block polymers face outwards, and hydrophobic chain segments face inwards; the preparation method comprises the following steps: and after the amphiphilic block polymer is prepared into the polymer nano particles by using a macromolecular self-assembly technology, depositing a precursor of silicon on the polymer nano particles to perform in-situ reaction to prepare the high-performance epoxy resin toughening agent for winding and forming the composite material. The preparation method disclosed by the application is simple, and the obtained hybrid nano particles have good compatibility with epoxy resin and good toughening effect.
Description
Technical Field
The application belongs to the technical field of composite materials, and relates to a high-performance epoxy resin toughening agent for winding and forming of a composite material and a preparation method thereof.
Background
Fiber reinforced epoxy resin based composites are receiving increasing attention for their lightweight, high strength properties. The composite material is wound to form a symmetrical structure for preparing rotating bodies and positive curvatures, has low manufacturing cost, high product quality and high degree of mechanization, and is suitable for preparing shafts, pipes, pressure vessels and the like. With the development of winding technology, the product performance requirement is higher and higher, and the requirement on winding molding epoxy resin is higher and higher, and particularly, the use of high-temperature-resistant epoxy resin is more and more, but most high-temperature-resistant epoxy resin has poor impact resistance, and the composite material is easy to generate invisible damage when impacted. The damage cannot be observed by naked eyes, the integrity of a composite material part can be damaged, the transmission of force is affected, the mechanical property is reduced, the deformation and damage of a component are easy to generate in the working process, the safety problem is caused, and the application of a plurality of high-temperature-resistant epoxy resins is limited.
The prior art generally adopts a mode of adding toughening agents such as rubber, thermoplastic resin, dendritic polymer, block polymer, nano filler and the like to improve the impact resistance of the epoxy resin, and the toughening agents are mainly divided into an organic toughening agent and an inorganic toughening agent, wherein the organic toughening agent has good compatibility with the epoxy resin, can achieve a better toughening effect, and the rigidity loss caused by the organic toughening agent is small; most inorganic toughening agents are rigid inorganic nano particles, such as silicon dioxide, titanium dioxide, zirconium dioxide, calcium carbonate and the like, and due to the unique physical and mechanical properties, not only can the toughening effect be achieved, but also the rigidity lost due to toughening can be obviously improved, however, the inorganic toughening agents are poor in dispersibility in an epoxy resin matrix and easy to aggregate, and when the inorganic toughening agents are excessive or uneven in dispersion, an agglomeration phenomenon can be generated, so that the toughening effect of a system is influenced.
In order to overcome the defect that the organic toughening agent and the inorganic toughening agent are independently used, organic-inorganic hybrid nano particles are prepared in the prior art. Document 1 (Improving the fracture toughness ofepoxy with nanosilica-rubber core-shell nanoparticles) shows that after caprolactone and meso-lactide are grafted on the surface of nano-silica, the Young's modulus, tensile strength and fracture toughness of epoxy resin are improved, and when the added mass fraction of modified grafted silica particles is 2%, the impact strength of the epoxy resin is improved by 39.4%; document 2 (Fast-curing epoxy poly-mers with silica nanoparticles: properties and rheo-kinetic modelling) compares the influence of different contents of silica particles and hybridized core-shell rubber particles on fracture toughness of a Fast-curing epoxy resin, and finds that the organic-inorganic hybridized core-shell rubber particles have better toughening effect than inorganic silica nanoparticles, and are used in different hybridized rubber particlesThe breaking energy of the epoxy resin is improved by 19.8 percent under the sub-content; document 3 (nano SiO) 2 Research of polyurethane elastomer synergistic toughening and reinforcing epoxy resin) research on inorganic nano SiO 2 Particles, polyurethane elastomer (PUR), epoxy resin (EP) prepared nano SiO 2 Mechanical properties of the PUR/EP ternary composite material, and the result shows that the nano SiO 2 Has the function of synergizing, toughening and enhancing EP with PUR, and nano SiO is adopted when the PUR mass fraction is 20 percent 2 Impact strength ratio nano SiO of PUR/EP ternary composite material 2 The improvement of the EP by 11 percent is 7 percent higher than the PUR/EP;
document 4 (Hybrid silane-treated glass fabric/epoxy composites: tensile properties by micromechanical approach) has studied the influence of organic-inorganic Hybrid nano silica particles on the mechanical properties of epoxy resin composites, and has determined a nano silica sol/silane coupling agent slurry formulation through experiments, and has used the slurry to perform sizing surface modification on glass fiber fabrics, and the modified reinforcing material is infiltrated with epoxy resin and cured to form composites, wherein the flexural strength, flexural modulus and impact strength are respectively improved by 42%, 22% and 35%.
In summary, the organic-inorganic hybrid nanoparticles in the prior art have limited toughening effect on epoxy resin, and the degree of enhancement of the impact strength of the toughened epoxy resin needs to be further improved.
Disclosure of Invention
The application aims to solve the problems in the prior art and provides a high-performance epoxy resin toughening agent for winding and forming of a composite material and a preparation method thereof.
The block polymer is a novel epoxy resin toughening agent, and non-reactive and reactive block polymers can be mixed into resin to achieve the toughening effect by self-assembly or reaction-induced phase separation; the silicon dioxide has unique physical and mechanical properties, so that not only can the toughening effect be achieved, but also the rigidity lost due to toughening can be obviously improved; the application aims to prepare a novel organic-inorganic hybrid nanoparticle (namely the high-performance epoxy resin toughening agent for winding and forming of the composite material) by hybridizing a block polymer and silicon dioxide, so that the impact strength improvement degree of the toughened epoxy resin is remarkably improved.
In order to achieve the above purpose, the application adopts the following technical scheme:
a high-performance epoxy resin toughening agent for winding and forming a composite material is composed of hollow or solid polymer nanoparticles and silicon dioxide, wherein the silicon dioxide is deposited on the outer surface of the polymer nanoparticles, the polymer nanoparticles are composed of amphiphilic block polymers, hydrophilic chain segments of the amphiphilic block polymers face outwards, and hydrophobic chain segments face inwards.
As a preferable technical scheme:
the high-performance epoxy resin toughening agent for composite material winding molding has the average particle size of 20-600 nm, and the average particle size of the high-performance epoxy resin toughening agent for composite material winding molding is set so as to avoid the problem that the size is difficult to control due to the excessively small average particle size and the problem that the contact surface between the toughening agent and the epoxy resin is small and difficult to disperse due to the excessively small specific surface area of the toughening agent due to the excessively large average particle size.
The high-performance epoxy resin toughening agent for winding and forming the composite material is characterized in that the polymer nanoparticles are micelles, vesicles, microspheres, vermicular objects or core-shell structure nanoparticles.
The high-performance epoxy resin toughening agent for winding and forming the composite material is characterized in that the amphiphilic block polymer is polyethylene glycol-polystyrene (PEG-b-PS), the weight average molecular weight is 5000-40000, the polymerization degree of a polyethylene glycol chain segment is 10-100, and the polymerization degree of a polystyrene chain segment is 40-200; the synthesis method of the amphiphilic block polymer is an Atom Transfer Radical Polymerization (ATRP), a chain transfer radical polymerization (ATRP), a reversible addition-fragmentation chain transfer polymerization (RAFT), a click chemistry or a ring-opening polymerization (ROP); the length of the polyethylene glycol chain segment (i.e. the polymerization degree) is the length of a common hydrophilic chain segment, which is closely related to the morphology of the hydrophobic chain segment and the nanoparticle, and setting the polyethylene glycol chain segment to 10-100 is easy to realize for each morphology of the polymer.
The high-performance epoxy resin toughening agent for the winding molding of the composite material has the advantages that the impact strength of the epoxy resin containing the high-performance epoxy resin toughening agent for the winding molding of the composite material, namely, the high-toughness epoxy resin, is improved by 40-90% compared with that of the unmodified epoxy resin; the unmodified epoxy resin is different from the high-toughness epoxy resin only in that the modified epoxy resin does not contain a high-performance epoxy resin toughening agent for winding and forming of the composite material;
the organic-inorganic hybrid nano particles in the prior art have limited toughening effect on the epoxy resin, and the toughened epoxy resin has limited degree of improvement on impact strength, but the degree of improvement on impact strength of the toughened epoxy resin can reach 40-90%, and the application has obvious progress compared with the prior art;
the preparation process of the high-toughness epoxy resin comprises the following steps: the solution of the high-performance epoxy resin toughening agent for winding and forming the composite material and the epoxy resin are mixed and stirred for 0.5 to 12 hours according to the mass ratio of 1:50 to 500, and then a curing agent and other auxiliary agents are added to obtain the high-toughness epoxy resin, wherein the adding amount of the toughening agent is not too small or too large, the toughening effect is poor due to too small, and the mechanical property of the material is reduced due to too large.
The high-performance epoxy resin toughening agent for winding and forming the composite material is characterized in that the epoxy resin is more than one of bisphenol A epoxy resin, bisphenol F epoxy resin, polyphenol glycidyl ether epoxy resin, aliphatic glycidyl ether epoxy resin, glycidyl ester epoxy resin and glycidylamine epoxy resin; the curing agent is one or more of ethylenediamine, diethylenetriamine, polymethylenediamine, diethylaminopropylamine, high-carbon tree aliphatic diamine, aliphatic amide polyamine, maleic anhydride and phthalic anhydride; the mass ratio of the curing agent to the epoxy resin is 1:1-5; the mass ratio of other auxiliary agents to the epoxy resin is 1:200-500.
The application also provides a preparation method of the high-performance epoxy resin toughening agent for winding and forming the composite material, which comprises the steps of preparing the amphiphilic block polymer into polymer nanoparticles by using a macromolecular self-assembly technology, depositing a precursor of silicon onto the polymer nanoparticles, and carrying out in-situ reaction to obtain the high-performance epoxy resin toughening agent for winding and forming the composite material.
As a preferable technical scheme:
the method comprises the following specific steps:
(1) Dissolving amphiphilic block polymer in good solvent A to obtain solution with concentration of 0.1-100 mg/mL, dripping poor solvent B into the solution for self-assembly, and stirring for 5-50 h to obtain polymer nanoparticle solution with concentration of 0.01-100 mg/mL;
(2) Dissolving a silicon precursor in an organic solvent C to obtain a solution with the concentration of 0.01-100 mg/mL, dropwise adding the polymer nanoparticle solution obtained in the step (1) into the solution, stirring the solution for 2-100 h to obtain a solution of the high-performance epoxy resin toughening agent for winding forming of the composite material, wherein the mass ratio of the polymer nanoparticle to the silicon precursor is 1:0.1-100, and removing all the solvents to obtain the high-performance epoxy resin toughening agent for winding forming of the composite material; it should be noted that the "solution of the high-performance epoxy resin toughening agent for winding and forming of composite material" in the above description is obtained by dissolving the high-performance epoxy resin toughening agent for winding and forming of composite material in a solvent, and the operation of "removing all solvents" may not be performed when preparing the high-performance epoxy resin toughening agent for winding and forming of composite material, and the final product is the solution of the high-performance epoxy resin toughening agent for winding and forming of composite material, and the "solution of the high-performance epoxy resin toughening agent for winding and forming of composite material" in the embodiments of the present application refers to the latter.
In the above method, in the step (1), the good solvent A is one or more of tetrahydrofuran, dichloromethane, dimethylformamide, chloroform and dimethyl sulfoxide; the poor solvent B is one or more of acetone, methanol, ethanol, glycerol and butanol.
In the method, in the step (2), the precursor of silicon is more than one of tetraethoxysilane, silicate, silicon chloride and tetramethyl silicate; the organic solvent C is one or more of tetrahydrofuran, methanol, ethanol, glycerol and butanol.
The principle of the application is as follows:
the application synthesizes a new organic-inorganic hybrid nanoparticle, firstly uses macromolecule self-assembly technology to prepare polymer nanoparticle with soft shell and hard core (the shell is a softer macromolecule chain segment, the inner core is a rigid group containing benzene ring), the particle diameter of the nanoparticle is controllable, then deposits the precursor of silicon on the nanoparticle assembled by the polymer to perform in-situ reaction to form silicon dioxide, the silicon dioxide can keep the shape and structure of the polymer nanoparticle, because: the three-dimensional network structure with the highly crosslinked silica can absorb energy and has higher specific surface area, and the surface of the nano silica is provided with active groups (-OH or H) + ) The bonding effect between the nano-particles and the block polymer is improved, the block polymer is unstable in structure and easy to agglomerate after self-assembling into nano-particles, and the hybridized nano-particles are more stable in structure and difficult to agglomerate due to the bonding effect of silicon dioxide.
The organic-inorganic hybrid nano particles contain block polymers, so that the dispersibility of the organic-inorganic hybrid nano particles in epoxy resin is good, and the interface effect is strong; the loss of rigidity is small due to the silica content. The organic-inorganic hybrid nano particles can toughen the epoxy resin on the premise of smaller rigidity loss, effectively improve the practical application effect of the epoxy resin, and the impact strength improvement degree of the toughened epoxy resin can reach 40-90%, because: (1) The specific surface area of the nano particles is large, and the used materials have good compatibility with the epoxy resin, so that the dispersibility in the epoxy resin is good; (2) The hybrid nanoparticle also has a rigid group of benzene ring, so that the toughness is improved and the loss of rigidity is reduced at the same time; (3) The particle size of the nano particles is uniform and controllable, agglomeration is not easy to generate among the hybrid particles, and the dispersibility is good.
The epoxy resin toughened by the organic-inorganic hybrid nano particles can be widely applied to winding and forming composite material parts in the industrial fields of aviation, aerospace, weapons, rail transit, ships, automobiles and the like, such as rocket shells, aircraft bodies, transmission shafts of transmission systems, pressure vessels, conveying pipelines, sports equipment and the like.
The beneficial effects are that:
(1) The application can obtain polymer nano particles with uniform particle size by utilizing a macromolecular self-assembly technology, thereby effectively controlling the particle size distribution and size;
(2) The application can obtain a series of hybridized silica nanoparticles with different particle diameters and uniform distribution by controlling the size of the polymer nanoparticles;
(3) The solvent used in the preparation process of the application has good compatibility with the epoxy resin, and the nano particles do not need to be dried or purified;
(4) The organic-inorganic hybrid nano particles prepared by the application can keep better dispersibility in epoxy resin, and the morphology and structure are not easy to damage;
(5) The preparation method provided by the application is simple, the operability is strong, and the obtained organic-inorganic hybrid nano particles have good compatibility with epoxy resin.
Detailed Description
The application is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
Example 1
A preparation method of a high-performance epoxy resin toughening agent for winding and forming of composite materials comprises the following specific steps:
(1) Preparing an amphiphilic block polymer by adopting an atom transfer radical polymerization method;
the prepared amphiphilic block polymer is polyethylene glycol-polystyrene (PEG-b-PS), the weight average molecular weight is 9000, the polymerization degree of a polyethylene glycol chain segment is 43, and the polymerization degree of a polystyrene chain segment is 80;
(2) Dissolving amphiphilic block polymer in tetrahydrofuran to obtain a solution with the concentration of 50mg/mL, dropwise adding ethanol into the solution for self-assembly, and stirring for 50h to obtain a polymer nanoparticle solution with the concentration of 1 mg/mL;
(3) Dissolving ethyl orthosilicate in ethanol to obtain a solution with the concentration of 5mg/mL, dropwise adding the polymer nanoparticle solution obtained in the step (2) into the solution, stirring the solution for 20 hours to obtain a solution of the high-performance epoxy resin toughening agent for winding forming of the composite material, wherein the mass ratio of the polymer nanoparticle to the ethyl orthosilicate is 1:0.4, and removing all solvents to obtain the high-performance epoxy resin toughening agent for winding forming of the composite material.
The finally prepared high-performance epoxy resin toughening agent for winding and forming the composite material is composed of polymer nanoparticles and silicon dioxide, wherein the polymer nanoparticles are core-shell structure nanoparticles, the silicon dioxide is deposited on the outer surfaces of the polymer nanoparticles, the polymer nanoparticles are composed of amphiphilic block polymers, hydrophilic chain segments of the amphiphilic block polymers face outwards, and hydrophobic chain segments face inwards; the average grain diameter of the high-performance epoxy resin toughening agent for winding and forming the composite material is 50nm.
Blending and stirring the solution of the high-performance epoxy resin toughening agent for winding and forming the composite material in the step (3) and bisphenol A epoxy resin (with the mark of E-52D) according to the mass ratio of 1:100 for 10 hours, and then adding polymethylene diamine and phthalic acid cool to obtain high-toughness epoxy resin; wherein the mass ratio of the polymethylene diamine to the bisphenol A type epoxy resin is 1:1; the mass ratio of the phthalic acid cool to the bisphenol A type epoxy resin is 1:200.
The impact strength of the prepared high-toughness epoxy resin is improved by 73.1 percent compared with that of unmodified epoxy resin; the unmodified epoxy resin is different from the high-toughness epoxy resin only in that the high-performance epoxy resin toughening agent for winding and forming the composite material is not contained.
Example 2
A preparation method of a high-performance epoxy resin toughening agent for winding and forming of composite materials comprises the following specific steps:
(1) Preparing an amphiphilic block polymer by adopting a chain transfer free radical polymerization method;
the prepared amphiphilic block polymer is polyethylene glycol-polystyrene (PEG-b-PS), the weight average molecular weight is 4800, the polymerization degree of a polyethylene glycol chain segment is 43, and the polymerization degree of a polystyrene chain segment is 30;
(2) Dissolving amphiphilic block polymer in dichloromethane to obtain a solution with the concentration of 30mg/mL, dropwise adding ethanol into the solution for self-assembly, and stirring for 50h to obtain a polymer nanoparticle solution with the concentration of 2 mg/mL;
(3) And (3) dissolving silicon chloride in ethanol to obtain a solution with the concentration of 5mg/mL, dropwise adding the polymer nanoparticle solution obtained in the step (2) into the solution, stirring the solution for 20 hours to obtain a solution of the high-performance epoxy resin toughening agent for winding forming of the composite material, wherein the mass ratio of the polymer nanoparticle to the silicon chloride is 1:0.8, and removing all solvents to obtain the high-performance epoxy resin toughening agent for winding forming of the composite material.
The finally prepared high-performance epoxy resin toughening agent for winding and forming the composite material is composed of polymer nanoparticles and silicon dioxide, wherein the polymer nanoparticles are core-shell structure nanoparticles, the silicon dioxide is deposited on the outer surfaces of the polymer nanoparticles, the polymer nanoparticles are composed of amphiphilic block polymers, hydrophilic chain segments of the amphiphilic block polymers face outwards, and hydrophobic chain segments face inwards; the average grain diameter of the high-performance epoxy resin toughening agent for winding and forming the composite material is 80nm.
Blending and stirring the solution of the high-performance epoxy resin toughening agent for winding and forming the composite material in the step (3) and bisphenol F type epoxy resin (with the brand of NPEF-170) according to the mass ratio of 1:200 for 12 hours, and then adding diethylamine propylamine and phosphoric acid vinegar to obtain high-toughness epoxy resin; wherein the mass ratio of the diethylaminopropylamine to the bisphenol F type epoxy resin is 1:3; the mass ratio of the phosphoric acid vinegar to the bisphenol F type epoxy tree is 1:500.
The impact strength of the prepared high-toughness epoxy resin is improved by 62% compared with that of unmodified epoxy resin; the unmodified epoxy resin is different from the high-toughness epoxy resin only in that the high-performance epoxy resin toughening agent for winding and forming the composite material is not contained.
Example 3
A preparation method of a high-performance epoxy resin toughening agent for winding and forming of composite materials comprises the following specific steps:
(1) Preparing an amphiphilic block polymer by adopting a reversible addition-fragmentation chain transfer polymerization method;
the prepared amphiphilic block polymer is polyethylene glycol-polystyrene (PEG-b-PS), the weight average molecular weight is 22000, the polymerization degree of a polyethylene glycol chain segment is 10, and the polymerization degree of a polystyrene chain segment is 200;
(2) Dissolving amphiphilic block polymer in dimethylformamide to obtain a solution with the concentration of 0.1mg/mL, dropwise adding acetone into the solution for self-assembly, and stirring for 5h to obtain a polymer nanoparticle solution with the concentration of 0.01 mg/mL;
(3) Dissolving aluminosilicate (CAS number: 1327-36-2) in methanol to obtain a solution with the concentration of 0.01mg/mL, dropwise adding the polymer nanoparticle solution obtained in the step (2) into the solution, stirring the solution for 2 hours to obtain a solution of the high-performance epoxy resin toughening agent for winding forming of the composite material, wherein the mass ratio of the polymer nanoparticle to the aluminosilicate is 1:0.1, and removing all solvents to obtain the high-performance epoxy resin toughening agent for winding forming of the composite material.
The finally prepared high-performance epoxy resin toughening agent for winding and forming the composite material is composed of polymer nanoparticles and silicon dioxide, wherein the polymer nanoparticles are micelles, the silicon dioxide is deposited on the outer surfaces of the polymer nanoparticles, the polymer nanoparticles are composed of amphiphilic block polymers, hydrophilic chain segments of the amphiphilic block polymers face outwards, and hydrophobic chain segments face inwards; the average grain diameter of the high-performance epoxy resin toughening agent for winding and forming the composite material is 120nm.
Blending and stirring the solution of the high-performance epoxy resin toughening agent for winding and forming the composite material in the step (3) and the polyphenol type glycidyl ether epoxy resin (with the mark of E51) according to the mass ratio of 1:50 for 5 hours, and then adding ethylenediamine and benzoate to obtain high-toughness epoxy resin; wherein the mass ratio of ethylenediamine to the polyphenol type glycidyl ether epoxy resin is 1:1; the mass ratio of the benzoate to the polyphenol type glycidyl ether epoxy resin is 1:300.
The impact strength of the prepared high-toughness epoxy resin is improved by 47.5 percent compared with that of unmodified epoxy resin; the unmodified epoxy resin is different from the high-toughness epoxy resin only in that the high-performance epoxy resin toughening agent for winding and forming the composite material is not contained.
Example 4
A preparation method of a high-performance epoxy resin toughening agent for winding and forming of composite materials comprises the following specific steps:
(1) Preparing an amphiphilic block polymer by adopting click chemistry;
the prepared amphiphilic block polymer is polyethylene glycol-polystyrene (PEG-b-PS), the weight average molecular weight is 18200, the polymerization degree of a polyethylene glycol chain segment is 30, and the polymerization degree of a polystyrene chain segment is 160;
(2) Dissolving amphiphilic block polymer in chloroform to obtain a solution with the concentration of 1mg/mL, dropwise adding methanol into the solution for self-assembly, and stirring for 10h to obtain a polymer nanoparticle solution with the concentration of 10 mg/mL;
(3) Dissolving tetramethyl silicate in tetrahydrofuran to obtain a solution with the concentration of 15mg/mL, dropwise adding the polymer nanoparticle solution obtained in the step (2) into the solution, stirring the solution for 10 hours to obtain a solution of the high-performance epoxy resin toughening agent for winding forming of the composite material, wherein the mass ratio of the polymer nanoparticle to the tetramethyl silicate is 1:10, and removing all solvents to obtain the high-performance epoxy resin toughening agent for winding forming of the composite material.
The finally prepared high-performance epoxy resin toughening agent for winding and forming the composite material is composed of polymer nanoparticles and silicon dioxide, wherein the polymer nanoparticles are vesicles, the silicon dioxide is deposited on the outer surfaces of the polymer nanoparticles, the polymer nanoparticles are composed of amphiphilic block polymers, hydrophilic chain segments of the amphiphilic block polymers face outwards, and hydrophobic chain segments face inwards; the average grain diameter of the high-performance epoxy resin toughening agent for winding and forming the composite material is 160nm.
Blending and stirring the solution of the high-performance epoxy resin toughening agent for winding and forming the composite material in the step (3) and aliphatic glycidyl ether epoxy resin (with the trademark of ERISYS GE-60) for 0.5h according to the mass ratio of 1:150, and then adding diethylenetriamine and phosphoric acid vinegar to obtain high-toughness epoxy resin; wherein the mass ratio of diethylenetriamine to aliphatic glycidyl ether epoxy resin is 1:2; the mass ratio of the phosphoric acid vinegar to the aliphatic glycidyl ether epoxy resin is 1:400.
The impact strength of the prepared high-toughness epoxy resin is improved by 56.8 percent compared with that of unmodified epoxy resin; the unmodified epoxy resin is different from the high-toughness epoxy resin only in that the high-performance epoxy resin toughening agent for winding and forming the composite material is not contained.
Example 5
A preparation method of a high-performance epoxy resin toughening agent for winding and forming of composite materials comprises the following specific steps:
(1) Preparing an amphiphilic block polymer by adopting a ring-opening polymerization method;
the prepared amphiphilic block polymer is polyethylene glycol-polystyrene (PEG-b-PS), the weight average molecular weight is 17000, the polymerization degree of a polyethylene glycol chain segment is 60, and the polymerization degree of a polystyrene chain segment is 140;
(2) Dissolving amphiphilic block polymer in dimethyl sulfoxide to obtain a solution with the concentration of 10mg/mL, dropwise adding glycerol into the solution for self-assembly, and stirring for 20h to obtain a polymer nanoparticle solution with the concentration of 30 mg/mL;
(3) Dissolving ethyl orthosilicate in glycerol to obtain a solution with the concentration of 30mg/mL, dropwise adding the polymer nanoparticle solution obtained in the step (2) into the solution, stirring the solution for 30 hours to obtain a solution of the high-performance epoxy resin toughening agent for winding forming of the composite material, wherein the mass ratio of the polymer nanoparticle to the ethyl orthosilicate is 1:20, and removing all solvents to obtain the high-performance epoxy resin toughening agent for winding forming of the composite material.
The finally prepared high-performance epoxy resin toughening agent for winding and forming the composite material is composed of polymer nanoparticles and silicon dioxide, wherein the polymer nanoparticles are microspheres, the silicon dioxide is deposited on the outer surfaces of the polymer nanoparticles, the polymer nanoparticles are composed of amphiphilic block polymers, hydrophilic chain segments of the amphiphilic block polymers face outwards, and hydrophobic chain segments face inwards; the average particle size of the high-performance epoxy resin toughening agent for winding and forming the composite material is 240nm.
Blending and stirring the solution of the high-performance epoxy resin toughening agent for winding and forming the composite material in the step (3) and glycidyl ester type epoxy resin (with the trademark of TDE-85) according to the mass ratio of 1:300 for 1h, and then adding polymethylene diamine and benzoate to obtain high-toughness epoxy resin; wherein the mass ratio of the polymethylene diamine to the glycidyl ester type epoxy resin is 1:3; the mass ratio of the benzoate to the glycidyl ester type epoxy resin is 1:350.
The impact strength of the prepared high-toughness epoxy resin is improved by 52% compared with that of unmodified epoxy resin; the unmodified epoxy resin is different from the high-toughness epoxy resin only in that the high-performance epoxy resin toughening agent for winding and forming the composite material is not contained.
Example 6
A preparation method of a high-performance epoxy resin toughening agent for winding and forming of composite materials comprises the following specific steps:
(1) Preparing an amphiphilic block polymer by adopting a chain transfer free radical polymerization method;
the prepared amphiphilic block polymer is polyethylene glycol-polystyrene (PEG-b-PS), the weight average molecular weight is 14000, the polymerization degree of a polyethylene glycol chain segment is 80, and the polymerization degree of a polystyrene chain segment is 100;
(2) Dissolving amphiphilic block polymer in tetrahydrofuran to obtain a solution with the concentration of 100mg/mL, dropwise adding butanol into the solution for self-assembly, and stirring for 30h to obtain a polymer nanoparticle solution with the concentration of 60 mg/mL;
(3) And (3) dissolving silicon chloride in butanol to obtain a solution with the concentration of 60mg/mL, dropwise adding the polymer nanoparticle solution obtained in the step (2) into the solution, stirring the solution for 100 hours to obtain a solution of the high-performance epoxy resin toughening agent for winding forming of the composite material, wherein the mass ratio of the polymer nanoparticle to the silicon chloride is 1:50, and removing all solvents to obtain the high-performance epoxy resin toughening agent for winding forming of the composite material.
The finally prepared high-performance epoxy resin toughening agent for winding and forming the composite material is composed of polymer nanoparticles and silicon dioxide, wherein the polymer nanoparticles are vermicular, the silicon dioxide is deposited on the outer surfaces of the polymer nanoparticles, the polymer nanoparticles are composed of amphiphilic block polymers, hydrophilic chain segments of the amphiphilic block polymers face outwards, and hydrophobic chain segments face inwards; the average grain diameter of the high-performance epoxy resin toughening agent for winding and forming the composite material is 180nm.
Blending and stirring the solution of the high-performance epoxy resin toughening agent for winding and forming the composite material in the step (3) and glycidylamine type epoxy resin (with the mark of TDE-85) according to the mass ratio of 1:500 for 2 hours, and then adding diethylaminopropylamine and citrate to obtain high-toughness epoxy resin; wherein the mass ratio of the diethylaminopropylamine to the glycidylamine type epoxy resin is 1:5; the mass ratio of the citrate to the glycidylamine type epoxy resin is 1:250.
The impact strength of the prepared high-toughness epoxy resin is improved by 63.4 percent compared with that of unmodified epoxy resin; the unmodified epoxy resin is different from the high-toughness epoxy resin only in that the high-performance epoxy resin toughening agent for winding and forming the composite material is not contained.
Example 7
A preparation method of a high-performance epoxy resin toughening agent for winding and forming of composite materials comprises the following specific steps:
(1) Preparing an amphiphilic block polymer by adopting an atom transfer radical polymerization method;
the prepared amphiphilic block polymer is polyethylene glycol-polystyrene (PEG-b-PS), the weight average molecular weight is 8000, the polymerization degree of a polyethylene glycol chain segment is 100, and the polymerization degree of a polystyrene chain segment is 40;
(2) Dissolving an amphiphilic block polymer in a mixture of chloroform and dimethyl sulfoxide in a mass ratio of 1:1 to obtain a solution with a concentration of 60mg/mL, dropwise adding a mixture of glycerol and butanol in a mass ratio of 1:1 to the solution for self-assembly, and stirring the solution for 40h to obtain a polymer nanoparticle solution with a concentration of 100 mg/mL;
(3) And (3) dissolving a mixture of ethyl orthosilicate and silicon chloride with the mass ratio of 1:1 in a mixture of glycerol and butanol with the mass ratio of 1:1 to obtain a solution with the concentration of 100mg/mL, dropwise adding the polymer nanoparticle solution obtained in the step (2) into the solution, stirring the solution for 70 hours to obtain a solution of the high-performance epoxy resin toughening agent for winding forming of the composite material, wherein the mass ratio of polymer nanoparticles to a precursor of silicon (the mixture of ethyl orthosilicate and silicon chloride with the mass ratio of 1:1) is 1:100, and removing all solvents to obtain the high-performance epoxy resin toughening agent for winding forming of the composite material.
The finally prepared high-performance epoxy resin toughening agent for winding and forming the composite material is composed of polymer nanoparticles and silicon dioxide, wherein the polymer nanoparticles are vesicles, the silicon dioxide is deposited on the outer surfaces of the polymer nanoparticles, the polymer nanoparticles are composed of amphiphilic block polymers, hydrophilic chain segments of the amphiphilic block polymers face outwards, and hydrophobic chain segments face inwards; the average grain diameter of the high-performance epoxy resin toughening agent for winding and forming the composite material is 200nm.
Blending and stirring the solution of the high-performance epoxy resin toughening agent for winding and forming the composite material in the step (3) and aliphatic glycidyl ether epoxy resin (with the trademark of ERISYS GE-60) for 4 hours according to the mass ratio of 1:400, and then adding high-carbon tree aliphatic diamine and phosphoric acid vinegar to obtain high-toughness epoxy resin; wherein the mass ratio of the high-carbon tree aliphatic diamine to the aliphatic glycidyl ether epoxy resin is 1:4; the mass ratio of the phosphoric acid vinegar to the aliphatic glycidyl ether epoxy resin is 1:500.
The impact strength of the prepared high-toughness epoxy resin is improved by 50.8 percent compared with that of unmodified epoxy resin; the unmodified epoxy resin is different from the high-toughness epoxy resin only in that the high-performance epoxy resin toughening agent for winding and forming the composite material is not contained.
Example 8
A method for preparing high-toughness epoxy resin is basically the same as in example 1, except that the curing agent is aliphatic diamine.
The impact strength of the prepared high-toughness epoxy resin is improved by 45% compared with that of unmodified epoxy resin; the unmodified epoxy resin is different from the high-toughness epoxy resin only in that the high-performance epoxy resin toughening agent for winding and forming the composite material is not contained.
Example 9
A method for preparing high-toughness epoxy resin is basically the same as in example 1, except that the curing agent is maleic anhydride.
The impact strength of the prepared high-toughness epoxy resin is improved by 57.8 percent compared with that of unmodified epoxy resin; the unmodified epoxy resin is different from the high-toughness epoxy resin only in that the high-performance epoxy resin toughening agent for winding and forming the composite material is not contained.
Example 10
A method for preparing high-toughness epoxy resin is basically the same as in example 1, except that the curing agent is phthalic anhydride.
The impact strength of the prepared high-toughness epoxy resin is improved by 42% compared with that of unmodified epoxy resin; the unmodified epoxy resin is different from the high-toughness epoxy resin only in that the high-performance epoxy resin toughening agent for winding and forming the composite material is not contained.
Example 11
A method for preparing high-toughness epoxy resin is basically the same as in example 1, except that the curing agent is ethylenediamine.
The impact strength of the prepared high-toughness epoxy resin is improved by 51.3% compared with that of unmodified epoxy resin; the unmodified epoxy resin is different from the high-toughness epoxy resin only in that the high-performance epoxy resin toughening agent for winding and forming the composite material is not contained.
Example 12
A method for preparing high-toughness epoxy resin is basically the same as in example 1, except that the curing agent is diethylenetriamine.
The impact strength of the prepared high-toughness epoxy resin is improved by 48.6% compared with that of unmodified epoxy resin; the unmodified epoxy resin is different from the high-toughness epoxy resin only in that the high-performance epoxy resin toughening agent for winding and forming the composite material is not contained.
Example 13
A preparation method of high-toughness epoxy resin is basically the same as in example 1, except that the curing agent is a mixture of maleic anhydride and phthalic anhydride in a mass ratio of 2:1.
The impact strength of the prepared high-toughness epoxy resin is improved by 64.3 percent compared with that of unmodified epoxy resin; the unmodified epoxy resin is different from the high-toughness epoxy resin only in that the high-performance epoxy resin toughening agent for winding and forming the composite material is not contained.
Example 14
A preparation method of high-toughness epoxy resin is basically the same as in example 1, except that the curing agent is a mixture of maleic anhydride and phthalic anhydride in a mass ratio of 1:1.
The impact strength of the prepared high-toughness epoxy resin is improved by 58.2 percent compared with that of unmodified epoxy resin; the unmodified epoxy resin is different from the high-toughness epoxy resin only in that the high-performance epoxy resin toughening agent for winding and forming the composite material is not contained.
Claims (7)
1. The application of the high-performance epoxy resin toughening agent for winding and forming of the composite material in preparing the high-toughness epoxy resin is characterized in that the preparation process of the high-toughness epoxy resin is as follows: blending and stirring a solution of a high-performance epoxy resin toughening agent for winding and forming the composite material and epoxy resin according to a mass ratio of 1:50-500 for 0.5-12 h, and then adding a curing agent and other auxiliary agents to obtain high-toughness epoxy resin;
the high-performance epoxy resin toughening agent for winding and forming the composite material is composed of hollow or solid polymer nanoparticles and silicon dioxide, wherein the silicon dioxide is deposited on the outer surface of the polymer nanoparticles, the polymer nanoparticles are composed of amphiphilic block polymers, hydrophilic chain segments of the amphiphilic block polymers face outwards, and hydrophobic chain segments face inwards;
the average grain diameter of the high-performance epoxy resin toughening agent for winding and forming the composite material is 20-600 nm;
the polymer nano particles are micelles, vesicles, microspheres, vermicules or core-shell structure nano particles;
the amphiphilic block polymer is polyethylene glycol-polystyrene, the weight average molecular weight is 5000-40000, the polymerization degree of a polyethylene glycol chain segment is 10-100, and the polymerization degree of a polystyrene chain segment is 40-200; the synthesis method of the amphiphilic block polymer is an atom transfer radical polymerization method, a chain transfer radical polymerization method, a reversible addition-fragmentation chain transfer polymerization method, a click chemistry method or a ring-opening polymerization method.
2. The application of the high-performance epoxy resin toughening agent for winding and forming of the composite material in preparing high-toughness epoxy resin, disclosed in claim 1, is characterized in that the impact strength of the high-toughness epoxy resin is improved by 40-90% compared with that of unmodified epoxy resin; the unmodified epoxy resin is different from the high-toughness epoxy resin only in that the high-performance epoxy resin toughening agent for winding and forming the composite material is not contained.
3. The application of the high-performance epoxy resin toughening agent for winding forming of the composite material in preparing high-toughness epoxy resin according to claim 2, wherein the epoxy resin is more than one of bisphenol A type epoxy resin, bisphenol F type epoxy resin, polyphenol type glycidyl ether epoxy resin, aliphatic glycidyl ether epoxy resin, glycidyl ester type epoxy resin and glycidyl amine type epoxy resin; the curing agent is one or more of ethylenediamine, diethylenetriamine, polymethylenediamine, diethylaminopropylamine, high-carbon tree aliphatic diamine, aliphatic amide polyamine, maleic anhydride and phthalic anhydride; the mass ratio of the curing agent to the epoxy resin is 1:1-5; the mass ratio of other auxiliary agents to the epoxy resin is 1:200-500.
4. The application of the high-performance epoxy resin toughening agent for composite material winding forming in preparing high-toughness epoxy resin according to any one of claims 1-3, wherein the preparation method of the high-performance epoxy resin toughening agent for composite material winding forming is as follows: and after the amphiphilic block polymer is prepared into the polymer nano particles by using a macromolecular self-assembly technology, depositing a precursor of silicon on the polymer nano particles to perform in-situ reaction to prepare the high-performance epoxy resin toughening agent for winding and forming the composite material.
5. The application of the high-performance epoxy resin toughening agent for composite material winding forming in preparing high-toughness epoxy resin according to claim 4, wherein the preparation method of the high-performance epoxy resin toughening agent for composite material winding forming comprises the following specific steps:
(1) Dissolving an amphiphilic block polymer in a good solvent A to obtain a solution with the concentration of 0.1-100 mg/mL, dropwise adding a poor solvent B into the solution to perform self-assembly, and stirring for 5-50 h to obtain a polymer nanoparticle solution with the concentration of 0.01-100 mg/mL;
(2) And (3) dissolving a silicon precursor in an organic solvent C to obtain a solution with the concentration of 0.01-100 mg/mL, dropwise adding the polymer nanoparticle solution obtained in the step (1) into the solution, stirring for 2-100 h to obtain a solution of the high-performance epoxy resin toughening agent for winding forming of the composite material, wherein the mass ratio of the polymer nanoparticle to the silicon precursor is 1:0.1-100, and removing all the solvents to obtain the high-performance epoxy resin toughening agent for winding forming of the composite material.
6. The application of the high-performance epoxy resin toughening agent for winding and forming of the composite material in preparing high-toughness epoxy resin, according to claim 5, wherein in the step (1), the good solvent A is more than one of tetrahydrofuran, dichloromethane, dimethylformamide, chloroform and dimethyl sulfoxide; the poor solvent B is one or more of acetone, methanol, ethanol, glycerol and butanol.
7. The application of the high-performance epoxy resin toughening agent for winding and forming of the composite material in preparing high-toughness epoxy resin, according to claim 5, wherein in the step (2), the precursor of silicon is more than one of tetraethoxysilane, silicate, silicon chloride and tetramethyl silicate; the organic solvent C is one or more of tetrahydrofuran, methanol, ethanol, glycerol and butanol.
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