CN115785618B - In-situ constructed core-shell bio-based flame-retardant nanoparticle/epoxy resin composite material and preparation method thereof - Google Patents
In-situ constructed core-shell bio-based flame-retardant nanoparticle/epoxy resin composite material and preparation method thereof Download PDFInfo
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Abstract
本发明公开了一种原位构筑核壳型生物基阻燃纳米粒子/环氧树脂复合材料的制备方法，包括步骤：将环氧植物油与DOPO发生加成反应，合成磷杂菲环氧植物油中间体；再将磷杂菲环氧植物油中间体与硅烷偶联剂反应引入硅氧烷基团，合成磷杂菲硅氧烷生物基大分子；最后将磷杂菲硅氧烷生物基大分子、三甲基氧基苯基硅烷、二羟基二苯基硅氧烷、引发剂与环氧树脂混合进行非水解溶胶‑凝胶反应，原位缩聚得到核壳型生物基阻燃纳米粒子/环氧树脂混合物，再加入固化剂固化成型制得原位构筑核壳型生物基阻燃纳米粒子/环氧树脂复合材料。本发明通过在环氧树脂基体中原位构筑核壳型生物基阻燃纳米粒子，使纳米粒子能够均匀、稳定地分散在环氧树脂基团中，从而显著改善了环氧树脂的阻燃性能和抗冲击性能。The invention discloses a method for preparing a core-shell bio-based flame-retardant nanoparticle/epoxy resin composite material constructed in situ, comprising the steps of: reacting epoxy vegetable oil with DOPO to synthesize a phosphaphenanthrene epoxy vegetable oil intermediate; then reacting the phosphaphenanthrene epoxy vegetable oil intermediate with a silane coupling agent to introduce a siloxane group to synthesize a phosphaphenanthrene siloxane bio-based macromolecule; finally, mixing the phosphaphenanthrene siloxane bio-based macromolecule, trimethyloxyphenylsilane, dihydroxydiphenylsiloxane, an initiator and an epoxy resin to carry out a non-hydrolyzed sol-gel reaction, and in situ polycondensation to obtain a core-shell bio-based flame-retardant nanoparticle/epoxy resin mixture, and then adding a curing agent to cure and shape to obtain an in situ construction of a core-shell bio-based flame-retardant nanoparticle/epoxy resin composite material. The present invention constructs core-shell bio-based flame-retardant nanoparticles in situ in an epoxy resin matrix, so that the nanoparticles can be evenly and stably dispersed in the epoxy resin group, thereby significantly improving the flame retardant and impact resistance of the epoxy resin.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to an in-situ constructed core-shell bio-based flame-retardant nanoparticle/epoxy resin composite material and a preparation method thereof.
Background
Epoxy resins are widely used in the fields of electronics, electrical industry, etc. due to their high tensile strength and modulus, low cure shrinkage, high adhesion, good chemical resistance and excellent dimensional stability. However, the epoxy resin has the problems of low fracture toughness, poor impact resistance, flammability and incapability of self-extinguishing after leaving fire in practical application due to high crosslinking density, so that the epoxy resin is limited to be widely applied in certain fields. Therefore, how to perform flame retardant modification and toughening modification on epoxy resin to obtain high-performance epoxy resin with excellent comprehensive performance is always a research focus and difficulty in the field.
A great deal of researches show that the balance among the toughness, the strength and the modulus of the epoxy composite material can be realized by adding organic-inorganic nano particles, particularly core-shell nano particles, into the epoxy resin. The silica nanoparticle is a nano filler which is the largest in production scale application in the world, is nontoxic and low in price, and has been used for the application research of reinforcing and toughening of various resins. However, in the research of the prior nanoparticle (including core-shell nanoparticle) modified epoxy composite material, the nanoparticle is added in a physical blending or solution blending mode to prepare the nanocomposite material. Because the specific surface area of the nano particles is large, the nano particles are easy to agglomerate to form stress concentration points, so that the strength and toughness of the material are reduced. Although surface treatments and modifications improve the dispersion or interfacial effect of nanoparticles in the polymer matrix, numerous studies have found that nanoparticles grafted to polymers are, instead, subject to more pronounced multiparticulate aggregation, which is difficult to separate by strong mechanical forces. In addition, the addition of nanoparticles often leads to an increase in the viscosity of the composite resin system, which reduces the processability to a certain extent, and is unfavorable for the single uniform dispersion of nanoparticles, resulting in limited performance improvement. In the solution blending method, the nano particles need to be dispersed with the aid of a solvent and then added with epoxy resin, and in the forming process, the solvent volatilizes, so that environmental pollution can be caused, and defects can be introduced due to residual solvent.
The addition of the flame retardant is an effective solution for rapidly improving the flame retardant property of the epoxy resin and meeting the flame retardant requirement of the material. The phosphorus flame retardant is degraded to generate phosphoric acid or polyphosphoric acid during high-temperature combustion, and a high-viscosity molten vitreous and compact charring layer is easily formed on the surface of a combustion object, so that an inner layer matrix of the material is separated from heat and oxygen, the smoke generation amount and the toxic gas release amount are small, and the flame retardant efficiency is high. Most of the existing phosphorus-containing flame retardants are non-reactive flame retardants, and the poor compatibility can cause the mechanical property degradation of the material due to the weak interface effect between the flame retardants and the epoxy resin matrix.
Under the great trend of development of halogen-free organophosphorus flame retardants, phosphaphenanthrene flame retardants are paid more attention to the research of flame retardant modification of epoxy resin due to higher thermal stability and higher efficient flame retardant effect. The preparation method is characterized in that 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) is taken as a main raw material by Fan Juanjuan et al of Guizhou university of June and university of materials science, a phosphaphenanthrene high-efficiency flame retardant 10- (2, 5-dihydroxydiphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-sulfide (DOPS-NQ) is synthesized through two-step reaction, and is used for flame retardant modification of epoxy resin, and research results show that the DOPS-NQ can obtain better flame retardant effect after being compounded with ammonium polyphosphate (APP) according to a certain proportion, and the compatibility of the APP and an epoxy resin matrix is poor, and part of APP is agglomerated in the matrix to cause stress concentration, so that the mechanical property of the material is reduced.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide an in-situ constructed core-shell type bio-based flame-retardant nanoparticle/epoxy resin composite material with excellent flame retardant property and impact resistance.
The invention also aims to provide a preparation method of the in-situ constructed core-shell bio-based flame-retardant nanoparticle/epoxy resin composite material.
The invention is realized by the following technical scheme:
the preparation method of the in-situ constructed core-shell bio-based flame-retardant nanoparticle/epoxy resin composite material comprises the following steps:
(1) Heating the epoxy vegetable oil and DOPO to 120-160 ℃ under the protection of inert gas atmosphere, and reacting for 24-48h to synthesize a phosphaphenanthrene epoxy vegetable oil intermediate, wherein the mass ratio of the epoxy vegetable oil to DOPO is 1 (0.2-1.2);
(2) Dissolving a phosphaphenanthrene epoxy vegetable oil intermediate in an organic solvent, adding a silane coupling agent, reacting for 1-5h under the protection of inert gas atmosphere, removing the solvent after the reaction is completed, and drying to obtain a phosphaphenanthrene siloxane bio-based macromolecule, wherein the silane coupling agent is selected from any one or more of an amino silane coupling agent and an isocyanate silane coupling agent, when the silane coupling agent is selected from the amino silane coupling agent, the mass ratio of the phosphaphenanthrene epoxy vegetable oil intermediate to the amino silane coupling agent is 1 (0.05-0.5), the reaction temperature is 80-100 ℃, and when the silane coupling agent is selected from the isocyanate silane coupling agent, the mass ratio of the phosphaphenanthrene epoxy vegetable oil intermediate to the isocyanate silane coupling agent is 1 (0.2-0.6), and the reaction temperature is 0-100 ℃;
(3) Uniformly mixing a phosphaphenanthrene siloxane bio-based macromolecule, trimethyloxyphenyl silane, dihydroxydiphenyl siloxane, an initiator and epoxy resin according to the mass ratio of (1-10) (1.5-15) (0.01-0.15) (100), and carrying out non-hydrolytic sol-gel reaction for 1-5h at the temperature of 80-100 ℃ to obtain the core-shell bio-based flame retardant nanoparticle/epoxy resin mixture through in-situ polycondensation.
(4) And (3) mixing the core-shell type bio-based flame-retardant nanoparticle/epoxy resin mixture and a curing agent according to the mass ratio of 100 (20-50), uniformly stirring, then vacuum defoaming at 20-40 ℃, pouring into a mold, and curing and forming to obtain the in-situ constructed core-shell type bio-based flame-retardant nanoparticle/epoxy resin composite material.
The DOPO is 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
The epoxidized vegetable oil is preferably selected from one or more of epoxidized soybean oil, epoxidized castor oil and epoxidized linseed oil.
The aminosilane coupling agent is preferably selected from any one or more of gamma-aminopropyl triethoxysilane, gamma-aminopropyl trimethoxysilane, N-beta (aminoethyl) -gamma-aminopropyl methyldimethoxysilane, N-beta (aminoethyl) -gamma-aminopropyl triethoxysilane, N-beta (aminoethyl) -gamma-aminopropyl methyldiethoxysilane, anilinomethyl triethoxysilane, anilinomethyl trimethoxysilane or aminoethylaminomethyl aminopropyl trimethoxysilane.
The isocyanate silane coupling agent is preferably any one or more of isocyanate propyl trimethoxy silane, isocyanate propyl triethoxy silane, isocyanate propyl methyl dimethoxy silane or isocyanate propyl methyl diethoxy silane.
The inert gas is preferably nitrogen, helium or argon.
The organic solvent is preferably selected from more than one of tetrahydrofuran, 1, 4-dioxane, diglyme, chloroform, ethanol, petroleum ether or n-hexane. Further preferably, the mass ratio of the phosphaphenanthrene epoxy vegetable oil intermediate to the organic solvent is 1 (5-10).
The epoxy resin is preferably any one or more of epoxy resin E51, epoxy resin E44, epoxy resin E42 and epoxy resin E31.
The initiator is preferably selected from any one or more of barium hydroxide and dibutyl tin dilaurate.
The curing agent is preferably any one or more of diaminodiphenyl methane, diaminodiphenyl aldehyde, polyether amine, amino-terminated trimethylolpropane tripropylene glycol ether, hexahydrophthalic anhydride and tetrahydrophthalic anhydride.
Preferably, the average epoxy value of the phosphaphenanthrene epoxy vegetable oil intermediate is 0.04mol/100g-0.42mol/100g. The average epoxy value is determined according to the determination of the epoxy value of the plasticizer according to the national standard GB/T1677-1981 (hydrochloric acid-acetone method).
Preferably, the average molecular weight of the phosphaphenanthrene siloxane bio-based macromolecules is 1000-7500g/mol, more preferably 1500-5500g/mol. If the molecular weight is too large, the mechanical properties of the epoxy resin are greatly affected by the epoxy resin, so that the impact property and the elongation at break are reduced. The phosphaphenanthrene siloxane bio-based macromolecule with the required molecular weight can be obtained by controlling the mass ratio of the phosphaphenanthrene epoxy vegetable oil intermediate to the silane coupling agent. The average molecular weight is determined according to the detection standard method (high performance size exclusion chromatography) of the average molecular weight and molecular weight distribution of the national standard GB/T21864-2008 polystyrene.
The average particle diameter of the core-shell type bio-based flame-retardant nano particles in the in-situ constructed core-shell type bio-based flame-retardant nano particle/epoxy resin composite material is 0.1nm-100nm, the diameter of the inner core is 10-100nm, and the thickness of the outer shell is less than or equal to 50nm. The average particle size is tested according to a standard GB/T29022 particle size analysis Dynamic Light Scattering (DLS) particle size analysis, and the diameter of the inner core and the thickness of the outer shell are obtained according to observation and measurement of a transmission electron microscope.
The weight content of the core-shell type bio-based flame-retardant nano particles in the in-situ constructed core-shell type bio-based flame-retardant nano particle/epoxy resin composite material is 1% -20%. The invention can control the content of the core-shell type bio-based flame-retardant nano particles in the composite material by controlling the addition of the phosphaphenanthrene siloxane bio-based macromolecules, the trimethyloxyphenyl silane and the dihydroxydiphenyl siloxane. The content of the core-shell type bio-based flame-retardant nano particles is within the required range, which is beneficial to ensuring the rigidity and toughness of the material, and the defect of the material is increased due to the excessively high content, so that the impact resistance of the material is reduced.
The invention also provides application of the in-situ constructed core-shell type bio-based flame-retardant nanoparticle/epoxy resin composite material, which can be particularly applied to the field of high-temperature structure flame-retardant materials such as aerospace, electronic and electric and power energy sources and the like.
The invention has the following beneficial effects:
According to the invention, epoxy vegetable oil is utilized to react with DOPO and aminosiloxane coupling agent, a flame-retardant element phosphaphenanthrene and siloxane structure is simultaneously introduced into an epoxy vegetable oil molecular structure, and a core-shell type bio-based flame-retardant nanoparticle with a 'hard core' being similar to polysilsesquioxane and a 'soft shell' being a phosphaphenanthrene epoxy branched macromolecule enrichment layer is formed in situ in an epoxy resin precursor by a non-hydrolytic sol-gel method, so that the nanoparticle can be uniformly and stably dispersed in an epoxy resin group, the compatibility between the surface of the nanoparticle and an epoxy resin matrix is effectively increased by the 'soft shell' phosphaphenanthrene epoxy branched macromolecule enrichment layer, the toughness and strength of the material can be greatly improved, and meanwhile, the flame-retardant performance of the material is remarkably improved by phosphorus-silicon synergistic flame retardance, so that the in-situ core-shell type bio-based flame-retardant nanoparticle/epoxy resin composite material with excellent flame-retardant performance and shock resistance is formed.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a phosphaphenanthrene siloxane bio-based macromolecule of example 1.
FIG. 2 is a nuclear magnetic resonance chromatogram of a phosphaphenanthrene siloxane bio-based macromolecule of example 1.
FIG. 3 is a distribution diagram of particle size of core-shell bio-based flame retardant nanoparticles of the in situ structured core-shell bio-based flame retardant nanoparticle/epoxy resin composite of example 1.
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of a phosphaphenanthrene siloxane bio-based macromolecule of example 8.
FIG. 5 is a cross-sectional microscopic morphology of the in-situ fabricated core-shell bio-based flame retardant nanoparticle/epoxy composite of example 10.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
The reagents and starting materials used in the examples and comparative examples of the invention were all commercially available.
Example 1
(1) Under the protection of high-purity nitrogen, sequentially adding DOPO and epoxidized soybean oil ESO (the mass ratio of the epoxidized soybean oil to the DOPO is 1:1) into a three-necked flask, raising the temperature to 120 ℃, raising the temperature and maintaining the temperature at 150 ℃ for reaction for 72 hours after the DOPO is completely melted, and obtaining a phosphaphenanthrene epoxidized soybean oil intermediate, wherein the average epoxy value is 0.07mol/100g;
(2) Dissolving a phosphaphenanthrene epoxy soybean oil intermediate in 1, 4-dioxane (the mass ratio of the phosphaphenanthrene epoxy soybean oil intermediate to the 1, 4-dioxane is 1:5), adding gamma-aminopropyl triethoxysilane (the mass ratio of the phosphaphenanthrene epoxy soybean oil intermediate to the gamma-aminopropyl triethoxysilane is 1:0.05), raising the temperature and maintaining the temperature at 90 ℃ for reaction for 3 hours, removing the solvent after the reaction is completed, and drying under vacuum to obtain a phosphaphenanthrene siloxane bio-based macromolecule with the average molecular weight of 3836g/mol;
(3) Uniformly mixing phosphaphenanthrene siloxane bio-based macromolecules, trimethyloxyphenyl silane, dihydroxydiphenyl siloxane, dibutyltin dilaurate and bisphenol A type epoxy resin E51 according to the mass ratio of 3:2:3:0.1:100, and carrying out non-hydrolytic sol-gel reaction for 4 hours at the temperature of 90 ℃ to obtain a core-shell bio-based flame retardant nanoparticle/epoxy resin mixture through in-situ polycondensation;
(4) The core-shell type bio-based flame-retardant nanoparticle/epoxy resin mixture and diaminodiphenyl methane (DDM) curing agent are mixed and stirred uniformly according to the mass ratio of 100:25, then vacuum defoamed for 2min at 25 ℃, poured into a silica gel mold, and cured and molded under the conditions of 100 ℃ per 2 hours, 150 ℃ per 2 hours and 180 ℃ per 2 hours, so that the core-shell type bio-based flame-retardant nanoparticle/epoxy resin composite material is prepared, wherein the average particle size of the core-shell type bio-based flame-retardant nanoparticle is 73.9nm, the diameter of the inner core is 50.3nm, the thickness of the outer shell is 23.6nm, and the weight content of the core-shell type bio-based flame-retardant nanoparticle is 5.9%.
The structure of the phosphaphenanthrene siloxane bio-based macromolecule synthesized in the step (2) of example 1 is subjected to nuclear magnetic resonance spectrum characterization, as shown in fig. 1 and 2. The 1 H-NMR characterization result shows that the chemical shift is between 6.9 and 8.0ppm and corresponds to five proton characteristic peaks on a phosphaphenanthrene ring, the chemical shift is between 5.1 and 5.3 ppm and delta=3.9 and 4.3ppm and corresponds to proton characteristic peaks on ester group middle carbon in epoxy soybean oil, the chemical shift is between 3.8 and 3.6ppm and corresponds to proton characteristic peaks on methylene beside methyl in silane coupling agent, the chemical shift is between 2.8 and 3.1ppm and corresponds to proton characteristic peaks on epoxy group, the chemical shift is between 0.9 and 2.4ppm and corresponds to proton characteristic peaks on aliphatic chain in epoxy soybean oil, the chemical shift is between 1.1ppm and corresponds to proton characteristic peaks on methyl in chain end methyl, the chemical shift is between 0.6 and 0.6ppm and corresponds to proton characteristic peaks on methylene beside silicon, and the chemical shift is between 0.8 and 0.6ppm and corresponds to proton characteristic peaks 31 P-P in the chemical shift is only in a flame retardant molecular branching element, and the chemical shift is only 14.7ppm.
The particle size distribution of the core-shell bio-based flame retardant nanoparticle of the in-situ construction core-shell bio-based flame retardant nanoparticle/epoxy resin composite material of example 1 was tested with reference to a standard GB/T29022 particle size analysis Dynamic Light Scattering (DLS) particle size analysis, and the results are shown in FIG. 3.
Example 2
Example 2 differs from example 1 only in that in step (3) the mass ratio of phosphaphenanthrene siloxane bio-based macromolecules, trimethyloxyphenyl silane, dihydroxydiphenyl siloxane, dibutyltin dilaurate to bisphenol a type epoxy resin E51 is 6:2:3:0.1:100.
The in-situ constructed core-shell type bio-based flame-retardant nanoparticle/epoxy resin composite material is finally prepared, wherein the average particle size of the core-shell type bio-based flame-retardant nanoparticle is 81.4nm, the inner core diameter is 51.5nm, the shell thickness is 29.9nm, and the weight content of the core-shell type bio-based flame-retardant nanoparticle is 7.9%.
Example 3
Example 3 differs from example 1 only in that in step (3) the mass ratio of phosphaphenanthrene siloxane bio-based macromolecules, trimethyloxyphenyl silane, dihydroxydiphenyl siloxane, dibutyltin dilaurate to bisphenol a type epoxy resin E51 is 9:2:3:0.1:100.
The in-situ constructed core-shell type bio-based flame-retardant nanoparticle/epoxy resin composite material is prepared finally, the average particle size of the core-shell type bio-based flame-retardant nanoparticle is 86.2 nm, the inner core diameter is 52.7nm, the thickness of the outer shell layer is 33.5nm, and the weight content of the core-shell type bio-based flame-retardant nanoparticle is 9.8%.
Example 4
The difference between the embodiment 4 and the embodiment 1 is that in the step (4), the core-shell type bio-based flame-retardant nanoparticle/epoxy resin mixture and the polyether amine (Hensman D230) curing agent are mixed and stirred uniformly according to the mass ratio of 100:29, then the mixture is defoamed for 2min under vacuum at 25 ℃, poured into a silica gel mold and cured and molded under the conditions of 80 ℃ per 2 hours, 110 ℃ per 2 hours and 130 ℃ per 2 hours, so as to prepare the in-situ constructed core-shell type bio-based flame-retardant nanoparticle/epoxy resin composite material, wherein the average particle size of the core-shell type bio-based flame-retardant nanoparticle is 73.9nm, the diameter of the core is 50.3nm, the thickness of the shell is 23.6nm, and the weight content of the core-shell type bio-based flame-retardant nanoparticle is 5.7%.
Example 5
(1) Under the protection of high-purity nitrogen, sequentially adding DOPO and epoxidized soybean oil ESO (the mass ratio of the epoxidized soybean oil to the DOPO is 1:1.2) into a three-necked flask, raising the temperature to 120 ℃, raising the temperature and maintaining the temperature at 150 ℃ for reaction for 72 hours after the DOPO is completely melted, so as to obtain a phosphaphenanthrene epoxidized soybean oil intermediate, wherein the average epoxy value is 0.02mol/100g;
(2) Dissolving a phosphaphenanthrene epoxy soybean oil intermediate in 1, 4-dioxane (the mass ratio of the phosphaphenanthrene epoxy soybean oil intermediate to the 1, 4-dioxane is 1:5), adding gamma-aminopropyl triethoxysilane (the mass ratio of the phosphaphenanthrene epoxy soybean oil intermediate to the gamma-aminopropyl triethoxysilane is 1:0.05), raising the temperature and maintaining the temperature at 90 ℃ for reaction for 3 hours, removing the solvent after the reaction is completed, and drying under vacuum to obtain a phosphaphenanthrene siloxane bio-based macromolecule with the average molecular weight of 2316g/mol;
(3) Uniformly mixing phosphaphenanthrene siloxane bio-based macromolecules, trimethyloxyphenyl silane, dihydroxydiphenyl siloxane, dibutyltin dilaurate and bisphenol A type epoxy resin E51 according to the mass ratio of 3:2:3:0.1:100, and carrying out non-hydrolytic sol-gel reaction for 4 hours at the temperature of 90 ℃ to obtain a core-shell bio-based flame retardant nanoparticle/epoxy resin mixture through in-situ polycondensation;
(4) The core-shell type bio-based flame-retardant nanoparticle/epoxy resin mixture and diaminodiphenyl methane (DDM) curing agent are mixed and stirred uniformly according to the mass ratio of 100:25, then vacuum defoamed for 2min at 25 ℃, poured into a silica gel mold, and cured and molded under the conditions of 100 ℃ per 2 hours, 150 ℃ per 2 hours and 180 ℃ per 2 hours, so that the core-shell type bio-based flame-retardant nanoparticle/epoxy resin composite material is prepared, wherein the average particle size of the core-shell type bio-based flame-retardant nanoparticle is 91.3nm, the diameter of the inner core is 63.5nm, the thickness of the outer shell is 27.8nm, and the weight content of the core-shell type bio-based flame-retardant nanoparticle is 5.9%.
Example 6
(1) Under the protection of high-purity nitrogen, sequentially adding DOPO and epoxidized soybean oil ESO (the mass ratio of the epoxidized soybean oil to the DOPO is 1:0.2) into a three-necked flask, raising the temperature to 120 ℃, raising the temperature and maintaining the temperature at 150 ℃ for reaction for 72 hours after the DOPO is completely melted, so as to obtain a phosphaphenanthrene epoxidized soybean oil intermediate, wherein the average epoxy value is 0.41mol/100 g;
(2) Dissolving a phosphaphenanthrene epoxy soybean oil intermediate in 1, 4-dioxane (the mass ratio of the phosphaphenanthrene epoxy soybean oil intermediate to the 1, 4-dioxane is 1:5), adding gamma-aminopropyl triethoxysilane (the mass ratio of the phosphaphenanthrene epoxy soybean oil intermediate to the gamma-aminopropyl triethoxysilane is 1:0.05), raising the temperature and maintaining the temperature at 90 ℃ for reaction for 3 hours, removing the solvent after the reaction is completed, and drying under vacuum to obtain a phosphaphenanthrene siloxane bio-based macromolecule with the average molecular weight of 3532g/mol;
(3) Uniformly mixing phosphaphenanthrene siloxane bio-based macromolecules, trimethyloxyphenyl silane, dihydroxydiphenyl siloxane, dibutyltin dilaurate and bisphenol A type epoxy resin E51 according to the mass ratio of 3:2:3:0.1:100, and carrying out non-hydrolytic sol-gel reaction for 4 hours at the temperature of 90 ℃ to obtain a core-shell bio-based flame retardant nanoparticle/epoxy resin mixture through in-situ polycondensation;
(4) The core-shell type bio-based flame-retardant nanoparticle/epoxy resin mixture and diaminodiphenyl methane (DDM) curing agent are mixed and stirred uniformly according to the mass ratio of 100:25, then vacuum defoamed for 2min at 25 ℃, poured into a silica gel mold, and cured and molded under the conditions of 100 ℃ per 2 hours, 150 ℃ per 2 hours and 180 ℃ per 2 hours, so that the core-shell type bio-based flame-retardant nanoparticle/epoxy resin composite material is prepared, wherein the average particle size of the core-shell type bio-based flame-retardant nanoparticle is 73.1nm, the diameter of the inner core is 50.7nm, the thickness of the outer shell is 22.4nm, and the weight content of the core-shell type bio-based flame-retardant nanoparticle is 5.9%.
Example 7
(1) Under the protection of high-purity nitrogen, sequentially adding DOPO and epoxidized soybean oil ESO (the mass ratio of the epoxidized soybean oil to the DOPO is 1:1) into a three-necked flask, raising the temperature to 120 ℃, raising the temperature and maintaining the temperature at 150 ℃ for reaction for 72 hours after the DOPO is completely melted, and obtaining a phosphaphenanthrene epoxidized soybean oil intermediate, wherein the average epoxy value is 0.07mol/100 g;
(2) Dissolving a phosphaphenanthrene epoxy soybean oil intermediate in 1, 4-dioxane (the mass ratio of the phosphaphenanthrene epoxy soybean oil intermediate to the 1, 4-dioxane is 1:5), adding gamma-aminopropyl triethoxysilane (the mass ratio of the phosphaphenanthrene epoxy soybean oil intermediate to the gamma-aminopropyl triethoxysilane is 1:0.2), raising the temperature and maintaining the temperature at 90 ℃ for reaction for 3 hours, removing the solvent after the reaction is completed, and drying under vacuum to obtain a phosphaphenanthrene siloxane bio-based macromolecule with the average molecular weight of 6714g/mol;
(3) Uniformly mixing phosphaphenanthrene siloxane bio-based macromolecules, trimethyloxyphenyl silane, dihydroxydiphenyl siloxane, dibutyltin dilaurate and bisphenol A type epoxy resin E51 according to the mass ratio of 3:2:3:0.1:100, and carrying out non-hydrolytic sol-gel reaction for 4 hours at the temperature of 90 ℃ to obtain a core-shell bio-based flame retardant nanoparticle/epoxy resin mixture through in-situ polycondensation;
(4) And (3) mixing the core-shell type bio-based flame-retardant nanoparticle/epoxy resin mixture and diaminodiphenyl methane (DDM) curing agent according to the mass ratio of 100:25, uniformly stirring, then vacuum defoaming for 2min at 25 ℃, pouring into a silica gel mold, and curing and molding under the conditions of 100 ℃ per 2 hours, 150 ℃ per 2 hours and 180 ℃ per 2 hours to obtain the in-situ constructed core-shell type bio-based flame-retardant nanoparticle/epoxy resin composite material, wherein the average particle size of the core-shell type bio-based flame-retardant nanoparticle is 95.1nm, the diameter of the inner core is 53.4nm, the thickness of the outer shell layer is 41.7nm, and the weight content of the core-shell type bio-based flame-retardant nanoparticle is 5.9%.
Example 8
(1) Under the protection of high-purity nitrogen, sequentially adding DOPO and epoxidized soybean oil ESO (the mass ratio of the epoxidized soybean oil to the DOPO is 1:1) into a three-necked flask, raising the temperature to 120 ℃, raising the temperature and maintaining the temperature at 160 ℃ for reaction for 72 hours after the DOPO is completely melted, and obtaining a phosphaphenanthrene epoxidized soybean oil intermediate, wherein the average epoxy value is 0.07mol/100g;
(2) Under the protection of high-purity nitrogen, dissolving a phosphaphenanthrene epoxy soybean oil intermediate in 1, 4-dioxane (the mass ratio of the phosphaphenanthrene epoxy soybean oil intermediate to the 1, 4-dioxane is 1:5), adding isocyanatopropyl triethoxysilane (the mass ratio of the phosphaphenanthrene epoxy soybean oil intermediate to the isocyanatopropyl triethoxysilane is 1:0.57), raising the temperature and maintaining the temperature at 30 ℃ for reaction for 3 hours, removing the solvent after the reaction is finished, and drying under vacuum to obtain a phosphaphenanthrene siloxane bio-based macromolecule with the average molecular weight of 2573g/mol;
(3) Uniformly mixing phosphaphenanthrene siloxane bio-based macromolecules, trimethyloxyphenyl silane, dihydroxydiphenyl siloxane, dibutyltin dilaurate and bisphenol A type epoxy resin E51 according to the mass ratio of 2:2:3:0.1:100, and carrying out non-hydrolytic sol-gel reaction for 5 hours at the temperature of 90 ℃ to obtain a core-shell bio-based flame retardant nanoparticle/epoxy resin mixture through in-situ polycondensation;
(4) And (3) mixing the core-shell type bio-based flame-retardant nanoparticle/epoxy resin mixture and diaminodiphenyl methane (DDM) curing agent according to the mass ratio of 100:25, uniformly stirring, then vacuum defoaming for 2min at 25 ℃, pouring into a silica gel mold, and curing and molding under the conditions of 100 ℃ per 2 hours, 150 ℃ per 2 hours and 180 ℃ per 2 hours to obtain the in-situ constructed core-shell type bio-based flame-retardant nanoparticle/epoxy resin composite material, wherein the average particle size of the core-shell type bio-based flame-retardant nanoparticle is 71.9nm, the diameter of the inner core is 51.6nm, the thickness of the outer shell layer is 20.3nm, and the weight content of the core-shell type bio-based flame-retardant nanoparticle is 5.2%.
The structure of the phosphaphenanthrene siloxane bio-based macromolecule synthesized in step (2) of example 8 was subjected to nuclear magnetic resonance spectroscopy as shown in fig. 4. The characteristic result of 1 H-NMR is that five proton characteristic peaks corresponding to phosphaphenanthrene rings are located between 6.9 and 8.0ppm, five proton characteristic peaks corresponding to phosphorus-phenanthrene rings are located between 5.1 and 5.3 ppm and 3.9 and 4.3ppm, one proton characteristic peak corresponding to intermediate carbon of ester groups in epoxy soybean oil is located between 3.7 and 3.4ppm, one proton characteristic peak corresponding to methyl beside methyl groups in silane coupling agents is located between 2.8 and 3.1ppm, one proton characteristic peak corresponding to epoxy groups is located between 0.9 and 2.4ppm, one proton characteristic peak corresponding to aliphatic chains in epoxy soybean oil is located between 1.2 and 1.5ppm, one proton characteristic peak corresponding to methyl groups at chain ends is located between 0.6 and 0.9ppm, and one proton characteristic peak corresponding to silicon beside methyl groups is located between 0.5 and 0.6 ppm.
Example 9
Example 9 differs from example 8 only in that in step (3) the mass ratio of phosphaphenanthrene siloxane bio-based macromolecules, trimethyloxyphenyl silane, dihydroxydiphenyl siloxane, dibutyltin dilaurate to bisphenol a type epoxy resin E51 is 2:4:6:0.1:100.
The in-situ constructed core-shell type bio-based flame-retardant nanoparticle/epoxy resin composite material is finally prepared, wherein the average particle size of the core-shell type bio-based flame-retardant nanoparticle is 87.2nm, the diameter of the inner core is 67.4nm, the thickness of the outer shell is 19.8nm, and the weight content of the core-shell type bio-based flame-retardant nanoparticle is 8.5%.
Example 10
Example 10 differs from example 8 only in that in step (3) the mass ratio of phosphaphenanthrene siloxane bio-based macromolecules, trimethyloxyphenyl silane, dihydroxydiphenyl siloxane, dibutyltin dilaurate to bisphenol a type epoxy resin E51 is 2:6:9:0.3:100.
The in-situ constructed core-shell type bio-based flame-retardant nanoparticle/epoxy resin composite material is finally prepared, wherein the average particle size of the core-shell type bio-based flame-retardant nanoparticle is 92.2nm, the diameter of the inner core is 71.6nm, the thickness of the outer shell is 20.6nm, and the weight content of the core-shell type bio-based flame-retardant nanoparticle is 11.6%.
The microscopic cross-section morphology (before the sample test, the metal spraying treatment is performed) of the core-shell type bio-based flame-retardant nanoparticle/epoxy resin composite material in the in-situ construction of example 10 is observed by using a scanning electron microscope, and as shown in fig. 5, it can be seen that the nanoparticles can be uniformly and stably dispersed in the composite material.
Example 11
The difference between the embodiment 11 and the embodiment 8 is that in the step (4), the core-shell type bio-based flame-retardant nanoparticle/epoxy resin mixture and the polyether amine (Hensman D230) curing agent are mixed and stirred uniformly according to the mass ratio of 100:29, then the mixture is defoamed for 2min under vacuum at 25 ℃, poured into a silica gel mold and cured and molded under the conditions of 80 ℃ per 2 hours, 110 ℃ per 2 hours and 130 ℃ per 2 hours, so as to prepare the in-situ constructed core-shell type bio-based flame-retardant nanoparticle/epoxy resin composite material, wherein the average particle size of the core-shell type bio-based flame-retardant nanoparticle is 71.9nm, the diameter of the core is 51.6nm, the thickness of the shell is 20.3nm, and the weight content of the core-shell type bio-based flame-retardant nanoparticle is 5.1%.
Example 12
(1) Under the protection of high-purity nitrogen, sequentially adding DOPO and epoxy castor oil ECO (the mass ratio of the epoxy castor oil to the DOPO is 1:0.5) into a three-necked flask, raising the temperature to 120 ℃, raising the temperature after the DOPO is completely melted, and maintaining the temperature at 160 ℃ for reaction for 50 hours to prepare a phosphaphenanthrene epoxy castor oil intermediate, wherein the average epoxy value is 0.23mol/100g;
(2) Dissolving a phosphaphenanthrene epoxy castor oil intermediate in tetrahydrofuran (the mass ratio of the phosphaphenanthrene epoxy castor oil intermediate to the tetrahydrofuran is 1:7) under the protection of high-purity nitrogen, adding gamma-aminopropyl trimethoxysilane (the mass ratio of the phosphaphenanthrene epoxy castor oil intermediate to the gamma-aminopropyl trimethoxysilane is 1:0.07), raising the temperature and maintaining the temperature at 90 ℃ for reaction for 3 hours, removing a solvent after the reaction is finished, and drying under vacuum to obtain a phosphaphenanthrene siloxane bio-based macromolecule with the average molecular weight of 3536 g/mol;
(3) Uniformly mixing phosphaphenanthrene siloxane bio-based macromolecules, trimethyloxyphenyl silane, dihydroxydiphenyl siloxane, barium hydroxide and bisphenol A type epoxy resin E44 according to the mass ratio of 3:2:3:0.1:100, and performing non-hydrolytic sol-gel reaction for 3 hours at the temperature of 100 ℃, so as to obtain a core-shell bio-based flame retardant nanoparticle/epoxy resin mixture through in-situ polycondensation;
(4) The core-shell type bio-based flame-retardant nanoparticle/epoxy resin composite material is prepared by mixing and stirring a core-shell type bio-based flame-retardant nanoparticle/epoxy resin mixture and a diaminodiphenyl methane (DDM) curing agent according to a mass ratio of 100:21.5, then conducting vacuum defoaming for 2min at 25 ℃, pouring the mixture into a silica gel mold, and conducting curing molding under the conditions of 100 ℃ per 2 hours, 150 ℃ per 2 hours and 180 ℃ per 2 hours, wherein the average particle size of the core-shell type bio-based flame-retardant nanoparticle is 71.9nm, the diameter of the core is 50.3nm, the thickness of the shell layer is 21.6nm, and the weight content of the core-shell type bio-based flame-retardant nanoparticle is 6.1%.
Example 13
(1) Under the protection of high-purity nitrogen, sequentially adding DOPO and epoxy linseed oil ELO (the mass ratio of the epoxy linseed oil to the DOPO is 1:0.5) into a three-necked flask, raising the temperature to 120 ℃, raising the temperature and maintaining the temperature at 140 ℃ for reaction for 72 hours after the DOPO is completely melted, and obtaining a phosphaphenanthrene epoxy linseed oil intermediate with an average epoxy value of 0.21mol/100g;
(2) Under the protection of high-purity nitrogen, dissolving the phosphaphenanthrene epoxy linseed oil intermediate in1, 4-dioxane (the mass ratio of the phosphaphenanthrene epoxy linseed oil intermediate to the 1, 4-dioxane is 1:5), adding N-beta (aminoethyl) -gamma-aminopropyl trimethoxysilane (the mass ratio of the phosphaphenanthrene epoxy linseed oil intermediate to the N-beta (aminoethyl) -gamma-aminopropyl trimethoxysilane is 1:0.07), raising the temperature and maintaining the temperature at 90 ℃ for reaction for 3 hours, removing the solvent after the reaction is finished, and drying under vacuum condition to obtain the phosphaphenanthrene siloxane bio-based macromolecule with the average molecular weight of 3263 g/mol;
(3) Uniformly mixing phosphaphenanthrene siloxane bio-based macromolecules, trimethyloxyphenyl silane, dihydroxydiphenyl siloxane, dibutyltin dilaurate and bisphenol A type epoxy resin E51 according to the mass ratio of 3:2:3:0.1:100, and carrying out non-hydrolytic sol-gel reaction for 4 hours at the temperature of 90 ℃ to obtain a core-shell bio-based flame retardant nanoparticle/epoxy resin mixture through in-situ polycondensation;
(4) And (3) mixing the core-shell type bio-based flame-retardant nanoparticle/epoxy resin mixture and diaminodiphenyl methane (DDM) curing agent according to the mass ratio of 100:25, uniformly stirring, then vacuum defoaming for 2min at 25 ℃, pouring into a silica gel mold, and curing and molding under the conditions of 100 ℃ per 2 hours, 150 ℃ per 2 hours and 180 ℃ per 2 hours to obtain the in-situ constructed core-shell type bio-based flame-retardant nanoparticle/epoxy resin composite material, wherein the average particle size of the core-shell type bio-based flame-retardant nanoparticle is 70.1nm, the diameter of the inner core is 49.6nm, the thickness of the outer shell layer is 20.5nm, and the weight content of the core-shell type bio-based flame-retardant nanoparticle is 5.9%.
Comparative example 1
Bisphenol A epoxy resin E51 and 4, 4-diaminodiphenyl methane (DDM) curing agent are mixed and stirred uniformly according to the mass ratio of 100:25, then vacuum defoamed for 2min at 25 ℃, poured into a silica gel mold, and cured and molded under the conditions of 100 ℃ per 2 hours, 150 ℃ per 2 hours and 180 ℃ per 2 hours, so that the cured epoxy resin material is prepared.
Comparative example 2:
Bisphenol A epoxy resin E51 and polyetheramine (Hunsman D230) curing agent are mixed and stirred uniformly according to the mass ratio of 100:29, then vacuum defoamed for 2min at 25 ℃, poured into a silica gel mold and cured and molded under the conditions of 80 ℃ per 2 hours, 110 ℃ per 2 hours and 130 ℃ per 2 hours, and the cured epoxy resin material is prepared.
Comparative example 3
Bisphenol A epoxy resin E44 and 4, 4-diaminodiphenyl methane (DDM) curing agent are mixed and stirred uniformly according to the mass ratio of 100:21.5, then vacuum defoamed for 2min at 25 ℃, poured into a silica gel mold and cured and molded under the conditions of 100 ℃ per 2 hours, 150 ℃ per 2 hours and 180 ℃ per 2 hours, and the cured epoxy resin material is prepared.
Comparative example 4
Comparative example 4 differs from example 1 only in that the mass ratio of phosphaphenanthrene siloxane bio-based macromolecules, trimethyloxyphenyl silane, dihydroxydiphenyl siloxane, dibutyltin dilaurate to bisphenol a type epoxy resin E51 in step (3) is 18:6:9:0.3:100.
The in-situ constructed core-shell type bio-based flame-retardant nanoparticle/epoxy resin composite material is finally prepared, wherein the average particle size of the core-shell type bio-based flame-retardant nanoparticle is 127.3nm, the inner core diameter is 86.9nm, the shell thickness is 40.4nm, and the weight content of the core-shell type bio-based flame-retardant nanoparticle is 20.1%.
Correlation performance test:
(1) Notched impact strength-the test piece was 80 mm X10 mm X4 mm in size and the notched residual thickness was 8mm, as measured by reference to standard GB/T1843-1996.
(2) Limiting oxygen index the sample size was 80mm x 6.5mm x 3mm tested with reference to standard GB/T2406-2009.
(3) Flame retardant rating UL94 vertical oxygen index, test sample size 120 mm x 13 x mm x 3mm, with reference to standard GB/T2408-2008.
TABLE 1 results of the correlation Performance test of examples 1-13 and comparative examples 1-4
。
As shown by the results of the examples and the comparative examples, the core-shell type bio-based flame retardant nanoparticle is constructed in situ in the epoxy resin matrix, so that the nanoparticle can be uniformly and stably dispersed in the epoxy resin matrix, and the in-situ constructed core-shell type bio-based flame retardant nanoparticle/epoxy resin composite material with excellent flame retardant performance and impact resistance is obtained.
Claims (11)
1. The preparation method of the in-situ constructed core-shell bio-based flame-retardant nanoparticle/epoxy resin composite material is characterized by comprising the following steps of:
(1) Heating the epoxy vegetable oil and DOPO to 120-160 ℃ under the protection of inert gas atmosphere, and reacting for 24-48h to synthesize a phosphaphenanthrene epoxy vegetable oil intermediate, wherein the mass ratio of the epoxy vegetable oil to DOPO is 1 (0.2-1.2);
(2) Dissolving a phosphaphenanthrene epoxy vegetable oil intermediate in an organic solvent, adding a silane coupling agent, reacting for 1-5h under the protection of inert gas atmosphere, removing the solvent after the reaction is completed, and drying to obtain a phosphaphenanthrene siloxane bio-based macromolecule, wherein the silane coupling agent is selected from any one or more of an amino silane coupling agent or an isocyanate silane coupling agent, when the silane coupling agent is selected from the amino silane coupling agent, the mass ratio of the phosphaphenanthrene epoxy vegetable oil intermediate to the amino silane coupling agent is 1 (0.05-0.5), the reaction temperature is 80-100 ℃, and when the silane coupling agent is selected from the isocyanate silane coupling agent, the mass ratio of the phosphaphenanthrene epoxy vegetable oil intermediate to the isocyanate silane coupling agent is 1 (0.2-0.6), and the reaction temperature is 0-100 ℃;
(3) Uniformly mixing a phosphaphenanthrene siloxane bio-based macromolecule, trimethyloxyphenyl silane, dihydroxydiphenyl silane, an initiator and epoxy resin according to the mass ratio of (1-10) (1.5-15) (0.01-0.15) (100), and carrying out non-hydrolytic sol-gel reaction for 1-5h at the temperature of 80-100 ℃ to obtain a core-shell bio-based flame retardant nanoparticle/epoxy resin mixture through in-situ polycondensation;
(4) And (3) mixing the core-shell type bio-based flame-retardant nanoparticle/epoxy resin mixture and a curing agent according to the mass ratio of 100 (20-50), uniformly stirring, then vacuum defoaming at 20-40 ℃, pouring into a mold, and curing and forming to obtain the in-situ constructed core-shell type bio-based flame-retardant nanoparticle/epoxy resin composite material.
2. The method for preparing the in-situ constructed core-shell type bio-based flame-retardant nanoparticle/epoxy resin composite material according to claim 1, wherein the epoxy vegetable oil is selected from any one or more of epoxy soybean oil, epoxy castor oil and epoxy linseed oil.
3. The preparation method of the in-situ constructed core-shell bio-based flame-retardant nanoparticle/epoxy resin composite material according to claim 1, wherein the aminosilane coupling agent is selected from any one or more of gamma-aminopropyl triethoxysilane, gamma-aminopropyl trimethoxysilane, N-beta (aminoethyl) -gamma-aminopropyl methyldimethoxysilane, N-beta (aminoethyl) -gamma-aminopropyl triethoxysilane, N-beta (aminoethyl) -gamma-aminopropyl methyldiethoxysilane, anilinomethyl triethoxysilane, anilinomethyl trimethoxysilane or aminoethylaminomethyl aminopropyl trimethoxysilane, and the isocyanato silane coupling agent is selected from any one or more of isocyanato propyl trimethoxysilane, isocyanato propyl triethoxysilane, isocyanato propyl methyldimethoxy silane or isocyanato propyl methyldiethoxy silane.
4. The method for preparing the in-situ structured core-shell bio-based flame retardant nanoparticle/epoxy resin composite material according to claim 1, wherein the average epoxy value of the phosphaphenanthrene epoxy vegetable oil intermediate is 0.04mol/100g-0.42mol/100g.
5. The method for preparing the in-situ structured core-shell bio-based flame retardant nanoparticle/epoxy resin composite material according to claim 1, wherein the average molecular weight of the phosphaphenanthrene siloxane bio-based macromolecules is 1000-7500g/mol.
6. The method for preparing the in-situ structured core-shell type bio-based flame-retardant nanoparticle/epoxy resin composite material according to claim 5, wherein the average molecular weight of the phosphaphenanthrene siloxane bio-based flame-retardant branched macromolecule is 1500-5500g/mol.
7. The method for preparing the in-situ constructed core-shell type bio-based flame-retardant nanoparticle/epoxy resin composite material according to claim 1, wherein the inert gas is nitrogen, helium or argon, and the organic solvent is more than one selected from tetrahydrofuran, 1, 4-dioxane, diglyme, chloroform, ethanol, petroleum ether or n-hexane.
8. The preparation method of the in-situ constructed core-shell type bio-based flame-retardant nanoparticle/epoxy resin composite material according to claim 1, wherein the epoxy resin is selected from any one or more of epoxy resin E51, epoxy resin E44, epoxy resin E42 and epoxy resin E31, and the initiator is selected from any one or more of barium hydroxide and dibutyltin dilaurate.
9. The method for preparing the in-situ structured core-shell bio-based flame-retardant nanoparticle/epoxy resin composite material according to claim 1, wherein the curing agent is selected from any one or more of diaminodiphenyl methane, diaminodiphenyl aldehyde, polyetheramine, amino-terminated trimethylolpropane tripropyleneglycol ether, hexahydrophthalic anhydride and tetrahydrophthalic anhydride.
10. The method for preparing the in-situ constructed core-shell type bio-based flame-retardant nanoparticle/epoxy resin composite material according to claim 1, wherein the average particle size of the core-shell type bio-based flame-retardant nanoparticle in the in-situ constructed core-shell type bio-based flame-retardant nanoparticle/epoxy resin composite material is 0.1nm-100nm, the diameter of the inner core is 10-100nm, and the thickness of the outer shell is less than or equal to 50nm.
11. The method for preparing the in-situ constructed core-shell type bio-based flame-retardant nanoparticle/epoxy resin composite material according to claim 1, wherein the weight content of the core-shell type bio-based flame-retardant nanoparticle in the in-situ constructed core-shell type bio-based flame-retardant nanoparticle/epoxy resin composite material is 1% -20%.
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