CN114456547B - High-strength high-toughness transparent flame-retardant epoxy resin and preparation method thereof - Google Patents

High-strength high-toughness transparent flame-retardant epoxy resin and preparation method thereof Download PDF

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CN114456547B
CN114456547B CN202210091654.4A CN202210091654A CN114456547B CN 114456547 B CN114456547 B CN 114456547B CN 202210091654 A CN202210091654 A CN 202210091654A CN 114456547 B CN114456547 B CN 114456547B
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epoxy resin
hyperbranched
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acid ester
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CN114456547A (en
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颜红侠
张渊博
俞睿之
郭留龙
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Northwestern Polytechnical University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/08—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing boron
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
    • C—CHEMISTRY; METALLURGY
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    • C08L2203/204—Applications use in electrical or conductive gadgets use in solar cells
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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Abstract

The invention relates to a high-strength high-toughness transparent flame-retardant epoxy resin and a preparation method thereof, wherein tributyl borate and 1, 3-propylene glycol are used for carrying out ester exchange polycondensation reaction, hyperbranched polyboronate is used as a phosphorus-free flame-retardant modifier, and bisphenol A type epoxy resin is modified by the hyperbranched polyboronate. The hyperbranched polyborate terminal contains a large number of active hydroxyl groups, has good compatibility with epoxy resin, can participate in the curing reaction of the epoxy resin, introduces hyperbranched cavity units, flexible aliphatic chain segments and organic/inorganic hybridized B-O-C framework structures into the crosslinking network of the epoxy resin, and can improve the limiting oxygen index of resin combustion and reduce the heat release and smoke release of combustion while synergistically improving the strength and toughness of the epoxy resin. In particular, the introduction of the hyperbranched polyboronic acid ester does not affect the excellent transparency and color of the epoxy resin, and meanwhile, the preparation is simple and the cost is low. Therefore, the epoxy resin containing hyperbranched polyboronic acid ester has wide application prospect.

Description

High-strength high-toughness transparent flame-retardant epoxy resin and preparation method thereof
Technical Field
The invention belongs to the technical field of advanced polymer material science, and relates to a high-strength high-toughness transparent flame-retardant epoxy resin and a preparation method thereof.
Background
The epoxy resin is used as a thermosetting resin with low price and good performance, and has wide application in solar panels, optical devices, transparent adhesives and packaging materials due to the advantages of excellent optical transparency, adhesion performance, chemical corrosion resistance and the like. However, the pure epoxy resin has poor mechanical properties and flame retardance, and the existing phosphorus flame retardant has high-efficiency flame retardance, but is expensive, generally affects the transparency of the epoxy resin material, and has limited improvement on mechanical properties. The hyperbranched polymer is used as a macromolecule with a topological structure, a large number of nanoscale cavities are contained in the molecule, and the tail end of a molecular chain contains rich active functional groups, so that the hyperbranched polymer has the characteristics of low viscosity, diversified molecular structures and the like, and can improve the strength and toughness of thermosetting resin. Patent cn201711045174.X uses an amphiphilic hyperbranched polyester ether toughened modified epoxy resin. Although the amphiphilic hyperbranched polyester ether has good compatibility with the epoxy resin, the strength and toughness of the epoxy resin are obviously improved, and satisfactory flame retardant performance still cannot be achieved.
In earlier studies, patent 201910856013.1 filed by the inventor group gave a high toughness flame retardant epoxy resin system which can enhance the flame retardance of the epoxy resin system while enhancing the toughness, but the introduction of the flame retardant would destroy the transparency of the epoxy resin itself. Patent 202110716028.5 utilizes a micromolecular phosphorus-containing flame retardant to prepare transparent halogen-free flame-retardant epoxy resin, and the components of the transparent halogen-free flame-retardant epoxy resin comprise 100-250 parts of phosphorus-containing flame retardant, 1000 parts of epoxy resin and 100-150 parts of diamine curing agent. Therefore, how to improve the strength, toughness and flame retardance of epoxy resins while maintaining their excellent transparency is a difficulty in developing high-performance epoxy resin substrates at present.
Based on the above research, tributyl borate and 1, 3-propylene glycol are used as reaction monomers, and the polyboronic acid ester with hyperbranched structure is synthesized by an A2+B3 one-pot method without solvent or catalyst, and the polyboronic acid ester is used for modifying epoxy resin. The hyperbranched polyboronate (HBPB) contains a large number of active hydroxyl groups at the end position, gathers in a resin matrix and participates in curing and crosslinking to form a dynamic supermolecular polymer network which is easy to dissipate impact energy. In addition, hyperbranched cavity units, flexible aliphatic chain segments and organic/inorganic hybridized B-O-C framework structures are introduced into the cross-linked network of the epoxy resin, so that the strength and toughness of the epoxy resin are improved cooperatively, the limiting oxygen index of resin combustion can be improved, and the heat release and smoke release of combustion can be reduced. In particular, the introduction of the hyperbranched polyboronic acid ester does not affect the excellent transparency and color of the epoxy resin, and the preparation is simple and convenient and the cost is low. Therefore, the high-strength high-toughness transparent flame-retardant epoxy resin based on hyperbranched polyborate modification has wide application prospect.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides the high-strength high-toughness transparent flame-retardant epoxy resin and the preparation method thereof, which solve the problems that the prior phosphorus flame retardant is high in price, the transparency of an epoxy resin material is generally affected, and the improvement on mechanical properties is limited. Provides a transparent flame-retardant epoxy resin system with high strength and high toughness by a simple and low-cost process.
Technical proposal
The high-strength high-toughness transparent flame-retardant epoxy resin is characterized by comprising 1-20 parts by mass of hyperbranched polyboronic acid ester HBPB, 80-100 parts by mass of bisphenol A epoxy resin and 20-30 parts by mass of diamine curing agent.
The trifunctional borates include, but are not limited to: tributyl borate, triethyl borate, or other types of trifunctional borates.
The difunctional diols include, but are not limited to: ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, or other types of diols.
The bisphenol A type epoxy resin comprises but is not limited to bisphenol A type epoxy resins with the national trade names of E51 and E44.
The curing agent includes, but is not limited to, 4-diaminodiphenyl sulfone, 4-diaminodiphenyl ether, 4-diaminodiphenyl methane or diamine based curing agents.
The method for preparing the high-strength high-toughness transparent flame-retardant epoxy resin is characterized by comprising the following steps:
step 1: preheating 80-100 parts by mass of bisphenol A epoxy resin at 100-130 ℃, adding 20-30 parts by mass of diamine curing agent, stirring, adding 1-20 parts by mass of hyperbranched polyboronic acid ester after the curing agent is completely dissolved, and stirring uniformly to obtain a resin prepolymer;
Step 2: pouring the prepolymer into a mould, vacuum defoaming for 1-2 h in a vacuum oven at 120-140 ℃, and placing the prepolymer into a blast drying oven for heating and curing at the stage of 150 ℃/2h+180/4h; and (3) after cooling and demoulding, carrying out post-treatment for 1-2 h at 200 ℃ to obtain the hyperbranched polyboronic acid ester/epoxy resin system with high transparency, strong flame retardance, high strength and high toughness.
The hyperbranched polyboronate is obtained by reacting trifunctional borate monomer and difunctional glycol monomer for 2-12 hours under the protection of nitrogen at 120-190 ℃ according to the molar ratio of 1:1.5-3.
The stirring time in the step 1 is 30-60 min.
Advantageous effects
According to the high-strength high-toughness transparent flame-retardant epoxy resin and the preparation method thereof, the epoxy resin has good transparency, but has poor toughness and flame retardance, the original transparency of the epoxy resin is generally damaged by the existing phosphorus-containing flame retardant, and the improvement on mechanical properties is limited. The invention utilizes tributyl borate and 1, 3-propylene glycol to carry out ester exchange polycondensation reaction, and synthesizes hyperbranched polyboronate which is used as a phosphorus-free flame retardant modifier and is used for modifying bisphenol A epoxy resin. The hyperbranched polyborate terminal contains a large number of active hydroxyl groups, has good compatibility with epoxy resin, can participate in the curing reaction of the epoxy resin, introduces hyperbranched cavity units, flexible aliphatic chain segments and organic/inorganic hybridized B-O-C framework structures into the crosslinking network of the epoxy resin, and can improve the limiting oxygen index of resin combustion and reduce the heat release and smoke release of combustion while synergistically improving the strength and toughness of the epoxy resin. In particular, the introduction of the hyperbranched polyboronic acid ester does not affect the excellent transparency and color of the epoxy resin, and meanwhile, the preparation is simple and the cost is low. Therefore, the epoxy resin containing hyperbranched polyboronic acid ester has wide application prospect.
The resin system consists of 1-20 parts by mass of hyperbranched polyboronic acid ester (HBPB), 80-100 parts by mass of bisphenol A epoxy resin and 20-30 parts by mass of diamine curing agent. Wherein, hyperbranched polyboronic acid ester is synthesized by A2+B3 ester exchange polycondensation, tributyl borate and 1,3 propylene glycol are taken as examples, and the synthesis and structural formula of the hyperbranched polyboronic acid ester are shown in figure 6; the composite epoxy resin system is prepared by adding the synthesized hyperbranched polyboronic acid ester into the pre-polymerized epoxy resin according to a certain proportion, and heating, curing and demoulding.
The invention provides a high-strength high-toughness transparent flame-retardant epoxy resin system and a preparation method thereof. Firstly, preparing the hyperbranched polymer through A2+B3 reaction, synthesizing hyperbranched polyboronate with hydroxyl end groups by utilizing transesterification reaction between alkoxy in the borate and active hydrogen in dihydric alcohol, and modifying epoxy resin by using the hyperbranched polyboronate. As the multi-functional hyperbranched polyboronate component is added into the epoxy resin component, a large number of active hydroxyl groups exist at the end position of the hyperbranched polyboronate, the hydroxyl groups can participate in the ring-opening reaction of epoxy groups and the curing reaction of resin, and hyperbranched cavity units, flexible aliphatic chain segments and organic/inorganic hybridized B-O-C framework structures are simultaneously introduced into the epoxy resin cross-linked network, the toughness, the strength and the flame retardance of a resin system can be effectively improved, and the good transparency of the epoxy resin is maintained, and relevant experimental data are shown in figures 3, 4,5 and 6. Wherein the modified process of the present invention is not simply determinable. The high-strength high-toughness transparent flame-retardant epoxy resin system is expected to be applied to the fields of solar panels, optical devices, transparent adhesives, packaging materials and the like.
Drawings
Fig. 1: an infrared spectrum (a) of the hyperbranched polyboronate in example 1; infrared spectrum of the distillate (b).
Fig. 2: nuclear magnetic spectrum of hyperbranched polyboronates in example 1: (a) nuclear magnetic hydrogen spectroscopy; (b) Nuclear magnetic carbon spectrum
Fig. 3: impact strength (a) and bending strength (b) of hyperbranched polyborate modified epoxy resin system with different addition amounts
Fig. 4: conical calorimetric test of hyperbranched polyborate modified epoxy resin system with different addition amounts
Fig. 5: ultraviolet absorption of hyperbranched polyborate modified epoxy resin (a); transparent digital photograph of hyperbranched polyborate modified epoxy resin (b)
Fig. 6: synthesis and structural schematic diagram of hyperbranched polyboronate HBPB
Detailed Description
The invention will now be further described with reference to examples, figures:
The first step: preheating 80-100 parts of bisphenol A epoxy resin (E51) at 100-130 ℃, taking 20-30 parts of 4, 4-diaminodiphenyl sulfone (DDS) as a curing agent, adding the curing agent into the epoxy resin, stirring the mixture for 30-60 min until the DDS is completely dissolved, adding 1-20 parts of hyperbranched polyboronic acid ester, and uniformly stirring the mixture to obtain the resin prepolymer. Wherein the hyperbranched polyboronate is obtained by reacting trifunctional borate monomer and difunctional glycol monomer according to the molar ratio of 1:1.5-3 under the protection of nitrogen for 2-12 hours at 120-190 ℃.
And a second step of: pouring the prepolymer into a mould, vacuum defoaming for 1-2 h in a vacuum oven at 120-140 ℃, placing the mould into a blast drying oven for stage heating and solidification, wherein the solidification process is 150 ℃/2h+180/4h, cooling and demoulding, and then post-treating for 1-2 h at 200 ℃ to obtain the high-strength high-toughness transparent flame-retardant hyperbranched polyborate/epoxy resin system.
Implementation example 1:
The first step: preheating 100 parts of bisphenol A epoxy resin (E51) at 130 ℃, taking 30 parts of 4, 4-Diamino Diphenyl Sulfone (DDS) as a curing agent, adding the curing agent, stirring for 30-60 min until the DDS is completely dissolved, adding 5 parts of hyperbranched polyboronic acid ester, and stirring uniformly to obtain a resin prepolymer. Wherein the hyperbranched polyboronate is obtained by feeding trifunctional borate monomer and difunctional glycol monomer according to the molar ratio of 1:1.94, and reacting for 2-12 hours at 120-190 ℃ under nitrogen protection.
And a second step of: pouring the prepolymer into a mould, vacuum defoaming for 1h in a vacuum oven at 130 ℃, placing the mould into a blast drying box for stage heating and solidification, wherein the solidification process is 150 ℃/2h+180/4h, cooling and demoulding, and then post-treating for 1h at 200 ℃ to obtain the high-strength high-toughness transparent flame-retardant hyperbranched polyborate/epoxy resin system.
The infrared spectrum is shown in figure 1, hyperbranched polyborate is synthesized by using tributyl borate (TBB) and 1, 3-Propanediol (PDO) as raw materials, and telescopic vibration absorption of-OH and-CH 2 -of PDO and HBPB spectra appears at 3360cm -1 and 2920cm -1, and the hydroxyl peak of HBPB is wider than PDO, thus proving that the product HBPB contains abundant hydroxyl groups. Meanwhile, the product HBPB is obviously different from the spectrogram of the raw material in a fingerprint area, characteristic peaks at 1050cm -1 in TBB and HBPB spectra are B-O telescopic vibration, and an absorption peak of B-O in HBPB moves to a higher area relative to TBB due to the electron conjugate average effect of hyperbranched structure macromolecules, so that the absorption peak is promoted to move to a high wave number direction. The absorption peak of the C-O/C-O-B bond in the main chain structure of the hyperbranched molecule is located from 1280cm -1 to 1500cm -1. Furthermore, as can be seen from FIG. 1b, the distillate of the reaction remained substantially identical to the standard butanol, demonstrating that the transesterification polycondensation reaction in the present reaction proceeds as expected, whereby it can be preliminarily judged HBPB that the synthesis was successful.
Implementation example 2:
The first step: preheating 100 parts of bisphenol A epoxy resin (E51) at 130 ℃, taking 30 parts of 4, 4-Diamino Diphenyl Sulfone (DDS) as a curing agent, adding the curing agent, stirring for 30-60 min until the DDS is completely dissolved, adding 10 parts of hyperbranched polyboronic acid ester, and stirring uniformly to obtain the resin prepolymer. Wherein the hyperbranched polyboronate is obtained by feeding trifunctional borate monomer and difunctional glycol monomer according to the molar ratio of 1:1.94, and reacting for 2-12 hours at 120-190 ℃ under nitrogen protection.
And a second step of: pouring the prepolymer into a mould, vacuum defoaming for 1h in a vacuum oven at 130 ℃, placing the mould into a blast drying box for stage heating and solidification, wherein the solidification process is 150 ℃/2h+180/4h, cooling and demoulding, and then post-treating for 1h at 200 ℃ to obtain the high-strength high-toughness transparent flame-retardant hyperbranched polyborate/epoxy resin system.
As shown in FIG. 2, 1H-NMR and 13C-NMR characterization was performed on both the monomers and the synthesized HBPB, further determining the chemical structure and hyperbranched structure of HBPB. In the nuclear magnetic hydrogen spectrum of HBPB (fig. 2 a), small shifts and new peaks can be identified compared to TBB and PDO, and these changes can be indicative of the occurrence of polymerization. Since A2+B3 transesterification tends to generate hyperbranched structures, the methylene protons from TBB (H1) and PDO (H2) split into H2, H3 and H4 on the HBPB spectra corresponding to the branching units, the linear units and the terminal units (D, L and T units), respectively, where we note three different but similar chemical shifts of 3.82ppm (H2), 4.02ppm (H3) and 3.66 ppm (H4), corresponding to the D, L, T units, respectively, confirming the unique hyperbranched structure in the synthesis HBPB. FIG. 3b is a nuclear magnetic carbon spectrum, HBPB in which 34.09ppm, 61.51ppm, 59.10 ppm, 62.71ppm, 34.83ppm and 27.26ppm signals (labeled 1&2&3&4&5& 6) correspond to methylene carbons, while 18.30ppm (C7) is methyl carbons belonging to the terminal unit (-CH 2-CH2-CH 3). After the polycondensation reaction is completed, the resulting hyperbranched structure separates 3.82ppm of the C1 (TBB) and C2 (PDO) signals into C2, C3 and C4 in HBPB, associated with dendritic, linear and terminal carbons in B-O-CH 2. The offset of HBPB (C2) is small compared to TBB, due to conjugation effects in large hyperbranched molecules. The nuclear magnetic hydrogen and nuclear magnetic carbon spectra in fig. 2 further demonstrate the successful synthesis of HBPB and its unique hyperbranched structure.
Implementation example 3:
The first step: preheating 100 parts of bisphenol A epoxy resin (E51) at 130 ℃, taking 30 parts of 4, 4-Diamino Diphenyl Sulfone (DDS) as a curing agent, adding the curing agent, stirring for 30-60 min until the DDS is completely dissolved, adding 15 parts of hyperbranched polyboronic acid ester, and stirring uniformly to obtain a resin prepolymer. Wherein the hyperbranched polyboronate is obtained by feeding trifunctional borate monomer and difunctional glycol monomer according to the molar ratio of 1:1.94, and reacting for 2-12 hours at 120-190 ℃ under nitrogen protection.
And a second step of: pouring the prepolymer into a mould, vacuum defoaming for 1h in a vacuum oven at 130 ℃, placing the mould into a blast drying box for stage heating and solidification, wherein the solidification process is 150 ℃/2h+180/4h, cooling and demoulding, and then post-treating for 1h at 200 ℃ to obtain the high-strength high-toughness transparent flame-retardant hyperbranched polyborate/epoxy resin system.
As shown in fig. 3, the impact strength of the modified epoxy resin increases and then decreases with increasing HBPB content. Of these, the addition of 1% HBPB greatly improved the impact strength from 21.38 kJ.m -2 to 31.56 kJ.m -2, while the addition of 3% HBPB almost doubled the impact strength to a maximum value (40.50 kJ.m -2). In addition, the bending strength of the modified epoxy resin is increased and gradually leveled with the increase of HBPB content, and the bending strength of the modified epoxy resin is increased from 137.03 kJ.m -2 to 197.08 kJ.m -2 compared with the pure epoxy resin at the content of 12% HBPB. The remarkable reinforcing and toughening effects are mainly due to the fact that hyperbranched polyboronic acid ester can participate in the curing reaction of resin, the supermolecular polymer interpenetrating network of epoxy resin/hyperbranched polyboronic acid ester is aggregated and formed in the resin, free volume is improved through the introduction of nanoscale holes in the hyperbranched structure in the epoxy resin crosslinking network, meanwhile, the mobility of an epoxy resin chain segment is enhanced through the introduction of aliphatic carbon chains and dynamic boric acid ester bonds, impact energy is absorbed favorably, and excellent toughening effects are achieved.
Implementation example 4:
The first step: preheating 100 parts of bisphenol A epoxy resin (E51) at 130 ℃, taking 30 parts of 4, 4-Diamino Diphenyl Sulfone (DDS) as a curing agent, adding the curing agent, stirring for 30-60 min until the DDS is completely dissolved, adding 15 parts of hyperbranched polyboronic acid ester, and stirring uniformly to obtain a resin prepolymer. Wherein the hyperbranched polyboronate is obtained by feeding trifunctional borate monomer and difunctional glycol monomer according to the molar ratio of 1:2.5, and reacting for 2-12 hours at 120-190 ℃ under nitrogen protection.
And a second step of: pouring the prepolymer into a mould, vacuum defoaming for 1h in a vacuum oven at 130 ℃, placing the mould into a blast drying box for stage heating and solidification, wherein the solidification process is 150 ℃/2h+180/4h, cooling and demoulding, and then post-treating for 1h at 200 ℃ to obtain the high-strength high-toughness transparent flame-retardant hyperbranched polyborate/epoxy resin system.
FIG. 4 is a cone calorimetric test for evaluating the flame retardant and smoke suppression properties of hyperbranched polyborate modified epoxy resin systems. First, the amount of heat released is used to evaluate the thermal hazard of the material. As shown, with the addition of HBPB, the Heat Release Rate (HRR) of the epoxy combustion was reduced from 733.6kw.m -2 to 422.7 kw.m 2, and the secondary heat release was almost lost in the secondary combustion zone (at 400 s). The Total Heat Release (THR) of epoxy resin burning is reduced from 116.5 kJ.m 2 to 106.7 kJ.m 2, which shows that HBPB prepared by the method can effectively play roles in inhibiting burning and inhibiting material burning heat release. In addition, by adding HBPB, the smoke release of epoxy resin combustion, carbon monoxide, carbon dioxide and other non-thermal hazards are effectively reduced, the maximum smoke generation rate (SPR) is reduced from 0.26m 2·s-1 to 0.17m 2·s-1, the secondary smoke release area disappears, the generation of carbon monoxide and carbon dioxide is obviously reduced, and HBPB has good smoke suppression and toxic gas release inhibition effects.
FIG. 5 is a digital photograph of UV absorption and transparency of different hyperbranched polyborate addition modified epoxy resin systems. As shown in fig. 5b, the addition of the hyperbranched polyborate has little effect on the transparency and color of the epoxy resin itself. FIG. 5a illustrates that in the wavelength band above 500nm, the transmittance of the resin material to light is almost maintained at a higher level with the addition of HBPB, and the hyperbranched polyborate modified epoxy resin has a stronger transmittance than the pure epoxy resin in the ultraviolet region around 400 nm.
The hyperbranched polyboronate designed by the invention has reasonable raw material components and technological parameter chains participating in the reaction, and can complete the reaction. On the contrary, the aim and the effect of the invention can not be achieved due to unreasonable selection of component parameters or the chain of process parameters participating in the reaction. The following examples are reversed:
Example 1:
tributyl borate and 1, 3-propylene glycol are added into a three-neck flask according to the mol ratio of 1:1.94, stirring is carried out under the protection of nitrogen, the reaction temperature is controlled between 60 ℃ and 120 ℃, no distillate is seen after the reaction is carried out for 8 to 12 hours, two-phase substances are still separated in the flask, and the reaction does not occur. This is mainly due to the fact that the reaction temperature is low and the conditions for transesterification are not satisfied.
Example 2:
The preparation method comprises the steps of preheating 100 parts by mass of bisphenol A epoxy resin (E51) at 80 ℃, taking 30 parts by mass of 4, 4-Diamino Diphenyl Sulfone (DDS) as a curing agent, adding the curing agent, stirring for more than 60 minutes without dissolving the DDS, and adding hyperbranched polyboronic acid ester without dissolving the DDS. The resin is low in temperature during the prepolymerization, the viscosity of the resin is high at the temperature, the curing agent cannot be dissolved and uniformly dispersed, and the hyperbranched polyboronic acid ester cannot be uniformly dispersed in the resin system.
Comparative example 1:
The first step: preheating bisphenol A epoxy resin (E51) with the mass fraction of 100 parts at 130 ℃, taking 30 parts of 4, 4-Diamino Diphenyl Sulfone (DDS) as a curing agent, adding the curing agent into the bisphenol A epoxy resin, and stirring the mixture for 30 to 60 minutes until the DDS is completely dissolved to obtain a resin prepolymer;
And a second step of: pouring the prepolymer into a mould, vacuum defoaming for 1h in a vacuum oven at 130 ℃, placing the mould into a blast drying box for stage heating and solidification, wherein the solidification process is 150 ℃/2h+180/4h, cooling and demoulding, and post-treating for 1h at 200 ℃, thus obtaining the pure epoxy resin comparative example without hyperbranched polyboronic acid ester.
TABLE 1 limiting oxygen resin and vertical Combustion results for hyperbranched polyborate modified epoxy resin System
The performance test is carried out on the hyperbranched polyborate/epoxy resin system with high transparency, high flame retardance and high strength and high toughness, which is prepared by the method, and the performance test is shown in the attached drawing of the specification.
The foregoing is a further detailed description of the present invention in connection with specific embodiments thereof, and is not intended to limit the invention to the specific embodiments thereof, but rather to be construed according to the teachings of the present invention.

Claims (5)

1. The high-strength high-toughness transparent flame-retardant epoxy resin is characterized by comprising 1-20 parts by mass of hyperbranched polyboronic acid ester HBPB, 80-100 parts by mass of bisphenol A epoxy resin and 20-30 parts by mass of diamine curing agent;
the hyperbranched polyboronic acid ester is synthesized by taking trifunctional boric acid ester and difunctional diol as raw materials through transesterification polycondensation reaction;
The trifunctional borate esters include: tributyl borate or triethyl borate;
the difunctional diols include: ethylene glycol, 1, 3-propanediol or1, 4-butanediol;
the diamine curing agent comprises 4, 4-diaminodiphenyl sulfone, 4-diaminodiphenyl ether or 4, 4-diaminodiphenyl methane;
the high-strength high-toughness transparent flame-retardant epoxy resin is prepared according to the following steps:
Step 1: preheating 80-100 parts by mass of bisphenol A epoxy resin at 100-130 ℃, adding 20-30 parts by mass of diamine curing agent, stirring, adding 1-20 parts by mass of hyperbranched polyboronic acid ester after the curing agent is completely dissolved, and stirring uniformly to obtain a resin prepolymer;
Step 2: pouring the prepolymer into a mould, vacuum defoaming for 1-2 h in a vacuum oven at 120-140 ℃, and placing the prepolymer into a blast drying oven for heating and curing at the stage of 150 ℃/2h+180/4h; and (3) after cooling and demoulding, carrying out post-treatment for 1-2 h at 200 ℃ to obtain the hyperbranched polyboronic acid ester/epoxy resin system with high transparency, strong flame retardance, high strength and high toughness.
2. The high-strength high-toughness transparent flame-retardant epoxy resin according to claim 1, wherein: the bisphenol A type epoxy resin comprises bisphenol A type epoxy resins with the national brands of E51 and E44.
3. A method for preparing the high-strength high-toughness transparent flame-retardant epoxy resin as claimed in claim 1 or 2, which is characterized by comprising the following steps: step 1: preheating 80-100 parts by mass of bisphenol A epoxy resin at 100-130 ℃, adding 20-30 parts by mass of diamine curing agent, stirring, adding 1-20 parts by mass of hyperbranched polyboronic acid ester after the curing agent is completely dissolved, and stirring uniformly to obtain a resin prepolymer; step 2: pouring the prepolymer into a mould, vacuum defoaming for 1-2 h in a vacuum oven at 120-140 ℃, and placing the prepolymer into a blast drying oven for heating and curing at the stage of 150 ℃/2h+180/4h; and (3) after cooling and demoulding, carrying out post-treatment for 1-2 h at 200 ℃ to obtain the hyperbranched polyboronic acid ester/epoxy resin system with high transparency, strong flame retardance, high strength and high toughness.
4. A method according to claim 3, characterized in that: the hyperbranched polyboronate is obtained by reacting trifunctional borate monomer and difunctional glycol monomer for 2-12 hours under the protection of nitrogen at 120-190 ℃ according to the molar ratio of 1:1.5-3.
5. A method according to claim 3, characterized in that: the stirring time in the step 1 is 30-60 min.
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