CN119875137A - Ablation-resistant hybrid resin containing covalent-ion bicontinuous network and preparation method and application thereof - Google Patents
Ablation-resistant hybrid resin containing covalent-ion bicontinuous network and preparation method and application thereof Download PDFInfo
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Abstract
本发明属于热防护材料领域，具体涉及一种含共价‑离子双连续网络的耐烧蚀杂化树脂及其制备方法和用途。本发明通过在硼酚醛树脂中引入有机分子官能化的无机离子寡聚体，得到有机无机‑杂化树脂；首次在杂化树脂中实现热固性网络与无机离子网络同步交联和聚合，得到共价‑离子双连续网络。本发明制备的杂化树脂具有优异的机械性能和耐烧蚀性能，在结构材料、复合材料、热防护材料等领域具有广阔的应用前景。
The present invention belongs to the field of thermal protection materials, and specifically relates to an ablation-resistant hybrid resin containing a covalent-ion dual continuous network, and a preparation method and use thereof. The present invention obtains an organic-inorganic hybrid resin by introducing inorganic ion oligomers functionalized with organic molecules into a boron phenolic resin; for the first time, the thermosetting network and the inorganic ion network are simultaneously crosslinked and polymerized in the hybrid resin to obtain a covalent-ion dual continuous network. The hybrid resin prepared by the present invention has excellent mechanical properties and ablation resistance, and has broad application prospects in the fields of structural materials, composite materials, thermal protection materials, etc.
Description
Technical Field
The invention belongs to the field of thermal protection materials, and particularly relates to ablation-resistant hybrid resin containing a covalent-ion bicontinuous network, and a preparation method and application thereof.
Background
The resin-based ablative thermal protection material has high thermal protection efficiency and reliable operation, is the most widely used thermal protection material and structure at present, and the phenolic resin-based composite material plays a very important role in the thermal protection composite material of the aircraft. Phenolic resin has the advantages of simple molding process, good heat resistance, high mechanical strength and outstanding instantaneous high-temperature ablation resistance, and is often used as a matrix of the ablation-resistant composite coating. PhenCarb series of light charring type ablation materials are prepared by taking phenolic resin as a matrix in NASA in the United states, the surface ablation rate is low, and the thickness of the ablated carbon layer is low. Phenolic impregnated carbon ablative materials (PICA) prepared by using phenolic resin as a matrix in the American AMES center have been successfully applied to "Star dust" number return cabin thermal protection systems.
However, the new generation of high-speed aircrafts need to fly for a long time in an aerobic environment, the traditional phenolic resin has difficulty in meeting the requirements of heat protection due to the problems of low carbon residue rate, no antioxidation and the like, and development of novel high-performance high-temperature antioxidation phenolic resin is urgently needed. The long-term oxidation resistance of the resin can be effectively improved by introducing an inorganic component into the resin structure to form an organic-inorganic hybrid structure, and the traditional organic-inorganic hybrid resin is generally prepared by three methods of (1) adding an inorganic filler, (2) bonding with inorganic ions through ionic bonds or coordination bonds, and (3) copolymerizing and grafting modification with inorganic element-containing monomers typified by silane through covalent bonds. For the organic-inorganic hybrid resin, the size of an inorganic unit is reduced, so that the interaction between two phases can be effectively improved, the boundary between an organic phase and an inorganic phase in the hybrid material is reduced or eliminated, and the comprehensive performance of the hybrid resin is effectively improved, but the molecular structure design of the existing organic-inorganic hybrid resin has the problems that the introduced inorganic element is limited in variety, the material is difficult to have high heterogeneous element content and excellent two-phase interface, the synergistic enhancement mechanism of the inorganic antioxidant ceramic and a high-strength graphitized carbon layer is difficult to develop in the high-temperature antioxidant process, and the like.
Based on the problems of the existing organic-inorganic hybrid resins, there is a need to design an organic-inorganic hybrid resin that can eliminate interface defects and also exhibits excellent heat and ablation resistance during high temperature oxidation resistance.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an ablation-resistant hybrid resin containing a covalent-ion bicontinuous network, and a preparation method and application thereof.
The hybrid resin with ablation resistance is prepared by curing the following raw materials in parts by weight:
10-30 parts of salt containing metal cation,
4-10 Parts of acid radical ion donor,
150-900 Parts of end capping agent,
5-30 Parts of monomer compound,
2-120 Parts of modified phenolic resin;
The monomer compound is a compound having a carboxyl group at one end and a group capable of reacting with a phenolic resin at the other end.
Preferably, the group capable of reacting with the phenolic resin is selected from at least one of epoxy group, maleimide group, cyanate group, isocyanate group, amino group, carboxyl group, hydroxyl group, aldehyde group, thiol group, and boric acid group.
Preferably, the adhesive is prepared from the following raw materials in parts by weight through curing:
12 parts of a salt containing metal cations,
8 Parts of acid radical ion donor,
166 Parts of end capping agent,
7 Parts of monomer compound,
30 Parts of modified phenolic resin.
Preferably, the metal cation is at least one of calcium ion, copper ion, manganese ion, zirconium ion, hafnium ion, magnesium ion and iron ion, and the anion of the salt containing metal cation is at least one of chloride ion, carbonate ion, sulfate ion, nitrate ion and phosphate ion;
Preferably, the monomer compound is at least one selected from phenylboronic acid compounds, hydroxybenzoic acid compounds, hydroxyphenylacetic acid compounds, hydroxyphenylpropionic acid compounds, mercaptoacetic acid compounds and mercaptobenzoic acid compounds.
Preferably, the modified phenolic resin is selected from any one of boron phenolic resin, epoxy modified phenolic resin, polyamide modified phenolic resin, organosilicon modified phenolic resin, dicyandiamide modified phenolic resin, polyvinyl acetal modified phenolic resin and diphenyl ether formaldehyde resin.
Preferably, the acid radical ion donor is selected from at least one of phosphoric acid, CO 2, sulfuric acid and nitric acid, and/or the end capping agent is selected from triethylamine.
The invention also provides a preparation method of the hybrid resin with ablation resistance, comprising the following steps of step 1, preparing inorganic ion oligomer by adopting salt containing metal cations, a blocking agent and an acid radical ion donor;
Step 2, reacting a monomer compound with the inorganic ion oligomer obtained in the step 1 to obtain an organic functional inorganic ion oligomer;
And 3, reacting the modified phenolic resin with the organic functional inorganic ion oligomer obtained in the step 2 to obtain the hybrid resin with ablation resistance.
Preferably, in the step 1, the preparation method of the inorganic ion oligomer comprises the steps of 1.1, reacting a salt containing metal cations with a complexing agent to obtain a solution A;
step 1.2, reacting an acid radical ion donor with a complexing agent to obtain a solution B;
step 1.3, after the solution A reacts with the solution B, a dispersion liquid 1 of inorganic ion oligomer is obtained;
step 1.4, centrifuging the dispersion liquid 1 of the inorganic ion oligomer to obtain inorganic ion oligomer gel, and washing and dispersing to obtain the inorganic ion oligomer gel;
and/or, in the step 2, the preparation method of the organic functional inorganic ion oligomer comprises the following steps:
Step 2.1, reacting a monomer compound with the inorganic ion oligomer to obtain a dispersion liquid 1 of the organic functional inorganic ion oligomer;
Step 2.2, centrifuging the dispersion liquid 1 of the organic functional inorganic ion oligomer to obtain organic functional inorganic ion oligomer gel, and washing and dispersing to obtain the organic functional inorganic ion oligomer gel;
And/or in the step 3, the preparation method of the hybrid resin comprises the steps of reacting the organic functional inorganic ion oligomer with the modified phenolic resin, centrifuging to obtain hybrid resin gel, washing and drying to obtain hybrid resin powder, and solidifying to obtain the hybrid resin.
Preferably, in the steps 1.1 and 1.2, the solvent for the reaction is absolute ethyl alcohol, in the step 1.3, the reaction time is 6-24 hours, in the step 1.4, the centrifugation speed is 5000-12000rpm, the centrifugation time is 1-10 minutes, the reagent for flushing is ethanol, and the dispersing agent is absolute ethyl alcohol.
Preferably, in the step 2.1, the solvent of the monomer compound is anhydrous methanol, the reaction time is 6-24 hours, and in the step 2.2, the centrifugation speed is 5000-12000rpm, the centrifugation time is 1-10 minutes, the reagent used for flushing is ethanol, and the dispersing agent is anhydrous ethanol.
Preferably, in the step 3, the reaction temperature is 70-90 ℃, the reaction time is 4-8h under the inert atmosphere condition, the centrifugation speed is 5000-12000rpm, the centrifugation time is 1-10min, the reagent used for flushing is ethanol, the drying condition is 70-90 ℃, the drying condition is 0.08-0.1 MPa, the curing condition is 100-120 ℃ and keeps the temperature for 20-40min, the holding pressure is 25-35MPa, the temperature is raised from 100-120 ℃ to 130-150 ℃, the heating rate is 5-20 ℃ per min, the heating rate is 130-150 ℃ and keeps the temperature for 20-40min, the holding pressure is 25-35MPa, the heating rate is raised from 130-150 ℃ to 170-190 ℃, the holding pressure is 25-35MPa, the heating rate is 5-20 ℃ and keeps the pressure for 0.5-35 MPa, the holding pressure is 190-210 ℃ and finally the holding pressure is 25-35MPa, and the holding pressure is 25-35MPa.
The invention also provides application of the hybrid resin with the ablation resistance in preparation and/or as an ablation resistant material.
The molecular precision of the functionalized inorganic ion oligomer is defined.
According to the invention, the organic group functionalized inorganic ion oligomer with molecular precision is introduced into the boron phenolic resin, the thermosetting network and the inorganic ion network are simultaneously started to crosslink and polymerize in the hybrid resin for the first time, so that the covalent-ion bicontinuous network with a continuous structure from macroscopic scale to microscopic scale is obtained, and the construction method of the covalent-ion bicontinuous network between the functionalized inorganic ion oligomer and the phenolic resin enables the precise regulation and control of other organic-inorganic thermosetting hybrid resins to be possible. Meanwhile, the hybrid resin has excellent high-temperature oxidation resistance and ablation resistance, and has wide application prospect in the field of heat protection materials.
It should be apparent that, in light of the foregoing, various modifications, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
The above-described aspects of the present invention will be described in further detail below with reference to specific embodiments in the form of examples. It should not be understood that the scope of the above subject matter of the present invention is limited to the following examples only. All techniques implemented based on the above description of the invention are within the scope of the invention.
Drawings
FIG. 1 is a molecular structural characterization of functionalized inorganic ion oligomers. (a) is a 3-BAPO synthesis and structure schematic diagram, (b) is a 3-BAPO infrared spectrogram, (c) is an ICP-OES plasma spectrometer for carrying out element analysis on the 3-BAPO.
FIG. 2 is a representation of the supramolecular interactions between functionalized inorganic ion oligomers and boron phenolic resins in 3-BRPO. (a) An infrared spectrum test chart, (b) a Raman spectrum chart, and (c-e) an X-ray photoelectron spectroscopy (XPS).
FIG. 3 shows the relative amounts of inorganic elements in the 3-BRPO hybrid resin powder (before curing).
FIG. 4 is a representation of the cross-linked network structure of the hybrid resin before and after curing of the 3-BRPO.
FIG. 5 is an optical morphology of a 3-BRPO hybrid resin.
FIG. 6 is a bicontinuous phase structure of 3-BRPO hybrid resins.
FIG. 7 is a small angle X-ray scattering (SAXS) characterization of 3-BRPO hybrid resins.
FIG. 8 is a graph of thermal gravimetric analysis characterizing the heat resistance of hybrid resins.
FIG. 9 is a tube furnace characterization of the static ablative properties of hybrid resins. (a) photos before and after static ablation of a 3-BPROa tubular furnace, (b) photos before and after static ablation of a BPR tubular furnace, and (c) XRD of carbonized ceramic products after static ablation of 3-BRPOa.
FIG. 10 is a graph of the characterization of dynamic ablation performance of a plasma ablator in an oxygen-rich atmosphere of 3-BPRO hybrid resins.
FIG. 11 is a nanoindenter characterization of the mechanical properties of 3-BPRO hybrid resins.
Detailed Description
In the following examples and experimental examples, reagents and raw materials not specifically described are commercially available.
EXAMPLE 13 preparation of carboxyphenylboronic acid functionalized calcium phosphate inorganic ion oligomer boron phenolic resin (3-BRPO)
1. Preparation of calcium phosphate inorganic ion oligomer (CPO)
80Mmol of calcium chloride dihydrate is taken and dissolved in 1L of absolute ethyl alcohol, 800mmol of triethylamine is added and stirring is continued for 10min, so that a solution A is obtained. 80mmol of phosphoric acid and 800mmol of triethylamine were dispersed in 1L of absolute ethanol to obtain a solution B. Dropwise adding the solution B into the solution A, continuing to react for 24 hours after the dropwise adding is finished to obtain CPO ethanol dispersion liquid 1, obtaining CPO gel through high-speed centrifugation (10000 rpm,2 min), flushing the CPO gel with ethanol for a plurality of times to remove residual triethylamine, and re-dispersing the CPO gel in 1L absolute ethyl alcohol to obtain CPO ethanol dispersion liquid 2.
2. Preparation of 3-carboxyphenylboronic acid functionalized calcium phosphate inorganic ion oligomer (3-BAPO)
42Mmol of 3-carboxyphenylboronic acid (3-CPBA) is weighed and dissolved in 800mL of absolute methanol, the obtained CPO ethanol dispersion 2 is dropwise added into the methanol solution of the 3-CPBA, the reaction is continued for 24 hours after the dropwise addition is finished, 3-BAPO ethanol dispersion 1 is obtained, 3-BAPO gel is obtained through high-speed centrifugation (10000 rpm,2 min), residual 3-CPBA is removed from the 3-BAPO gel through multiple ethanol flushing, and the 3-BAPO gel is redispersed in 1L of absolute ethanol to obtain 3-BAPO ethanol dispersion 2.
3. Preparation of 3-BAPO/boron phenolic resin hybrid Material (3-BRPO)
Boron phenolic resin (THC-400 of Shaanxi TaiguangZhuo fire retardant company) and 200g of ethanol are taken and added into a flask together, the mixture is stirred at room temperature until the Boron Phenolic Resin (BPR) is completely dissolved, then the temperature is raised to 80 ℃, 3-BAPO ethanol dispersion liquid 2 is dropwise added through a constant pressure dropping funnel under the argon condition, and after the dropwise addition is finished, the reaction is continued for 6 hours at 80 ℃. After the reaction was completed, 3-BRPO gel was obtained by high-speed centrifugation (10000 rpm,2 min), and 3-BRPO gel was washed with ethanol several times to remove residual BPR, and then the solvent was removed in a vacuum oven (80 ℃ -0.1 MPa) to obtain 3-BRPO powder. The curing process comprises the steps of preserving heat for 30min at 110 ℃ and 30MPa at the temperature, raising the temperature from 110 ℃ to 140 ℃, preserving heat for 30min at the temperature of 140 ℃, preserving heat for 30MPa at the temperature of 140 ℃, raising the temperature from 140 ℃ to 180 ℃, preserving heat for 2h at the temperature of 180 ℃, preserving heat for 30MPa at the temperature of 180 ℃, raising the temperature from 180 ℃ to 200 ℃, preserving heat for 1h at the temperature of 200 ℃ at the temperature of 5 ℃ and preserving heat for 30MPa at the temperature of 180 ℃, and finally preserving heat for 30MPa at the pressure of 30MPa, and naturally cooling to room temperature to obtain the modified polyurethane foam. Wherein the amounts of the Boron Phenolic Resin (BPR) are shown in Table 1, and 3-BRPOa, 3-BRPOb and 3-BRPOc are respectively prepared.
TABLE 1
| Name of the name | BPR | Absolute ethyl alcohol |
| 3-BRPOa | 60g | 200g |
| 3-BRPOb | 30g | 200g |
| 3-BRPOc | 5g | 200g |
The following is a method for preparing a control sample.
Comparative example 1
1. Calcium phosphate (Ca 3(PO4)2)
The sample was calcium phosphate inorganic ion oligomer (CPO) and was prepared according to step 1 of example 1.
2、BPR
The sample was a boron phenolic resin.
3、3-BAPO
The sample was prepared according to step 2 of example 1.
4、3-CPBA
The sample was 3-carboxyphenylboronic acid.
The technical scheme of the invention is further described through experiments.
Experimental example 1 characterization of the molecular Structure of functionalized inorganic ion oligomer (3-BAPO)
The 3-BAPO, 3-CPBA and Ca 3(PO4)2 in this experimental example were prepared in the same manner as in comparative example 1.
1. Experimental method
The molecular structure of the 3-BAPO molecules was characterized by infrared spectroscopic testing and passing through an ICP-OES plasma spectrometer.
2. Experimental results
As shown in FIG. 1 (a), the 3-BAPO synthesis and structure diagram are that calcium phosphate inorganic ion oligomer (CPO) and 3-carboxyphenylboronic acid (3-CPBA) are reacted to obtain 3-carboxyphenylboronic acid functionalized calcium phosphate inorganic ion oligomer (3-BAPO). In the infrared spectrum of fig. 1 (b), a c=o peak can be observed at 1686cm -1 in the 3-CPBA spectrum, and as the neutralization reaction between 3-CPBA and CPO acid and base proceeds, this peak red shifts to 1545cm -1, and the change in FTIR spectrum verifies that an ionic bond is formed between the carboxyl group in 3-CPBA and the phosphoric acid of CPO, indicating a strong chemical interaction between the two. As shown in FIG. 1 (c), ICP-OES confirmed that 3-BAPO was supported by a molecular formula of 3-CPBA 3Ca3PO4(Ca3(PO4)2)4 when the average Ca/B and P/B molar ratios were about 5:1 and 3:1, respectively.
The supermolecular interactions between functionalized inorganic ion oligomers and boron phenolic resins are characterized in Experimental examples 2:3-BRPO
In this experimental example, 3-BRPO b, BPR, 3-BAPO, 3-CPBA and Ca 3(PO4)2 were prepared in the same manner as in example 1 and comparative example 1.
1. Experimental method
The supramolecular interactions between functionalized inorganic ion oligomers and the borophenol resins in 3-BRPO hybrid resin powders (before curing) were characterized by infrared spectroscopy testing, raman spectroscopy and X-ray photoelectron spectroscopy (XPS).
2. Experimental results
In the infrared spectrum of FIG. 2a, the B-O peak intensities at 1380cm -1 and 654cm -1 were significantly reduced, indicating that 3-BAPO coordinated with B and O in the BPR. In addition, it was also observed that the Ph-OH peak at 1200cm -1 shifted toward the high wavenumber direction, indicating that the hydroxyl groups in the BPR formed hydrogen bonds with the phosphate groups in the calcium phosphate oligomer.
FIG. 2b shows a shift in peak broadening of P-O in the Raman spectrum, indicating that hydroxyl groups in the BPR form hydrogen bonds with calcium phosphate.
In the fine spectrum of FIG. 2cXPSCa p, the Ca2p peak shifted toward high binding energy after 3-carboxyphenylboronic acid functionalization due to higher binding energy between Ca 2+ and carboxylate, demonstrating the success of the organic functionalization of calcium phosphate oligomers by acid-base neutralization reactions. In addition, the Ca2p peak of the hybrid resin powder moves further toward the high binding energy direction, and the orbital electron density of the calcium changes, which indicates that the supermolecular interaction is generated between the functionalized inorganic ion oligomer and the boron phenolic resin, and the binding energy of Ca 2+ and the surrounding chemical environment is increased.
In the fine spectrum of FIG. 2dXPS O1s, the phosphate peak position and the boron phenolic resin peak position in the hybrid resin powder are obviously shifted compared with the 3-BAPO and the BPR, and respectively move towards the directions of high binding energy and low binding energy, which indicates that the oxygen-containing structures in the two structures mutually generate supermolecular interaction.
In the fine spectrum of FIG. 2eXPS B1s, the characteristic peak of boron-oxygen coordination can be observed in the hybrid resin powder, and the 3-BAPO and the BPR simultaneously contain B element and O element, so that the peak shows that the B element and the O element of the inorganic structure and the organic structure in the hybrid resin coordinate with each other.
Experimental example 3:3-BRPO characterization of elemental content of hybrid resin
In this experimental example 3-BRPO a, 3-BRPO b and 3-BRPO c were prepared according to the procedure of example 1.
1. Experimental method
The relative content of inorganic elements in the hybrid resin powder (before curing) was characterized by ICP-OES plasma spectroscopy.
2. Experimental results
As shown in fig. 3, the results show that the hybrid resin with the total inorganic element content of 13.5-25.9wt.% is successfully prepared by regulating the concentration of the ethanol solution of the boron phenolic resin.
Experimental example 4:3-BRPO characterization of crosslinked network Structure before and after curing hybrid resin
In this experimental example, 3-BRPO b (Cured) was 3-BRPO hybrid resin after curing, 3-BRPO b was 3-BRPO hybrid resin before curing, BPR (Cured) was boron phenolic resin after curing, and BPR was boron phenolic resin before curing, which were prepared in the same manner as in example 1 and comparative example 1.
1. Experimental method
The boron phenolic resin curing and amorphous calcium phosphate network inorganic ion polymerization in the hybrid resin can be simultaneously excited by an X-ray diffractometer (XRD) characterization through a strong pressure gradient heating process.
2. Experimental results
As shown in fig. 4, the boron phenolic resin has a passivated amorphous diffraction peak at about 20 degrees, which corresponds to an amorphous resin network, and the peak moves towards a low angle direction along with the curing, which indicates that the crosslinked network formed after the resin is cured is more disordered. Amorphous diffraction peaks corresponding to an amorphous resin network (20 DEG) and an amorphous calcium phosphate network (30 DEG) can be simultaneously observed in XRD spectrum lines of the hybrid resins 3-BRPOb. Consistent with the results observed for the boron phenolic resin described above, the amorphous diffraction peaks of the resin network in the hybrid resin shifted in the low angle direction after curing, indicating that crosslinking of the organic moiety in the hybrid resin was successfully activated. The amorphous diffraction peak corresponding to the amorphous calcium phosphate network moves towards a high angle direction after solidification, which shows that Ca-O coordination number in the system is increased, and proves that the inorganic ion part in the hybrid resin can be polymerized into the amorphous calcium phosphate network through inorganic ions by a strong pressure gradient heating process.
In conclusion, XRD proves that the boron phenolic resin curing and amorphous calcium phosphate network inorganic ion polymerization in the hybrid resin can be simultaneously excited by a strong pressure gradient heating process.
Experimental example 5:3-BRPO characterization of organic-inorganic bicontinuous network after curing of hybrid resin
In this experimental example 3-BRPO a, 3-BRPO b and 3-BRPO c were prepared according to the procedure of example 1.
1. Experimental method
The bicontinuous network after curing of the hybrid resin was characterized by optical topography, high angle annular dark field scanning transmission electron microscopy (HAADF-STEM), and small angle X-ray scattering (SAXS).
2. Experimental results
As shown in FIG. 5, all the hybrid resins do not scatter visible light, show a uniform and transparent macroscopic morphology, indicating that the resulting resin castings are all nano-scale bicontinuous materials.
As shown in fig. 6, a continuous calcium-containing microphase-separated structure (light areas) is clearly observed, and interpenetrates with a BPR uniform osmotic phase (dark areas) to form a bicontinuous phase structure.
As shown in fig. 7, it can be observed that the single scattering peak centered on the vector of q=0.038a-1 shows a typical scattering pattern of a bicontinuous structure, and further the curve is fitted by the Teubner-Strey model to obtain dTS of 16.3nm, and the amphiphilic factor fa= -0.42, which proves that a molecular scale bicontinuous network exists in 3-BRPO.
The Teubner-Strey model is from literature ：Bobrin,V.A.,Yao,Y.,Shi,X.et al.Na no-to macro-scale control of 3D printed materials via polymerization induc ed microphase separation.Nat Commun 13,3577(2022).
Experimental example 6 characterization of Heat resistance of 3-BRPO hybrid resin
In this experimental example, 3-BRPO a, 3-BRPO b, 3-BRPO c and BPR were prepared in the same manner as in example 1 and comparative example 1.
1. Experimental method
The heat resistance of the hybrid resin was characterized by a thermal weight loss (TG).
2. Experimental results
As shown in fig. 8, the constructed organic-inorganic bicontinuous network can significantly improve the residual weight of the material at 1200 ℃ in the air atmosphere, and slow down or inhibit the degradation of the resin at 800-1200 ℃ to a certain extent, and the constructed organic-inorganic bicontinuous network can significantly improve the residual weight of the material at 1200 ℃ in the air atmosphere, and slow down or inhibit the degradation of the resin at 800-1200 ℃ to a certain extent, so that the hybrid resin shows good heat resistance.
Experimental example 7 static ablative Properties of 3-BRPO hybrid resins
In this experimental example 3-BRPO a, BPR was prepared according to the method in example 1 and comparative example 1.
1. Experimental method
The static ablation performance of the hybrid resin was characterized by a tube furnace (1200 ℃ C. For 30min, and a heating rate of 5 ℃ C./min).
2. Experimental results
FIGS. 9a, b show that the hybrid resin is statically ablated at high temperature under an oxidizing atmosphere to form a dense ceramic layer, the structure remains intact, and the glass char obtained from the pure phenolic resin is fully oxidized. The results in FIG. 9c show that the carbonized ceramic product after static ablation of the hybrid resin is mainly composed of amorphous carbon, calcium phosphate, calcium carbide and calcium oxide.
Experimental example 8 plasma dynamic ablative Properties of 3-BRPO hybrid resins
In this experimental example 3-BRPO b, BPR was prepared according to the method in example 1 and comparative example 1.
1. Experimental method
Dynamic ablation performance of the hybrid resin in an oxygen-rich atmosphere was characterized by a plasma ablator (0.5 MW/m2; nitrogen flow/oxygen flow = 1; ablation time 60 s).
2. Experimental results
As can be seen from fig. 10, the hybrid resin ablates the surface in an oxygen-enriched atmosphere to form a dense ceramic layer, while the glass carbon obtained from the pure phenolic resin is completely exposed to flame, and the covalent-ionic bicontinuous hybrid resin shows excellent ablation resistance in an oxygen-enriched environment, and the mass ablation rate is reduced by 24% compared with that of the boron phenolic resin (BPR group). Therefore, the covalent-ion bicontinuous network constructed by the invention can effectively improve the ablation resistance of the resin material.
Experimental example 9 mechanical Properties of 3-BRPO hybrid resin
In this experimental example, 3-BRPOb and BPR were prepared in the same manner as in example 1 and comparative example 1.
1. Experimental method
The mechanical properties of the 3-BRPO hybrid resin are characterized by a nano indentation instrument.
2. Experimental results
As can be seen in FIG. 11, the modulus of the 3-BRPO hybrid resin was 52.4% higher than that of the BPR neat sample. The successful construction of the organic-inorganic bicontinuous network in the hybrid resin is shown to greatly improve the modulus of the material, and the mechanical property of the resin material can be effectively improved.
In conclusion, the hybrid resin prepared by the invention has a covalent-ion bicontinuous network with a continuous structure from macroscopic scale to microscopic scale, has excellent high-temperature oxidation resistance, ablation resistance and mechanical property, and has wide application prospect in the field of thermal protection materials.
Claims (10)
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20090236132A1 (en) * | 2008-03-20 | 2009-09-24 | Industrial Technology Research Institute | Organic/inorganic hybrid composition with electrostatic discharge protection property |
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| CN118994575A (en) * | 2023-05-16 | 2024-11-22 | 四川大学 | Poly (dimethyl diphenyl imide) siloxane/phenolic group double-network hybrid resin and preparation method and application thereof |
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| US20090236132A1 (en) * | 2008-03-20 | 2009-09-24 | Industrial Technology Research Institute | Organic/inorganic hybrid composition with electrostatic discharge protection property |
| WO2018033161A1 (en) * | 2016-08-19 | 2018-02-22 | 山东圣泉新材料股份有限公司 | Modified phenolic-resin fiber and method for fabricating same and use of same, and composite material made of said modified phenolic-resin fiber and used for electrode |
| CN113621215A (en) * | 2021-07-28 | 2021-11-09 | 哈尔滨工业大学 | Preparation method of organic-inorganic hybrid biomass phenolic resin ablation-resistant material |
| CN118994575A (en) * | 2023-05-16 | 2024-11-22 | 四川大学 | Poly (dimethyl diphenyl imide) siloxane/phenolic group double-network hybrid resin and preparation method and application thereof |
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