Silicon / titanium / hybridized boron phenolic / silicone resin-based ceramic fluxing crystallization material, preparation method and application thereof

Abstract

The present application relates to the field of ceramic materials, in particular to a silicon / titanium / hybrid boron phenolic / silicone resin-based ceramic fluxing crystallization material and its preparation method and application. Triphenyl borate and diphenyl borate are subjected to hydroxymethylation reaction to obtain boron hybrid phenolic resin, which is then subjected to condensation dealcoholization reaction with dialkoxy silane to prepare silicon hybrid boron phenolic resin; or subjected to alcohol exchange reaction with titanate to prepare titanium hybrid boron phenolic resin; and then compounded with MQ silicone resin to obtain a polymer base; after being dissolved in alcohol / aromatic hydrocarbon mixed solvent, mixed with metal oxide, and added with an interface treatment agent, molding, drying and sintering are carried out to obtain a ceramic fluxing crystallization material, which is used for ceramic bonding to prepare ceramic and glaze, and can effectively reduce the sintering temperature of high-temperature ceramic, which is conducive to energy saving and consumption reduction.

Description

Technical Field

[0001] The invention relates to a silicon / titanium / hybrid boron phenolic aldehyde / silicone resin-based ceramic fluxing and crystallization material and a preparation method thereof, belonging to the technical field of ceramic materials. Background Art

[0002] Fluxing refers to the process of lowering the sintering temperature of the material and promoting the melting and crystallization of the material during the sintering process, thereby improving the density and strength of the ceramic. Ceramic flux is a substance that can form a liquid phase with the ceramic material. It can lower the softening, melting or liquefaction temperature of its ceramic raw materials during the sintering process, or react with ceramic powder to form a liquid phase, so that the ceramic powder can be better sintered together. Ceramic flux is usually some metal oxides, such as sodium oxide and potassium oxide. These fluxes can melt and crystallize at a lower temperature to form a liquid phase, which is conducive to lowering the hot melting temperature of the ceramic powder. By adding an appropriate amount of flux, the sintering temperature of the ceramic material can be reduced, and the efficiency and quality of the sintering process can be improved.

[0003] Using certain metal oxides as fluxes, such as rare earth metal oxides represented by Y2O3 and alkaline earth metal oxides represented by CaO, through interfacial depolarization treatment, and filling and compounding with the matrix as additives, can achieve densification of the sintered material. Furthermore, through reactive sintering with the matrix, CaO, MgO, Al2O3, etc., will form a glass phase, and the oxides pyrolyzed from the matrix will dissolve into the molten glass, forming a ceramic fluxing and crystallizing material. For example, CN105236993A discloses a Li2O-P2O5-B2O3-TiO2 ceramic flux and a preparation method thereof. The Li2O-P2O5-B2O3-TiO2 ceramic flux is prepared by mixing raw materials such as SiO2, Al2O3, B2O3, P2O5, TiO2, Li2O, and Cr2O3 in varying weight proportions, pre-sintering at 600-800°C, and melting at 1000-1280°C. It interacts with high-temperature ceramic binders to lower the sintering temperature of diamond ceramics, avoiding unnecessary damage to diamond abrasives during the sintering process. US2004071629A1 discloses an improved method for preparing highly crystalline, fine barium titanate powder. Specifically, when titanium oxide powder and a barium-containing powder material are mixed and calcined to prepare barium titanate powder, the barium compound on the surface of the titanium oxide powder particles inhibits the sintering or growth of titanium oxide during calcination, thereby producing a highly crystalline, fine barium titanate powder. US4788163A discloses a novel crystallized glass frit prepared at 900°C using materials such as zinc oxide, calcium oxide, magnesium oxide, barium oxide, silicon dioxide, and aluminum oxide. The frit exhibits a high softening temperature and excellent reheating stability, making it suitable for use in ink formulations for forming dielectric layers in multilayer circuits. It is also suitable for use as a substrate material for direct silicon chips or in thick film applications via filler inks. However, metal oxide ceramic fluxes lack plasticity, which limits their application.

[0004] Polymer-converted ceramics offer a unique approach to the manufacture of ceramic-based composites. By adjusting the polymer's molecular structure and molecular weight, the resulting materials can be processed using polymer composite processes such as paste resin coating, resin transfer molding, and filament winding. Organic polymers containing elements such as carbon, combined with powder or fibrous fillers, are easily processed and molded, resulting in powder-filled or fiber-reinforced ceramic-based composites that can be heat-treated under inert gas or reactive atmospheres. This has led to the emergence of polymer-derived ceramics.

[0005] However, the temperature limit of polymer materials is often low. For example, the heat-resistant operating temperature of epoxy resin is lower than 200°C, the maximum operating temperature of silicone polymer and bismaleimide can reach 300°C, the maximum operating temperature of polybenzimidazole and polyimide can reach 350°C, and the phenolic resin modified silicone polymer can withstand 450°C. When the ambient temperature rises, the main chain structure of the molecule breaks down, resulting in a sharp drop in its mechanical properties, which cannot meet the requirements of use. A large number of experimental studies have shown that the polymer-to-ceramic route can generate various components of ceramic-based composites, usually including ceramic components such as SiO2, Si-C, Si-CO, Si-N and Si-NC. The process of this method includes: (1) low-temperature molding; (2) high-temperature pyrolysis; (3) repeatable impregnation-pyrolysis cycles to achieve the appropriate density. The pre-ceramic polymer process of ceramic-based composites is very similar to the process of polymer composite applications. In principle, any method suitable for polymer composite forming can be used. The pyrolysis environment is slightly different, and the pyrolysis is carried out in an inert atmosphere or a reactive atmosphere at least above 700°C (usually 900-1200°C).

[0006] In addition, Cui Mengzhong et al. used polydisiloxane silicone elastomer to prepare and study the properties of high-conversion inorganic silicon-carbon-oxygen high-temperature ablation-resistant materials [Science Bulletin, 2007, 52(14):1625-1629]. The study showed that the pyrolysis products gradually transformed into a partial β-SiC crystalline structure under nitrogen atmosphere at 1050-1500°C. As the treatment temperature increased, the crystallinity of silicon carbide and cristobalite increased significantly. The weight loss at 1500°C was only 30%. However, because no inorganic filler was used, cracking occurred during the formation of the silicon-oxygen-carbon ceramic precursor.

[0007] Therefore, research on a novel ceramic flux that has good plasticity and workability and can reduce the ceramic sintering temperature and save energy has become a technical problem to be solved. Summary of the Invention

[0008] In light of the aforementioned state of the prior art, the inventors of the present invention conducted in-depth and extensive research on resin-based ceramic fluxes and discovered that using boron-hybridized phenolic resins, boron-silicon hybridized phenolic resins, and / or boron-titanium hybridized phenolic resins compounded with silicone resins as the polymer base and mixed with alkaline earth metal oxides to form ceramic fluxing and crystallization materials not only facilitates bonding and molding at the interface of inorganic materials or metals, improving the yield rate of bonded products after molding, but also reduces the sintering temperature of high-temperature ceramics, thereby achieving high-performance, high-strength ceramic glazes or ceramic bonding materials while also contributing to energy conservation and consumption reduction. The present invention was made possible based on this discovery.

[0009] Therefore, the first objective of the present invention is to provide a ceramic fluxing and crystallization material. Compared to existing fluxing agents that solely utilize metal oxides, the present invention utilizes a boron-hybridized phenolic resin, a boron-silicon hybridized phenolic resin, or / and a boron-titanium hybridized phenolic resin compounded with a silicone resin as a polymer base, which is then mixed with an alkaline earth metal oxide to form a ceramic fluxing and crystallization material. This material not only facilitates bonding and molding at the interface of inorganic materials or metals, but also reduces the sintering temperature of high-temperature ceramics, thereby contributing to energy conservation and consumption reduction.

[0010] A second object of the present invention is to provide a method for preparing the aforementioned ceramic fluxing and crystallizing material. The method comprises dissolving a polymer-based raw material in a solvent, compounding the material with a metal oxide, and using a silane coupling agent or a titanate coupling agent as a surface treatment agent for the metal oxide to prepare a dry silicon / titanium / hybrid boron phenolic / silicone resin-based / metal oxide composite. The composite is then sintered at a high temperature to obtain the ceramic fluxing and crystallizing material. The preparation process is simple.

[0011] The third object of the present invention is to provide the use of the above-mentioned ceramic fluxing and crystallization material in the preparation of ceramic binders, ceramic glazes, and high-temperature resistant ceramics.

[0012] The technical solutions for achieving the above-mentioned purpose of the present invention can be summarized as follows:

[0013] A ceramic fluxing crystallization material, the raw materials of the ceramic flux crystal material include: a composite material composed of a polymer-based raw material and a metal oxide;

[0014] The polymer-based raw material is a mixture of at least one of boron hybrid phenolic resin, silicon-boron hybrid phenolic resin, titanium-boron hybrid phenolic resin and organic silicon resin.

[0015] According to the present invention, preferably, the boron hybrid phenolic resin is hydroxymethylated diphenyl borate and / or hydroxymethylated triphenyl borate;

[0016] Further preferably, the hydroxymethylated diphenyl borate has the following structure:

[0017]

[0018] Further preferably, the hydroxymethylated triphenyl borate has the following structure:

[0019]

[0020] According to the present invention, preferably, the boron hybrid phenolic resin is tetrakishydroxymethyl diphenyl borate or hexahydroxymethyl triphenyl borate prepared by reacting diphenyl borate or triphenyl borate with formaldehyde for hydroxymethylation;

[0021] Further preferably, the reaction molar ratio of diphenyl borate to formaldehyde is 1.0:4.0 to 1:4.5, and the reaction molar ratio of triphenyl borate to formaldehyde is 1.0:6.0 to 1:7.0;

[0022] More preferably, the hydroxymethylation reaction is carried out using aqueous ammonia as a catalyst at a reaction temperature of 50 to 120°C.

[0023] According to the present invention, preferably, the silicon-boron hybrid phenolic resin is obtained by further reacting the boron hybrid phenolic resin with a dialkoxysilane R 1 R 2 Si(OR 3 )2 is subjected to chain extension reaction to obtain;

[0024] Further preferably, the molar ratio of dialkoxysilane to boron hybrid phenolic resin is 2.0:1.0 to 2.2:1.0, and the temperature of the chain extension reaction is 40-120°C;

[0025] Further preferably, the silicon-boron hybrid phenolic resin has the following structure:

[0026]

[0027] More preferably, the dialkoxysilane R 1 R 2 Si(OR 3 ) 2 is at least one selected from dimethyldimethoxysilane, dimethyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methylhydrogendimethoxysilane, and methylhydrogendiethoxysilane;

[0028] R 1 、R 2 、R 3 Each independently selected from a C1-C6 alkyl group or a phenyl group, more preferably a methyl group, an ethyl group, or a phenyl group.

[0029] According to the present invention, preferably, the titanium-boron hybrid phenolic resin is obtained by further transesterifying the boron hybrid phenolic resin with titanate;

[0030] More preferably, the molar ratio of titanate to boron hybrid phenolic resin is 4.0:1.0 to 4.2:1.0; the temperature of the transesterification reaction is 20-30°C;

[0031] More preferably, the titanate is at least one of ethyl titanate, isopropyl titanate, n-butyl titanate, and poly-n-butyl titanate;

[0032] Further preferably, the titanium-boron hybrid phenolic resin has the following structure:

[0033]

[0034]

[0035] According to the present invention, preferably, the organic silicone resin is an MQ silicone resin, further preferably at least one of methyl MQ silicone resin, methylphenyl MQ silicone resin, methylvinyl MQ silicone resin, and methylhydrogen MQ silicone resin; preferably, the M / Q ratio of the MQ silicone resin is between 0.30 and 1.20.

[0036] According to the present invention, preferably, the weight ratio of the boron hybrid phenolic resin, silicon-boron hybrid phenolic resin or titanium-boron hybrid phenolic resin to the MQ silicone resin is between 2:1 and 1:2.

[0037] According to the present invention, preferably, the metal oxide comprises at least calcium oxide, magnesium oxide and aluminum oxide, or further comprises at least one of silicon dioxide and boric acid (calculated as B2O3);

[0038] Further preferably, the molar ratio of the oxides is: CaO:MgO:Al2O3:B2O3:SiO2=(0.50-0.8):(0.10-0.30):(0.63-0.85):(5.30-6.00):(0.200-0.500), wherein SiO2 and B2O3 produced by the polymer-based raw materials are included in the composition;

[0039] More preferably, the metal oxide is a fine powder with a particle size of more than 200 meshes.

[0040] According to the present invention, preferably, in the composite material composed of the polymer-based raw material and the metal oxide, the weight ratio of the polymer-based raw material to the metal oxide is 1:9 to 9:1, and more preferably 2:8 to 4:6.

[0041] According to the present invention, preferably, the raw materials of the ceramic flux crystal material further include a surface treatment agent for the metal oxide;

[0042] Further preferably, the surface treatment agent for the metal oxide is a silane coupling agent and / or a titanate coupling agent;

[0043] More preferably, the silane coupling agent is at least one of methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and phenyltriethoxysilane, and the titanate coupling agent is at least one of ethyl titanate, isopropyl titanate, n-butyl titanate, and polyn-butyl titanate.

[0044] According to the present invention, preferably, the amount of the surface treatment agent for the metal oxide is 1% to 8% of the mass of the metal oxide.

[0045] According to the present invention, preferably, the ceramic flux crystallization material, wherein the crystal components include at least one of quartz, cristobalite, γ-phase alumina and perovskite crystals, has typical crystalline compound properties.

[0046] According to the present invention, the method for preparing the ceramic flux crystal material comprises the following steps:

[0047] The polymer-based raw material is dissolved in a solvent, and a metal oxide is added, or a surface treatment agent for the metal oxide is added, mixed evenly, dried, and formed to obtain a composite material; and then sintered to obtain a ceramic fluxing and crystallization material.

[0048] According to the present invention, preferably, the sintering temperature is 250-1250°C, most preferably 1000-1250°C.

[0049] According to the present invention, preferably, the solvent is a mixed solvent of alcohol / aromatic hydrocarbon;

[0050] More preferably, the alcohol is methanol or ethanol; the aromatic hydrocarbon is toluene or xylene;

[0051] Further preferably, the volume ratio of the alcohol to the aromatic hydrocarbon is between 2:1 and 1:2, and the amount of the mixed solvent is 1 to 3 times the volume of the polymer-based raw material.

[0052] According to the present invention, the above ceramic flux crystal material is used in the preparation of ceramic adhesives, ceramic glazes, and high-temperature resistant ceramics.

[0053] The beneficial effects of the present invention are as follows:

[0054] 1. The ceramic flux crystal material of the present invention has good plasticity and processability based on the polymer matrix, and can provide the toughness and impact resistance of the ceramic material.

[0055] 2. The ceramic flux crystal material of the present invention has a significant crystal precipitation phenomenon and a low melting temperature, which is very helpful in reducing the ceramic calcination temperature.

[0056] 3. The ceramic flux crystal material of the present invention is simple to prepare and can be conveniently formed in the form of an additive, and can be applied to the preparation process of ceramic glazes and high-temperature resistant ceramic materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] Figure 1 The H NMR spectra of the products of hydroxymethylated triphenyl borate (II-A) and hydroxymethylated diphenyl borate (II-B) in Example 2 ( 1 H NMR);

[0058] Figure 2 The H-NMR spectrum of the silicon-boron hybrid phenolic resin (triphenyl ester) (III-A-Si) product in Example 3 (1 H NMR);

[0059] Figure 3 The H-NMR spectrum of the titanium-boron hybrid phenolic resin (triphenyl ester) (III-A-Ti) product in Example 3 ( 1 H NMR);

[0060] Figure 4 Thermogravimetric spectra of boron hybrid phenolic resin (triphenyl ester) (II-A), silicon boron hybrid phenolic resin (triphenyl ester) (III-A-Si), and titanium boron hybrid phenolic resin (triphenyl ester) (III-A-Ti) in Example 3;

[0061] Figure 5 Thermal gravimetric spectra of the boron hybrid phenolic resin (diphenyl ester) (II-B), silicon-boron hybrid phenolic resin (diphenyl ester) (III-B-Si), and titanium-boron hybrid phenolic resin (diphenyl ester) (III-B-Ti) in Example 3;

[0062] Figure 6 In Example 4, the boron hybrid phenolic resin / methyl MQ silicone resin composite (1-1#), the silicon-boron hybrid phenolic resin / methyl MQ silicone resin composite (1-2#), and the titanium-boron hybrid phenolic resin / methyl MQ silicone resin composite (1-3#) were tested for their thermogravimetric spectra.

[0063] Figure 7 Thermogravimetric spectra of the boron hybrid phenolic resin / MQ silicone resin / metal oxide composite (2-1#), the silicon-boron hybrid phenolic resin (triphenyl ester) / methyl MQ silicone resin / metal oxide composite (2-2#), and the titanium-boron hybrid phenolic resin (triphenyl ester) / methyl MQ silicone resin / metal oxide composite (2-3#) in Example 5;

[0064] Figure 8 Schematic diagram of heating program 1 in Example 5.

[0065] Figure 9 Schematic diagram of heating program 2 in Example 5.

[0066] Figure 10 Schematic diagram of heating program 3 in Example 5.

[0067] Figure 11 XRD spectra of the boron hybrid phenolic resin / MQ silicone resin / metal oxide composite (2-1#), silicon-boron hybrid phenolic resin (triphenyl ester) / methyl MQ silicone resin / metal oxide composite (2-2#), and titanium-boron hybrid phenolic resin (triphenyl ester) / methyl MQ silicone resin / metal oxide composite (2-3#) samples treated at 600° C. in Example 5;

[0068] Figure 12XRD spectra of the boron hybrid phenolic resin / MQ silicone resin / metal oxide composite (2-1#), silicon-boron hybrid phenolic resin (triphenyl ester) / methyl MQ silicone resin / metal oxide composite (2-2#), and titanium-boron hybrid phenolic resin (triphenyl ester) / methyl MQ silicone resin / metal oxide composite (2-3#) samples treated at 1020° C. in Example 5;

[0069] Figure 13 XRD spectra of the boron hybrid phenolic resin / MQ silicone resin / metal oxide composite (2-1#), silicon-boron hybrid phenolic resin (triphenyl ester) / methyl MQ silicone resin / metal oxide composite (2-2#), and titanium-boron hybrid phenolic resin (triphenyl ester) / methyl MQ silicone resin / metal oxide composite (2-3#) samples treated at 1220°C in Example 5.

[0070] Figure 14 Schematic diagram of the heating program during the sintering process of Example 6.

[0071] Figure 15 The XRD spectrum of the zirconium silicate / zirconium oxide ceramic sample obtained after sintering at 1500° C. in Example 6.

[0072] Figure 16 The XRD spectrum of the ceramic sample obtained after sintering at 1500° C. in Comparative Example 1. DETAILED DESCRIPTION

[0073] Organic silicon resins have excellent weather resistance due to the long bond length and large bond angle of the Si-O-Si main chain structure, and they are converted into SiOC ceramic structures under high temperature conditions, thus having excellent high temperature resistance and ablation resistance. Phenolic resins contain a large number of rigid benzene ring structures in the main chain, which can form graphite structures under high temperature conditions, thus giving them excellent heat resistance. At the same time, the carbonized layer has ablation resistance and can take away the heat generated by the outer layer. Boron-hybridized phenolic resins are a type of boron-hybridized phenolic resin synthesized from formaldehyde, phenol and boron modifiers. They have good heat resistance and ablation resistance. The ablation resistance, instantaneous high temperature resistance, thermal oxidation resistance, and neutron radiation resistance of boron-hybridized phenolic resins are superior to ordinary phenolic resins. The present invention uses a resin-based polymer and an alkaline earth metal oxide to facilitate bonding and molding at the interface of inorganic materials or metals. The resin polymer undergoes a cross-linking and curing reaction under medium and low temperature conditions, so that the composite adhesive has early strength and improves the yield of the bonded products after molding. Furthermore, during sintering, a powdered ceramic fluxing and crystallization material is obtained. This material can be used as a high-temperature sintering flux and further compounded with high-temperature resistant ceramic powders such as silicon carbide, boron nitride, and silicon nitride to prepare ceramic glazes or for ceramic bonding, thereby reducing the sintering temperature of high-temperature ceramics. While obtaining high-performance, high-strength ceramic glazes or ceramic bonding materials, it is beneficial to energy conservation and consumption reduction.

[0074] The present invention is based on the fact that the polymer matrix has good plasticity and processability, and can provide the material with toughness and impact resistance. A simpler and more efficient ceramic fluxing material has been developed, which is convenient to shape in the form of an additive and can be applied to the preparation process of ceramic glazes, high-temperature resistant ceramic materials, etc.

[0075] The present invention adopts boron silicon titanium hybrid phenolic resin / silicone resin as a polymer base, dissolves it in an organic solvent, and mixes it with alkaline earth metal oxides such as calcium, magnesium, aluminum, etc. in the presence of an organic silicon or organic titanium surface treatment agent. After uniform mixing, a paste-like resin-based metal oxide complex is obtained. Under low temperature conditions, the above-mentioned paste-like resin-based metal oxide complex is desolvated, dried, and formed, and then heated from room temperature to a maximum of 1200°C in a high-temperature furnace for normal pressure sintering to prepare a ceramic fluxing and crystallization material. The ceramic fluxing and crystallization material of the present invention has a significant crystal precipitation phenomenon, which is more conducive to inducing a ceramic phase during subsequent ceramic sintering and has typical crystalline ceramic compound properties. This shows that under high-temperature calcination, a crystalline phase is generated from the glass melt phase to form a crystallizable fluxing material. Since the fluxing and crystallization material has a low melting point, it will be beneficial to reduce the ceramic calcining temperature. In addition, the preparation method of the present invention is simple and easy to process and shape. For the sintering of fluxing ceramic glazes or high-temperature resistant ceramics, it can reduce the sintering temperature and save energy.

[0076] The raw materials of the ceramic fluxing and crystallization material of the present invention include: a composite material composed of a polymer-based raw material and a metal oxide;

[0077] The polymer-based raw material is a mixture of at least one of boron hybrid phenolic resin, silicon-boron hybrid phenolic resin, titanium-boron hybrid phenolic resin and organic silicon resin.

[0078] The boron-modified phenolic resin of the present invention comprises: hydroxymethylated diphenyl borate and hydroxymethylated triphenyl borate (Formula 1). The two boron-modified phenolic resin sources can be prepared by hydroxymethylation reaction using diphenyl borate (Formula 2), triphenyl borate (Formula 3) and formaldehyde as raw materials according to the reference (Mohamed O. Abdalla, Adriane Ludwick, Temisha Mitchell. Boron-modified phenolic resins for high performance applications [J]. Polymer, 2003, 44 (24): 7353-7359). The molar ratio of diphenyl borate and triphenyl borate to formaldehyde is preferably 1.0:4.0 to 1:4.5 and 1.0:6.0 to 1:7.0, respectively. The reaction is preferably carried out at 50 to 120° C. under ammonia catalysis for 2 to 6 hours. The diphenyl borate and triphenyl borate of the present invention can be prepared by solid-phase borate esterification according to the prior art.

[0079]

[0080]

[0081]

[0082] In one or more preferred embodiments, the boron hybrid phenolic resin is hydroxymethylated diphenyl borate and / or hydroxymethylated triphenyl borate;

[0083] Preferably, the hydroxymethylated diphenyl borate has the following structure:

[0084]

[0085] Preferably, the hydroxymethylated triphenyl borate has the following structure:

[0086]

[0087] In one or more preferred embodiments, the boron hybrid phenolic resin is prepared by reacting diphenyl borate or triphenyl borate as raw materials with formaldehyde to form tetrakishydroxymethyl diphenyl borate or hexahydroxymethyl triphenyl borate;

[0088] Preferably, the reaction molar ratio of diphenyl borate to formaldehyde is 1.0:4.0 to 1:4.5, and the reaction molar ratio of triphenyl borate to formaldehyde is 1.0:6.0 to 1:7.0;

[0089] Preferably, the hydroxymethylation reaction is carried out using aqueous ammonia as a catalyst at a reaction temperature of 50-120°C.

[0090] The silicon-boron hybrid phenolic resin of the present invention is obtained by further reacting boron hybrid phenolic resin (hydroxymethylated diphenyl borate, hydroxymethylated triphenyl borate) with dialkoxysilane R 1 R 2 Si(OR 3 )2 is subjected to chain extension reaction to prepare silicon-boron hybrid phenolic resin (4); and the boron hybrid phenolic resin (hydroxymethylated diphenyl borate, hydroxymethylated triphenyl borate) is further subjected to ester exchange reaction with titanate to prepare titanium-boron hybrid phenolic resin (5).

[0091]

[0092]

[0093] Boron hybrid phenolic resin is further reacted with dialkoxysilane R 1 R 2 Si(OR 3)2In the chain extension reaction, the molar ratio of dialkoxysilane to boron hybrid phenolic resin is preferably 2.0:1.0 to 2.2:1.0, and the chain extension reaction is preferably carried out at a temperature of 40-120°C. After separating the solvent, the silicon-boron hybrid phenolic resin is obtained. The dialkoxysilane preferably includes: dimethyldimethoxysilane, dimethyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methylhydrogendimethoxysilane, methylhydrogendiethoxysilane, etc. When the boron hybrid phenolic resin further undergoes an ester exchange reaction with a titanate, the molar ratio of the titanate to the boron hybrid phenolic resin is preferably 4.0:1.0 to 4.2:1.0. The ester exchange reaction is carried out at room temperature, and then the solvent is separated to obtain the titanium-boron hybrid phenolic resin. The titanate preferably includes: ethyl titanate, isopropyl titanate, n-butyl titanate, poly-n-butyl titanate, etc.

[0094] In one or more preferred embodiments, the silicon-boron hybrid phenolic resin is obtained by further reacting the boron hybrid phenolic resin with a dialkoxysilane R 1 R 2 Si(OR 3 )2 is subjected to chain extension reaction to obtain;

[0095] Preferably, the molar ratio of dialkoxysilane to boron hybrid phenolic resin is 2.0:1.0 to 2.2:1.0, and the temperature of the chain extension reaction is 40-120°C;

[0096] Preferably, the silicon-boron hybrid phenolic resin has the following structure:

[0097]

[0098] Preferably, the dialkoxysilane R 1 R 2 Si(OR 3 ) 2 is at least one selected from dimethyldimethoxysilane, dimethyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methylhydrogendimethoxysilane, and methylhydrogendiethoxysilane;

[0099] Where: R 1 、R 2 、R 3 Each independently selected from a C1-C6 alkyl group or a phenyl group, more preferably a methyl group, an ethyl group, or a phenyl group.

[0100] In one or more preferred embodiments, the titanium-boron hybrid phenolic resin is obtained by further transesterifying the boron hybrid phenolic resin with titanate;

[0101] Preferably, the molar ratio of titanate to boron hybrid phenolic resin is 4.0:1.0 to 4.2:1.0; the temperature of the transesterification reaction is 20-30°C;

[0102] Preferably, the titanate is at least one of ethyl titanate, isopropyl titanate, n-butyl titanate, and poly-n-butyl titanate;

[0103] Preferably, the titanium-boron hybrid phenolic resin has the following structure:

[0104]

[0105]

[0106] The organic silicone resin of the present invention is an MQ silicone resin prepared by the alkoxysilane monomer / water glass process. MQ silicone resin is a type of polysiloxane, a mature commercial product, and can also be prepared according to existing technology. MQ silicone resin is composed of a single functional group R3SiO 1 / 2 Chain unit (M unit) and tetrafunctional SiO 4 / 2 A silicone resin composed of chain unit (Q unit for short) has a double-layer structure and is compact and spherical. In the MQ silicone resin used in the present invention, the alkoxysilane monomer preferably includes: methyltrimethoxysilane or methyltriethoxysilane, and any one of phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, trimethoxysilane and triethoxysilane. The M / Q ratio is preferably between 0.30 and 1.20. Depending on the type of alkoxysilane monomer, the MQ silicone resin can be methyl MQ silicone resin, methylphenyl MQ silicone resin, methylvinyl MQ silicone resin, methylhydrogen MQ silicone resin, etc.

[0107] The polymer-based raw material described in the present invention is a composite of at least one of the aforementioned boron hybrid phenolic resin, silicon-boron hybrid phenolic resin, and titanium-boron hybrid phenolic resin and MQ silicone resin, and the weight ratio of the boron hybrid phenolic resin, silicon-boron hybrid phenolic resin or titanium-boron hybrid phenolic resin to the MQ silicone resin is between 2:1 and 1:2.

[0108] In one or more preferred embodiments, the organic silicone resin is an MQ silicone resin, further preferably at least one of methyl MQ silicone resin, methylphenyl MQ silicone resin, methylvinyl MQ silicone resin, and methylhydrogen MQ silicone resin; preferably, the M / Q ratio of the MQ silicone resin is between 0.30 and 1.20.

[0109] In one or more preferred embodiments, the weight ratio of the boron hybrid phenolic resin, silicon boron hybrid phenolic resin or titanium boron hybrid phenolic resin to the MQ silicone resin is between 2:1 and 1:2.

[0110] The metal oxides described in the present invention include calcium oxide, magnesium oxide, aluminum oxide, or aluminum hydroxide (calculated as aluminum oxide), silicon dioxide, and boric acid (calculated as a B2O3 source). These metal oxides readily form a glass phase or glass ceramics under sintering conditions. Drawing on the successful theories and experience of glass ceramic preparation both domestically and internationally, the present invention incorporates CaO, MgO, Al2O3, B2O3, and SiO2, all of which are good high-temperature flux components. The metal oxides are fine powders with a particle size of 200 mesh or larger. For these oxides, according to a certain molar ratio composition, for example: CaO:MgO:Al2O3:B2O3:SiO2=(0.50~0.8):(0.10~0.30):(0.63~0.85):(5.30~6.00):(0.200~0.500) (SiO2 and B2O3, the sintered products of the polymer base material, are included in the composition), a molten softened glass phase or glass ceramic can be formed at a calcination temperature of 250-1250°C, preferably in the range of 1000~1250°C.

[0111] In one or more preferred embodiments, the metal oxide comprises at least calcium oxide, magnesium oxide and aluminum oxide, or further comprises at least one of silicon dioxide and boric acid (denoted as B2O3);

[0112] Preferably, the molar ratio of the oxides is: CaO:MgO:Al2O3:B2O3:SiO2=(0.50-0.8):(0.10-0.30):(0.63-0.85):(5.30-6.00):(0.200-0.500), wherein SiO2 and B2O3 produced by the polymer-based raw materials are included in the composition;

[0113] Preferably, the metal oxide is a fine powder with a particle size of 200 mesh or more.

[0114] The ceramic fluxing and crystallization material of the present invention is mainly a composite material composed of a polymer-based raw material and a metal oxide.

[0115] In one or more preferred embodiments, in the composite material composed of the polymer-based raw material and the metal oxide, the weight ratio of the polymer-based raw material to the metal oxide is 1:9 to 9:1, more preferably 2:8 to 4:6.

[0116] In the ceramic fluxing and crystallization material raw materials described herein, the metal oxide is preferably treated with an interface treatment agent. These can be organic silicon or organic titanium interface treatment agents, including coupling agents such as methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and phenyltriethoxysilane, or coupling agents such as isopropyl titanate, n-butyl titanate, and poly-n-butyl titanate. This improves the dispersibility of the metal oxide during the composite process with the polymer, resulting in a more uniform and efficient sintered material.

[0117] In one or more preferred embodiments, the raw materials of the ceramic flux crystal material further include a surface treatment agent for the metal oxide; further preferably, the surface treatment agent for the metal oxide is a silane coupling agent and / or a titanate coupling agent; more preferably, the silane coupling agent is at least one of methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and phenyltriethoxysilane, and the titanate coupling agent is at least one of ethyl titanate, isopropyl titanate, n-butyl titanate, and polyn-butyl titanate.

[0118] In one or more preferred embodiments, the amount of the surface treatment agent for the metal oxide is 1% to 8% by mass of the metal oxide.

[0119] The present invention also provides a method for preparing the ceramic flux crystal material, comprising the following steps:

[0120] The polymer-based raw material is dissolved in a solvent, and a metal oxide is added, or a surface treatment agent for the metal oxide is added, mixed evenly, dried, and formed to obtain a composite material; and then sintered to obtain a ceramic fluxing and crystallization material.

[0121] The solvent described in the present invention is an organic solvent, and a mixed solvent of methanol or ethanol and the aromatic hydrocarbons toluene or xylene can be used. The volume ratio of the alcohol / aromatic solvent is between 2:1 and 1:2, and the amount used is 1 to 3 times the volume of the polymer-based raw material. Silicon-boron hybrid phenolic resin or titanium-boron hybrid phenolic resin has good solubility with MQ silicone resin, and the paste-like resin-based composite formed with the metal oxide has excellent workability. At temperatures above 150°C, the hydroxymethyl and silanol groups contained in the two resins further undergo a condensation reaction to form a heat-curable cross-linked resin.

[0122] In one or more preferred embodiments, the solvent is a mixed solvent of alcohol / aromatic hydrocarbon;

[0123] Preferably, the alcohol is methanol or ethanol; the aromatic hydrocarbon is toluene or xylene;

[0124] Preferably, the volume ratio of alcohol to aromatic hydrocarbon is between 2:1 and 1:2, and the amount of the mixed solvent is 1 to 3 times the volume of the polymer-based raw material.

[0125] The sintering process involved in the present invention utilizes the simplest atmospheric pressure sintering method in a tubular high-temperature furnace. During the sintering process, as the polymer-based raw material pyrolyzes, chemical reactions occur between the cracked polymer components and the metal oxide, resulting in a certain amount of reactive sintering. The preferred sintering conditions are as follows: room temperature to 250°C for 60 to 120 minutes, held for 20 to 60 minutes, then 250 to 1250°C for 100 to 450 minutes, held for 10 to 120 minutes. After the temperature is gradually lowered to below 100°C, the sintered material is removed and ground to obtain a powdered fluxing and crystallization material.

[0126] The present invention uses a polymer-based raw material and an alkaline earth metal oxide, etc. to form a composite, which is easy to bond or form at the interface of inorganic materials or metals. Under medium and low temperature conditions, the resin polymer undergoes a cross-linking and curing reaction, so that the composite adhesive has early strength and improves the yield rate of the bonded products after molding. When further sintered at a sintering temperature, a fluxing crystallization material can be prepared, in which quartz, cristobalite, γ-phase alumina and perovskite crystals are generated, and it has typical crystalline compound properties.

[0127] Based on the above properties, the ceramic flux crystal material of the present invention can be applied to ceramic glazes or flux materials during high-temperature ceramic sintering, which will help to lower the sintering temperature of ceramics, thereby saving energy and reducing consumption while obtaining high-temperature resistant, high-strength ceramic materials.

[0128] Therefore, the present invention also provides the use of the above-mentioned ceramic flux crystal material in the preparation of ceramic adhesives, ceramic glazes, and high-temperature resistant ceramics.

[0129] The present invention will be further described below through specific embodiments in conjunction with the accompanying drawings, but is not limited thereto.

[0130] Example 1

[0131] This embodiment provides a method for preparing triphenyl borate and diphenyl borate, and the specific steps are as follows:

[0132] In a reactor equipped with a stirrer, thermometer, and water separator, after nitrogen purging, 1.000 kg of phenol and 2.190 kg of boric acid were added, along with an appropriate amount of a basic catalyst. Nitrogen was introduced and the temperature was gradually raised to approximately 50°C. Once the solid phenol melted, the temperature was rapidly raised to 150°C and allowed to react for 30 minutes. The temperature was then slowly raised to 170°C. The water separator was connected to a -0.01 MPa vacuum decompression system for dehydration. The temperature was then raised by 10°C per hour until it reached 180°C, where the reaction was continued for 2 hours before heating was stopped. The product was removed after cooling to approximately 120°C. The resulting product was triphenyl borate in a 93% yield.

[0133] When preparing diphenyl borate, 3.280 kg of boric acid was added, and the remaining materials and synthesis process were the same as above. The product was triphenyl borate with a yield of 95%.

[0134] Example 2

[0135] This embodiment provides a method for preparing boron hybrid phenolic resins, namely hydroxymethylated diphenyl borate (II-B) and hydroxymethylated triphenyl borate (II-A), and the specific steps are as follows:

[0136] In a reactor equipped with a stirrer, thermometer, and reflux / water separator, 0.580 kg of triphenyl borate, 1.260 kg of 36% formaldehyde solution (or depolymerized paraformaldehyde), 100 mL of toluene, and an appropriate amount of aqueous ammonia as a catalyst were added. The mixture was heated to 50°C with stirring until a homogeneous solution was obtained. The temperature was then raised to 70°C for 1 hour, followed by 90°C for 2 hours, and then 120°C for 2 hours. The reaction mixture was rotary evaporated to obtain hydroxymethylated triphenyl borate in a yield of 95.5%.

[0137] To prepare hydroxymethylated diphenyl borate, 0.580 kg of triphenyl borate and 0.840 kg of 36% formaldehyde solution (or depolymerized paraformaldehyde) were added, and the remaining materials and synthesis process were the same as above. The product was hydroxymethylated diphenyl borate with a yield of 96.1%.

[0138] The H NMR spectra of the products of hydroxymethylated diphenyl borate and hydroxymethylated triphenyl borate ( 1 H NMR) Figure 1 shown.

[0139] Example 3

[0140] This embodiment provides a method for preparing a silicon-boron hybrid phenolic resin, and the specific steps are as follows:

[0141] In a reactor equipped with a stirrer, a thermometer, and a reflux + water separation device, 0.470 kg of boron hybrid phenolic resin (hydroxymethylated triphenyl borate (II-A)) was dissolved in 200 mL of a methanol / toluene (volume ratio of 2:1) mixed solvent, 0.060 kg of dimethyldimethoxysilane and an appropriate amount of tetramethylammonium hydroxide were added as catalysts, and the mixture was heated to about 50 ° C with stirring for 1 hour, further heated to 80 ° C for 4 hours to separate some methanol, and then rotary evaporation was performed, gradually increasing the temperature while gradually increasing the vacuum degree. Under a vacuum degree of -0.094 MPa, the temperature was raised to 120 ° C and maintained for 30 minutes before distillation was stopped to obtain silicon-boron hybrid phenolic resin (III-A-Si) with a yield of 97.2%.

[0142] This embodiment also provides a method for preparing a titanium-boron hybrid phenolic resin, and the specific steps are as follows:

[0143] In a reactor equipped with a stirrer, a thermometer, and a reflux + water separation device, 0.470 kg of boron hybrid phenolic resin (hydroxymethylated triphenyl borate (II-A)) was dissolved in 200 mL of a methanol / toluene (volume ratio of 2:1) mixed solvent, and 0.085 kg of tetrabutyl titanate was added. The reaction was stirred at room temperature and exothermic to about 40°C for 1 hour. It was then further heated to 80°C for 2 hours to separate some methanol, and then rotary evaporation was performed. The temperature was gradually increased while the vacuum degree was gradually increased. Under a vacuum degree of -0.094 MPa, the temperature was raised to 110°C and maintained for 30 minutes before distillation was stopped to obtain titanium boron hybrid phenolic resin (III-A-Ti) with a yield of 98.3%.

[0144] The H NMR spectrum of the silicon-boron hybrid phenolic resin (triphenyl ester) product in this example ( 1 H NMR) Figure 2 As shown, the H NMR spectrum of the titanium boron hybrid phenolic resin (triphenyl ester) product ( 1 H NMR) Figure 3 shown.

[0145] The thermogravimetric spectra of boron hybrid phenolic resin (triphenyl ester) (II-A), silicon boron hybrid phenolic resin (triphenyl ester) (III-A-Si), and titanium boron hybrid phenolic resin (triphenyl ester) (III-A-Ti) were tested. Figure 4 shown.

[0146] The thermogravimetric spectra of boron hybrid phenolic resin (diphenyl ester) (II-B), silicon boron hybrid phenolic resin (diphenyl ester) (III-B-Si), and titanium boron hybrid phenolic resin (diphenyl ester) (III-B-Ti) were tested. Figure 5 shown.

[0147] Depend on Figure 4 、 Figure 5 It can be seen that compared with the boron hybrid phenolic resins II-A and II-B, the thermal degradation rate of the silicon-boron hybrid phenolic resins III-A-Si and III-B-Si slows down at 500-700℃, while the thermal degradation rate of the titanium-boron hybrid phenolic resins III-A-Ti and III-B-Ti remains basically unchanged at 500-700℃; the amount of thermal degradation residues of the boron hybrid phenolic resins II-A and II-B at 800℃ are both higher than those of the corresponding silicon-boron hybrid phenolic resins III-A-Si, III-B-Si and titanium-boron hybrid phenolic resins III-A-Ti, III-B-Ti.

[0148] Example 4

[0149] This embodiment provides a method for preparing a composite material of a boron hybrid phenolic resin, a silicon-boron hybrid phenolic resin, and a titanium-boron hybrid phenolic resin with an MQ silicone resin, and the specific steps are as follows:

[0150] Accurately weigh the boron hybrid phenolic resin (II-A), silicon-boron hybrid phenolic resin (III-A-Si), and titanium-boron hybrid phenolic resin (III-A-Ti), and mix them with the methyl MQ silicone resin with M:Q=0.8 according to the following weight ratio:

[0151] Boron hybrid phenolic resin / methyl MQ silicone resin = 0.75 / 0.25, silicon-boron hybrid phenolic resin / methyl MQ silicone resin = 0.50 / 0.50, titanium-boron hybrid phenolic resin / methyl MQ silicone resin = 0.25 / 0.75, and the total amount of each polymer base material is 100.0 g; they are respectively dissolved and mixed evenly with 50 mL of methanol / toluene mixed solvent, and the volume ratios of methanol / toluene mixed solvents corresponding to the aforementioned polymer base materials are: 4:1, 1:2, and 1:1, respectively.

[0152] The following materials were obtained: boron hybrid phenolic resin / methyl MQ silicone resin composite (1-1#), silicon-boron hybrid phenolic resin / methyl MQ silicone resin composite (1-2#), titanium-boron hybrid phenolic resin / methyl MQ silicone resin composite (1-3#). The thermogravimetric spectra of the above composites were tested, as shown in FIG. Figure 6 shown.

[0153] Depend on Figure 6 It can be seen that the thermal degradation rate and thermal residual weight of the composite resin samples can be effectively controlled by varying the ratio of the boron, silicon, and titanium hybrid phenolic resin to the MQ silicone resin. This is mainly due to the condensation reaction between the hydroxyl groups of the boron, silicon, and titanium hybrid phenolic resin and the MQ silicone resin.

[0154] Example 5

[0155] This embodiment provides a method for preparing a ceramic fluxing and crystallizing material, and the specific steps are as follows:

[0156] Accurately weigh 5.00 g of boron-hybridized phenolic resin (II-A), 5.00 g of methyl MQ silicone resin with an M:Q of 0.8, and 5 mL of a mixed solvent with a methanol / toluene volume ratio of 1:2. After the resin base is dissolved, add 4.68 g of calcium oxide, 0.64 g of magnesium oxide, 14.68 g of aluminum oxide, and 1.50 g of methyltrimethoxysilane. After mixing evenly, use an agate mortar to grind the uniformly viscous resin paste for later use.

[0157] Accurately weigh 5.00 g of silicon-boron hybrid phenolic resin (triphenyl ester) (III-A-Si), 5.00 g of methyl MQ silicone resin with M:Q = 0.8, and 5 mL of a mixed solvent with a methanol / toluene volume ratio of 1:2. After the resin base material is dissolved, add 4.68 g of calcium oxide, 0.64 g of magnesium oxide, 14.68 g of aluminum oxide, and 1.50 g of methyltrimethoxysilane. After mixing evenly, use an agate mortar to grind the uniformly viscous resin paste for later use.

[0158] Accurately weigh 5.00 g of titanium boron hybrid phenolic resin (triphenyl ester) (III-A-Ti), 5.00 g of methyl MQ silicone resin with M:Q = 0.8, and 5 mL of a mixed solvent with a methanol / toluene volume ratio of 1:2. After the resin base material is dissolved, add 4.68 g of calcium oxide, 0.64 g of magnesium oxide, 14.68 g of aluminum oxide and 1.50 g of methyltrimethoxysilane. After mixing evenly, use an agate mortar to grind the uniformly viscous resin paste for later use.

[0159] The above metal oxides are all fine powders with a mesh size of 200 or more.

[0160] Molding and drying: The three resin polymer base / metal oxide pastes were placed in a 20 mm × 10 mm × 10 mm fluoroplastic strip mold, placed in a room temperature drying oven to evaporate the solvent, and then transferred to a 50°C oven for further devolatilization to dryness.

[0161] After drying, the following samples were obtained: boron hybrid phenolic resin / MQ silicone resin / metal oxide composite (2-1#), silicon-boron hybrid phenolic resin (triphenyl ester) / methyl MQ silicone resin / metal oxide composite (2-2#), and titanium-boron hybrid phenolic resin (triphenyl ester) / methyl MQ silicone resin / metal oxide composite (2-3#). The thermogravimetric spectra of the above three samples were tested, as shown in FIG. Figure 7 shown.

[0162] Depend on Figure 7 It can be seen that the thermal weight loss of composites 2-2# and 2-3# slows significantly above 100°C, while the thermal weight loss rate of composite 2-1# is higher between 100°C and 600°C. This is presumably due to the significantly improved thermal stability of the reaction products between the polymer base and the metal oxide in composites 2-2# and 2-3#.

[0163] Sintering Preparation: The three previously dried resin polymer / metal oxide strips were transferred to a high-purity alumina ceramic boat and placed in a tubular high-temperature furnace. Sintering was performed at 600°C, 1020°C, and 1220°C, respectively, using the following temperature program. This resulted in a silicon / titanium / hybrid boron phenolic resin / MQ silicone resin-based ceramic flux-crystallization material.

[0164] Heating program 1: room temperature to 250℃×100min and hold for 60min, 250~600℃×100min and hold for 10min, then program cooling from 600℃ to 200℃×100min, then naturally cool to below 100℃. Figure 8 shown.

[0165] Heating program 2: room temperature to 250℃×100min and hold for 60min, 250~1020℃×300min and hold for 20min, then program cooling 1020℃~200℃×400min, then naturally cool to below 100℃. Figure 9 shown.

[0166] Heating program 3: room temperature to 250℃×100min and hold for 60min, 250~1220℃×400min and hold for 20min, then program cooling 1220℃~200℃×500min, then naturally cool to below 100℃. Figure 10 shown.

[0167] The XRD spectra of the boron hybrid phenolic resin / MQ silicone resin / metal oxide composite (2-1#), silicon-boron hybrid phenolic resin (triphenyl ester) / methyl MQ silicone resin / metal oxide composite (2-2#), and titanium-boron hybrid phenolic resin (triphenyl ester) / methyl MQ silicone resin / metal oxide composite (2-3#) samples treated at 600°C are as follows: Figure 11 As shown. Figure 11 It can be seen that when treated at 600°C, a small amount of quartz crystal phase appeared in the pyrolysis products of composite materials 2-1#, 2-2#, and 2-3#.

[0168] The XRD spectra of the boron hybrid phenolic resin / MQ silicone resin / metal oxide composite (2-1#), silicon-boron hybrid phenolic resin (triphenyl ester) / methyl MQ silicone resin / metal oxide composite (2-2#), and titanium-boron hybrid phenolic resin (triphenyl ester) / methyl MQ silicone resin / metal oxide composite (2-3#) samples treated at 1020°C are as follows: Figure 12 As shown. Figure 12 It can be seen that when treated at 1020℃, in addition to a small amount of quartz crystal phase, a small amount of aluminum oxide and cristobalite crystal phase appeared in the pyrolysis products of composites 2-1# and 2-2# respectively; while 2-3# produced a large amount of quartz, cristobalite crystal phase and a small amount of perovskite crystal phase.

[0169] The XRD spectra of the boron hybrid phenolic resin / MQ silicone resin / metal oxide composite (2-1#), silicon-boron hybrid phenolic resin (triphenyl ester) / methyl MQ silicone resin / metal oxide composite (2-2#), and titanium-boron hybrid phenolic resin (triphenyl ester) / methyl MQ silicone resin / metal oxide composite (2-3#) samples treated at 1220°C are as follows: Figure 13 As shown. Figure 13 It can be seen that when treated at 1220℃, a large amount of quartz crystal phase was generated in the pyrolysis products of composites 2-1#, 2-2# and 2-3#, in addition to a small amount of cristobalite crystal phase.

[0170] Example 6

[0171] This embodiment provides a method for preparing zirconium silicate ceramics using a silicon / titanium / hybrid boron phenolic resin / MQ silicone resin-based ceramic fluxing and crystallization material. The specific steps are as follows:

[0172] Weigh the formula of silicon hybrid boron phenolic resin (triphenyl ester) and methyl MQ silicone resin, calcium oxide, magnesium oxide and aluminum oxide in Example 5, obtain 10.0g of silicon / titanium / hybrid boron phenolic resin / MQ silicone resin-based ceramic fluxing crystallization material after sintering, add 45.0g zirconium diboride, 27.0g silicon nitride, 18.0g boron nitride and 1.50g methyltrimethoxysilane, add 10mL of mixed solvent with a methanol / toluene volume ratio of 1:2. After mixing, the resin paste is evenly ground into a viscous state using an agate mortar and is standby.

[0173] Molding and drying: Place the above-mentioned viscous resin-based metal oxide paste into a 20mm×10mm×10mm fluoroplastic strip mold, place it in a room temperature drying oven to evaporate and remove the solvent, and then transfer it to a 50°C oven for further devolatilization to dryness.

[0174] Sintering preparation: The dried strips were transferred to a high-purity alumina porcelain boat, placed in a tubular high-temperature furnace, and sintered at 1500°C under normal pressure using the following temperature program to obtain a ceramic with zirconium silicate as the main crystalline phase.

[0175] Heating program: room temperature to 250℃×100min and hold for 60min, 250~1500℃×500min and hold for 60min, then program cooling 1500℃~200℃×600min, then naturally cool to below 100℃. Figure 14 shown.

[0176] The XRD spectrum of the zirconium silicate / zirconia ceramic sample obtained after sintering at 1500°C is shown in FIG. Figure 15 shown.

[0177] Depend on Figure 15 It can be seen that zirconium silicate / zirconium oxide ceramic phases are produced after sintering at a temperature of 1500° C., indicating that the fluxing and crystallization material of the present invention can significantly reduce the sintering temperature of zirconium silicate ceramics.

[0178] Comparative Example 1

[0179] The sintering temperature of zirconium silicate ceramics is generally above 1600°C, and the sintering time is also relatively long, usually taking several hours or even dozens of hours.

[0180] Only silicon-boron hybrid phenolic resin (triphenyl ester) and methyl MQ silicone resin polymer base, zirconium diboride, silicon nitride, boron nitride and methyltrimethoxysilane are used as the components of zirconium silicate ceramics. The composition and preparation steps are as follows:

[0181] Accurately weigh 5.00 g of titanium-boron hybrid phenolic resin (triphenyl ester) (III-A-Ti) and 5.00 g of methyl MQ silicone resin (M:Q = 0.8). Add 45.0 g of zirconium diboride, 27.0 g of silicon nitride, 18.0 g of boron nitride, and 1.50 g of methyltrimethoxysilane. Add 10 mL of a methanol / toluene solvent mixture with a volume ratio of 1:2. After mixing thoroughly, grind the resulting viscous resin paste in an agate mortar and pestle and set aside.

[0182] According to the method of Example 6, the material components of Comparative Example 1 were subjected to a sintered zirconium silicate ceramic test.

[0183] The XRD data of the ceramic material obtained by detection show that the degree of sintering of zirconium silicate ceramics is greatly reduced when the sintering components of the metal oxides calcium oxide, magnesium oxide and aluminum oxide are absent.

[0184] The XRD spectrum of the ceramic sample obtained after sintering at 1500°C is shown in FIG. Figure 16 shown.

[0185] Depend on Figure 16 It can be seen that although zirconium silicate / zirconia ceramic crystal phase is produced after sintering at 1500°C, the strength is relatively low, indicating that in the absence of metal oxide flux, the sintering degree of the zirconium silicate ceramic crystal phase is greatly reduced.

Claims

1. A ceramic fluxing and crystallizing material, characterized in that: The raw materials of the ceramic flux crystal material include: a composite material composed of a polymer-based raw material and a metal oxide; The polymer-based raw material is a mixture of at least one of boron hybrid phenolic resin, silicon-boron hybrid phenolic resin, titanium-boron hybrid phenolic resin and organosilicon resin; The boron hybrid phenolic resin is hydroxymethylated diphenyl borate or / and hydroxymethylated triphenyl borate, and the silicon-boron hybrid phenolic resin is obtained by further reacting the boron hybrid phenolic resin with dialkoxysilane R 1 R 2 Si(OR 3 )2 undergoes chain extension reaction to obtain R 1 、R 2 、R 3 The alkyl or phenyl groups are independently selected from C1-C6 groups; the titanium-boron hybrid phenolic resin is obtained by further transesterifying the boron hybrid phenolic resin with titanate; the metal oxide includes at least calcium oxide, magnesium oxide and aluminum oxide, or further includes at least one of silicon dioxide and boric acid.

2. The ceramic fluxing and crystallization material according to claim 1, characterized in that The hydroxymethylated diphenyl borate has the following structure: or ; The hydroxymethylated triphenyl borate has the following structure: or ; The silicon-boron hybrid phenolic resin has the following structure: or ; or or ; The titanium-boron hybrid phenolic resin has the following structure: or ; or or ; The dialkoxysilane R 1 R 2 Si(OR 3 ) 2 is at least one selected from dimethyldimethoxysilane, dimethyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methylhydrogendimethoxysilane, and methylhydrogendiethoxysilane; The titanate is at least one of ethyl titanate, isopropyl titanate, n-butyl titanate, and poly-n-butyl titanate.

3. The ceramic fluxing and crystallizing material according to claim 1, characterized in that: The molar ratio of dialkoxysilane to boron hybrid phenolic resin is 2.0:1.0 to 2.2:1.0, and the temperature of the chain extension reaction is 40-120°C; The molar ratio of titanate to boron hybrid phenolic resin is 4.0:1.0 to 4.2:1.0; and the temperature of the transesterification reaction is 20-30°C.

4. The ceramic fluxing and crystallizing material according to claim 1, characterized in that: The organic silicone resin is MQ silicone resin.

5. The ceramic fluxing and crystallizing material according to claim 4, characterized in that: The MQ silicone resin is at least one of methyl MQ silicone resin, methylphenyl MQ silicone resin, methylvinyl MQ silicone resin, and methylhydrogen MQ silicone resin, and the M / Q ratio of the MQ silicone resin is between 0.30 and 1.

20.

6. The ceramic fluxing and crystallizing material according to claim 4, characterized in that: The weight ratio of the boron hybrid phenolic resin, silicon-boron hybrid phenolic resin or titanium-boron hybrid phenolic resin to the MQ silicone resin is between 2:1 and 1:

2.

7. The ceramic fluxing and crystallizing material according to claim 1, wherein Boric acid is calculated as B2O3, and the molar ratio of oxides is: CaO: MgO: Al2O3: B2O3: SiO2 = (0.50~0.8): (0.10~0.30): (0.63~0.85): (5.30~6.00): (0.200~0.500), of which SiO2 and B2O3 produced by polymer-based raw materials are included in the composition.

8. The ceramic fluxing and crystallizing material according to claim 7, characterized in that: The metal oxide is in the form of fine powder with a particle size of more than 200 meshes.

9. The ceramic fluxing and crystallization material according to claim 1, wherein In the composite material composed of the polymer-based raw material and the metal oxide, the weight ratio of the polymer-based raw material to the metal oxide is 1:9 to 9:

1.

10. The ceramic fluxing and crystallizing material according to claim 1, wherein In the composite material composed of the polymer-based raw material and the metal oxide, the weight ratio of the polymer-based raw material to the metal oxide is 2:8 to 4:

6.

11. The method for preparing the ceramic flux crystal material according to any one of claims 1 to 10, comprising the following steps: The polymer-based raw material is dissolved in a solvent, and a metal oxide is added, or a surface treatment agent for the metal oxide is added, mixed evenly, dried, and formed to obtain a composite material; and then sintered to obtain a ceramic fluxing and crystallization material.

12. The method for preparing ceramic flux crystal material according to claim 11, characterized in that: The sintering temperature is 250-1250°C.

13. Use of the ceramic flux crystal material according to any one of claims 1 to 10 in the preparation of ceramic adhesives, ceramic glazes, and high-temperature resistant ceramics.

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