阅读说明：本技术 一种制备氧化锆研磨珠用粘结剂 (Binder for preparing zirconium oxide grinding beads ) 是由 孟超 任永国 朱振宇 魏小威 范孝友 于 2021-01-26 设计创作，主要内容包括：本发明公开了一种制备氧化锆研磨珠用粘结剂,包括以下重量份原料：骨架树脂20-30份、弹性体树脂液8-15份、聚乙二醇0.1-10份、羟丙基甲基纤维素0.1-5份、三乙醇胺0.1-5份、去离子水85-99份、导热填料1-2份、润滑剂0.1-0.5份和抗氧化剂0.1-0.3份,本发明粘结剂使氧化锆珠在滚动成型法制备过程中赋予氧化锆粉一定的可塑性,保证在研磨珠成型过程中不发生分层现象和减少粉体在成型设备中的粘壁现象,能够提高氧化锆珠成型毛坯的致密度和球形度,保证氧化锆珠在烧结后的抗破碎强度和韧性,使其具有优异的耐磨性。(The invention discloses a binder for preparing zirconium oxide grinding beads, which comprises the following raw materials in parts by weight: 20-30 parts of skeleton resin, 8-15 parts of elastomer resin liquid, 0.1-10 parts of polyethylene glycol, 0.1-5 parts of hydroxypropyl methyl cellulose, 0.1-5 parts of triethanolamine, 85-99 parts of deionized water, 1-2 parts of heat-conducting filler, 0.1-0.5 part of lubricant and 0.1-0.3 part of antioxidant.)

1. The binder for preparing the zirconia grinding beads is characterized by comprising the following raw materials in parts by weight: 20-30 parts of skeleton resin, 8-15 parts of elastomer resin liquid, 0.1-10 parts of polyethylene glycol, 0.1-5 parts of hydroxypropyl methyl cellulose, 0.1-5 parts of triethanolamine, 85-99 parts of deionized water, 1-2 parts of heat-conducting filler, 0.1-0.5 part of lubricant and 0.1-0.3 part of antioxidant;

the binder for preparing the zirconia grinding beads is prepared by the following steps:

firstly, adding skeleton resin, elastomer resin liquid, polyethylene glycol, triethanolamine and deionized water into a reaction kettle, stirring and mixing for 30min at the room temperature and the rotation speed of 200-;

and secondly, transferring the mixture into a storage container, aging and standing for 20 hours to obtain the binder for preparing the zirconia grinding beads.

2. The binder of claim 1, wherein the thermally conductive filler is prepared by the steps of:

step S11, mixing sodium sulfate, potassium sulfate, aluminum sulfate and deionized water according to the ratio of 1 g: 1 g: 1 g: adding 5-10mL of the solution into a four-neck flask, stirring at the rotating speed of 60r/min for 5-8min under the condition of room temperature to obtain a solution A, preparing a saturated sodium carbonate solution from sodium carbonate and deionized water, adding the saturated sodium carbonate solution into the four-neck flask to adjust the pH value to 7 under the water bath heating condition of 60 ℃, then adding deionized water into the four-neck flask to dilute the volume of the solution to 3 times of the original volume of the solution, ultrasonically dispersing the solution for 20-40min at the frequency of 30-50kHz, standing the solution for 6-8h, filtering, drying a filter cake in a 100 ℃ constant temperature drying box for 5-10h, putting a dried product into a crucible, calcining the product in a muffle furnace at the temperature of 1200 ℃ for 5h, cooling and taking out the product, washing the product with deionized water for 3-5 times and filtering, and finally drying the product in a 90-100 ℃ drying box to;

step S12, mixing the nano-alumina, the deionized water, the anhydrous ethanol and the zirconate coupling agent according to the proportion of 1-3 g: 20-40 mL: 5-10 mL: adding 0.2g of the mixture into a reaction kettle, controlling the temperature at 50 ℃, stirring and reacting for 30-50min at the rotation speed of 100-200r/min, performing suction filtration, washing a filter cake for 3-5 times by using distilled water, and finally drying in an oven at 80-90 ℃ until the weight is constant to obtain the heat-conducting filler.

3. The binder of claim 1, wherein the skeleton resin is polyvinylpyrrolidone, polyacrylamide, and polymaleic anhydride at a mass ratio of 0.5: 1-3: 1 are mixed.

4. The binder of claim 1, wherein the antioxidant is phenothiazine, the polyethylene glycol has a molecular weight of 2000, and the hydroxypropyl methyl fiber has a molecular weight of 200000.

5. The binder of claim 1, wherein the elastomer resin liquid is prepared by the steps of:

step S21, adding aqueous epoxy resin into a three-neck flask, heating to 85-90 ℃, adding methoxyphenol into the three-neck flask, stirring at the rotation speed of 120r/min for 20-40min, and mixing methacrylic acid and N, N-dimethylbenzylamine according to the volume ratio of 1:1, dropwise adding the mixture into a three-neck flask by using a constant-pressure dropping funnel at the dropping speed of 1-3 drops/second, controlling the reaction temperature to be 100-;

and S22, adding polyether polyol, 1, 4-butanediol and a catalyst into a reaction kettle, stirring for 10min at the rotation speed of 50r/min, adding liquefied MDI, increasing the rotation speed to 130r/min, stirring for 30-50min to obtain a polyurethane component, adding benzoyl peroxide and N, N-dihydroxyethyl aniline into the polyurethane component, stirring for 5min at a constant rotation speed, adding the monomer mixture obtained in the step S21 into the reaction kettle, and stirring for 2-4h to obtain the elastomer resin liquid.

6. The binder for preparing zirconia grinding beads according to claim 5, wherein the mass ratio of the aqueous epoxy resin, the methoxyphenol, the methacrylic acid and the styrene in step S21 is 5-8:1:1: 1; in the step S22, the polyether polyol is polypropylene glycol 3000, the catalyst is MDI elastomer catalyst CUCAT-HSF, and the dosage ratio of the polyether polyol, 1, 4-butanediol, the catalyst, liquefied MDI, benzoyl peroxide, N-dihydroxyethylaniline and the monomer mixture is 5 mL: 10mL of: 0.1 g: 10mL of: 0.1 g: 0.1 g: 8-12 mL.

7. The binder for preparing zirconia grinding beads according to claim 1, wherein the lubricant is one or more of paraffin wax, microcrystalline wax or carnauba wax mixed in an arbitrary ratio.

Technical Field

The invention belongs to the technical field of preparation of zirconium oxide grinding beads made of inorganic non-metallic materials, and particularly relates to a binder for preparing zirconium oxide grinding beads.

Background

Zirconia ceramics have the advantages of high toughness, high bending strength, high wear resistance, thermal expansion coefficient close to that of steel and the like, so the zirconia ceramics are widely applied to the field of structural ceramics. Mainly comprises the fields of 3Y-TZP grinding balls, ball valve ball seats, optical fiber sleeves, optical fiber contact pins, watch chains, shells, mobile phone back plates and the like. The zirconia grinding bead forming method mainly comprises two methods, namely a rolling forming method and a pressing forming method, wherein zirconia ceramic powder belongs to ridge materials and does not have plasticity, glue with certain concentration is needed to be used in the process of preparing zirconia beads by the rolling forming method to ensure that no layering phenomenon occurs in the grinding bead forming process and the wall sticking phenomenon of powder in forming equipment is reduced, the density and the sphericity of zirconia bead forming blanks can be improved, the crushing resistance and the toughness of the zirconia beads after sintering are ensured, the zirconia beads have excellent wear resistance, and the raw material utilization rate and the yield of the zirconia bead blanks in the preparation process can be improved.

Chinese patent with publication number CN105967695A discloses a ceramic injection molding binder and a preparation method thereof, wherein the binder components comprise 50-60 parts of polyvinyl acetate, 5-10 parts of vinyl acetate, 5-8 parts of bone glue, 10-18 parts of paraffin, 3-5 parts of talc, 3-5 parts of bentonite, 2-4 parts of water glass, 1-3 parts of flurbiprofen, 2-6 parts of stearic acid and 2-6 parts of methylethanolamine, and the components are fully mixed at 60-70 ℃.

Disclosure of Invention

The invention aims to provide a binder for preparing zirconium oxide grinding beads.

The technical problems to be solved by the invention are as follows:

in the prior art, the binder used for preparing the zirconia grinding bead by rolling forming generally has the defects of single component structure and poor compatibility, and easily causes the problems of microcracks and deformation of the grinding bead after rolling forming, more gaps after sintering, poor strength and the like.

The purpose of the invention can be realized by the following technical scheme:

the binder for preparing the zirconia grinding beads comprises the following raw materials in parts by weight: 20-30 parts of skeleton resin, 8-15 parts of elastomer resin liquid, 0.1-10 parts of polyethylene glycol, 0.1-5 parts of hydroxypropyl methyl cellulose, 0.1-5 parts of triethanolamine, 85-99 parts of deionized water, 1-2 parts of heat-conducting filler, 0.1-0.5 part of lubricant and 0.1-0.3 part of antioxidant;

the binder for preparing the zirconia grinding beads is prepared by the following steps:

firstly, adding skeleton resin, elastomer resin liquid, polyethylene glycol, triethanolamine and deionized water into a reaction kettle, stirring and mixing for 30min at the room temperature and the rotation speed of 200-;

and secondly, transferring the mixture into a storage container, aging and standing for 20 hours to obtain the binder for preparing the zirconia grinding beads.

Further, the heat conductive filler is made by the following steps:

step S11, mixing sodium sulfate, potassium sulfate, aluminum sulfate and deionized water according to the ratio of 1 g: 1 g: 1 g: adding 5-10mL of the solution into a four-neck flask, stirring at the rotating speed of 60r/min for 5-8min under the condition of room temperature to obtain a solution A, preparing a saturated sodium carbonate solution from sodium carbonate and deionized water, adding the saturated sodium carbonate solution into the four-neck flask to adjust the pH value to 7 under the water bath heating condition of 60 ℃, then adding deionized water into the four-neck flask to dilute the volume of the solution to 3 times of the original volume of the solution, ultrasonically dispersing the solution for 20-40min at the frequency of 30-50kHz, standing the solution for 6-8h, filtering, drying a filter cake in a 100 ℃ constant temperature drying box for 5-10h, putting a dried product into a crucible, calcining the product in a muffle furnace at the temperature of 1200 ℃ for 5h, cooling and taking out the product, washing the product with deionized water for 3-5 times and filtering, and finally drying the product in a 90-100 ℃ drying box to;

step S12, mixing the nano-alumina, the deionized water, the anhydrous ethanol and the zirconate coupling agent according to the proportion of 1-3 g: 20-40 mL: 5-10 mL: adding 0.2g of the mixture into a reaction kettle, controlling the temperature at 50 ℃, stirring and reacting for 30-50min at the rotation speed of 100-200r/min, performing suction filtration, washing a filter cake for 3-5 times by using distilled water, and finally drying in an oven at 80-90 ℃ until the weight is constant to obtain the heat-conducting filler.

Aluminum sulfate is used as an aluminum source, saturated sodium carbonate solution is used as a precipitator, aluminum hydroxide gel is prepared by a sol-gel method, then deionized water is used for dilution, an aluminum hydroxide precursor is obtained by constant-temperature drying, then nano aluminum oxide is obtained by calcining, washing and drying, the nano aluminum oxide is dispersed in ethanol solution, the-OH on the surface of the nano aluminum oxide and the-COOH of a zirconate coupling agent are subjected to esterification reaction, the dispersibility of the nano aluminum oxide in a binder is improved, the thermal conductivity of the aluminum oxide is much higher than that of an organic polymer, the nano aluminum oxide is easy to combine with organic polymer macromolecular chains in the polymer to form a heat conduction channel with a cross-linking structure, in the early degreasing stage of the zirconium oxide grinding bead preparation process, the binder plays a role of maintaining the integrity of an embryo body and absorbing stress generated when a part of small molecular solvent leaves the embryo body, in the later degreasing stage, along with the removal of the small molecular solvent, the blank body is of a loose porous structure, the existence of the heat-conducting filler can avoid or relieve the warping and cracking caused by local high pressure generated by thermal cracking, the integrity of the blank body is ensured, the zirconium propoxy in the zirconate coupling agent is hydrolyzed while the dispersibility of the nano-alumina is improved, so that the molecules of the coupling agent are combined with the surface of the ceramic powder, the hydrophobic property of the ceramic powder is improved, the ceramic powder is uniformly dispersed in the binder, and in the thermal degreasing process, a trace amount of the zirconate coupling agent is decomposed into zirconium oxide, so that the wear resistance of the grinding bead is improved.

Further, the skeleton resin is prepared from polyvinylpyrrolidone, polyacrylamide and polymaleic anhydride according to a mass ratio of 0.5: 1-3: 1 are mixed.

Further, the antioxidant is phenothiazine, the molecular weight of the polyethylene glycol is 2000, and the molecular weight of the hydroxypropyl methyl fiber is 200000.

Further, the elastomer resin liquid is prepared by the following steps:

step S21, adding aqueous epoxy resin into a three-neck flask, heating to 85-90 ℃, adding methoxyphenol into the three-neck flask, stirring at the rotation speed of 120r/min for 20-40min, and mixing methacrylic acid and N, N-dimethylbenzylamine according to the volume ratio of 1:1, dropwise adding the mixture into a three-neck flask by using a constant-pressure dropping funnel at the dropping speed of 1-3 drops/second, controlling the reaction temperature to be 100-;

and S22, adding polyether polyol, 1, 4-butanediol and a catalyst into a reaction kettle, stirring for 10min at the rotation speed of 50r/min, adding liquefied MDI, increasing the rotation speed to 130r/min, stirring for 30-50min to obtain a polyurethane component, adding benzoyl peroxide and N, N-dihydroxyethyl aniline into the polyurethane component, stirring for 5min at a constant rotation speed, adding the monomer mixture obtained in the step S21 into the reaction kettle, and stirring for 2-4h to obtain the elastomer resin liquid.

Further, the mass ratio of the aqueous epoxy resin, the methoxyphenol, the methacrylic acid and the styrene in the step S21 is 5-8:1:1: 1; in the step S22, the polyether polyol is polypropylene glycol 3000, the catalyst is MDI elastomer catalyst CUCAT-HSF, and the dosage ratio of the polyether polyol, 1, 4-butanediol, the catalyst, liquefied MDI, benzoyl peroxide, N-dihydroxyethylaniline and the monomer mixture is 5 mL: 10mL of: 0.1 g: 10mL of: 0.1 g: 0.1 g: 8-12 mL.

Dispersing several comonomers into aqueous epoxy resin to obtain a monomer mixture, then mixing polyol and isocyanate to obtain a polyurethane component, taking benzoyl peroxide as an initiator and N, N-dihydroxyethyl aniline as an accelerator, adding the monomer mixture into the polyurethane component to obtain an elastomer resin liquid, and mutually crosslinking and penetrating polymer monomers through polymerization reaction to form the elastomer resin liquid.

Further, the lubricant is one or more of paraffin, microcrystalline wax or carnauba wax which are mixed according to any proportion.

The invention has the beneficial effects that:

the invention uses water-soluble high molecular polymer, heat conductive filler and adjuvant to prepare a binder for preparing zirconia grinding beads, wherein, several comonomers are dispersed in water-based epoxy resin to obtain a monomer mixture, then polyol and isocyanate are mixed to obtain a polyurethane component, benzoyl peroxide is used as an initiator, N-dihydroxyethyl aniline is used as an accelerant, the monomer mixture is added into the polyurethane component to obtain elastomer resin liquid, polymer monomers are mutually cross-linked and penetrated through a polymerization reaction to form the elastomer resin liquid, forced compatibility and synergistic effect are generated due to the mutual penetration among cross-linked networks, the resin vitrification temperature can be effectively improved, and the strength performance of the elastomer resin liquid as a supporting green body of a macromolecular framework in the degreasing process of zirconia grinding beads is further enhanced;

aluminum sulfate is used as an aluminum source, saturated sodium carbonate solution is used as a precipitator, aluminum hydroxide gel is prepared by a sol-gel method, then deionized water is used for dilution, an aluminum hydroxide precursor is obtained by constant-temperature drying, then nano aluminum oxide is obtained by calcining, washing and drying, the nano aluminum oxide is dispersed in ethanol solution, the-OH on the surface of the nano aluminum oxide and the-COOH of a zirconate coupling agent are subjected to esterification reaction, the dispersibility of the nano aluminum oxide in a binder is improved, the thermal conductivity of the aluminum oxide is much higher than that of an organic polymer, the nano aluminum oxide is easy to combine with organic polymer macromolecular chains in the polymer to form a heat conduction channel with a cross-linking structure, in the early degreasing stage of the zirconium oxide grinding bead preparation process, the binder plays a role of maintaining the integrity of an embryo body and absorbing stress generated when a part of small molecular solvent leaves the embryo body, in the later degreasing stage, along with the removal of the small molecular solvent, the blank body is of a loose porous structure, the existence of the heat-conducting filler can avoid or relieve the warping and cracking caused by local high pressure generated by thermal cracking, the integrity of the blank body is ensured, the zirconium propoxy in the zirconate coupling agent is hydrolyzed while the dispersibility of the nano-alumina is improved, so that the molecules of the coupling agent are combined with the surface of the ceramic powder, the hydrophobic property of the ceramic powder is improved, the ceramic powder is uniformly dispersed in the binder, and in the thermal degreasing process, a trace amount of the zirconate coupling agent is decomposed into zirconium oxide, so that the wear resistance of the grinding bead is improved;

the hydroxypropyl methyl cellulose has excellent surface activity and water solubility, plays a role of a bridge in a binder, ensures that the compatibility of each component in the binder is good, prevents polyvinyl alcohol from being oxidized in the mixing process due to the addition of an antioxidant phenothiazine, and can reduce the defect caused by the segregation of the binder due to the addition of polyvinylpyrrolidone in the skeleton resin, because the introduction of polyvinylpyrrolidone can effectively inhibit the crystallization of polyethylene glycol, improve the uniformity of a green body, reduce the pore size of the green body after a thermal desorption process, promote the progress of sintering densification, obviously reduce the sintering defect and improve the mechanical property of a sintered body, therefore, the binder of the invention ensures that zirconia beads endow zirconia powder with certain plasticity in the rolling forming method in the preparation process, ensures that the delamination phenomenon does not occur in the forming process of grinding beads and reduces the wall sticking phenomenon of powder in forming equipment, the compactness and sphericity of the zirconia bead forming blank can be improved, and the crushing resistance strength and toughness of the sintered zirconia beads are ensured, so that the zirconia beads have excellent wear resistance.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

The binder for preparing the zirconia grinding beads comprises the following raw materials in parts by weight: 20 parts of skeleton resin, 8 parts of elastomer resin liquid, 0.1 part of polyethylene glycol, 0.1 part of hydroxypropyl methyl cellulose, 0.1 part of triethanolamine, 85 parts of deionized water, 1 part of heat-conducting filler, 0.1 part of lubricant and 0.1 part of antioxidant;

the binder for preparing the zirconia grinding beads is prepared by the following steps:

firstly, adding skeleton resin, elastomer resin liquid, polyethylene glycol, triethanolamine and deionized water into a reaction kettle, stirring and mixing at the rotating speed of 200r/min for 30min at room temperature, adding a heat-conducting filler, hydroxypropyl methyl cellulose, a lubricant and an antioxidant into the reaction kettle, heating to 55 ℃, and continuously reacting for 30min under the condition that the rotating speed is not changed to obtain a mixture;

and secondly, transferring the mixture into a storage container, aging and standing for 20 hours to obtain the binder for preparing the zirconia grinding beads.

Wherein the heat conductive filler is prepared by the following steps:

step S11, mixing sodium sulfate, potassium sulfate, aluminum sulfate and deionized water according to the ratio of 1 g: 1 g: 1 g: adding 5mL of the solution into a four-mouth flask, stirring for 5min at the rotating speed of 60r/min under the condition of room temperature to obtain a solution A, preparing saturated sodium carbonate solution from sodium carbonate and deionized water, adding the saturated sodium carbonate solution into the four-mouth flask to adjust the pH value to 7 under the water bath heating condition of 60 ℃, then adding deionized water into the four-mouth flask to dilute the volume of the solution to 3 times of the original volume, ultrasonically dispersing the solution for 20min under the frequency of 30kHz, standing the solution for 6h, filtering, drying a filter cake in a 100 ℃ constant temperature drying oven for 5h, putting the dried product into a crucible, calcining the product in a muffle furnace at the temperature of 1200 ℃ for 5h, cooling the product, washing the product with deionized water for 3 times, filtering, and finally drying the product in a 90 ℃ oven to constant weight to obtain nano-dried aluminum;

step S12, mixing the nano-alumina, the deionized water, the anhydrous ethanol and the zirconate coupling agent according to the proportion of 1 g: 20mL of: 5mL of: adding 0.2g of the mixture into a reaction kettle, controlling the temperature to be 50 ℃, stirring and reacting for 30min under the condition of the rotating speed of 100r/min, carrying out suction filtration, washing a filter cake for 3 times by using distilled water, and finally drying in an oven at the temperature of 80 ℃ to constant weight to obtain the heat-conducting filler.

Wherein the skeleton resin is prepared from polyvinylpyrrolidone, polyacrylamide and polymaleic anhydride according to a mass ratio of 0.5: 1:1 are mixed.

Wherein the antioxidant is phenothiazine, the molecular weight of the polyethylene glycol is 2000, and the molecular weight of the hydroxypropyl methyl fiber is 200000.

Wherein the elastomer resin liquid is prepared by the following steps:

step S21, adding aqueous epoxy resin into a three-neck flask, heating to 85 ℃, adding methoxyphenol into the three-neck flask, stirring for 20min at the rotation speed of 120r/min, and mixing methacrylic acid and N, N-dimethylbenzylamine according to the volume ratio of 1:1, after mixing, dropwise adding the mixture into a three-neck flask by using a constant-pressure dropping funnel at the dropping speed of 1 drop/second, controlling the reaction temperature to be 100 ℃, after the dropwise adding is finished, reacting for 20min at the rotating speed of 200r/min, cooling to 80 ℃, adding styrene into the three-neck flask, and continuously stirring for 30min at the constant rotating speed to obtain a monomer mixture;

and S22, adding polyether glycol, 1, 4-butanediol and a catalyst into a reaction kettle, stirring for 10min at the rotation speed of 50r/min, adding liquefied MDI, increasing the rotation speed to 130r/min, stirring for 30min to obtain a polyurethane component, adding benzoyl peroxide and N, N-dihydroxyethyl aniline into the polyurethane component, stirring for 5min at a constant rotation speed, adding the monomer mixture obtained in the step S21 into the reaction kettle, and stirring for reaction for 2h to obtain the elastomer resin liquid.

Wherein the mass ratio of the waterborne epoxy resin, the methoxyphenol, the methacrylic acid and the styrene in the step S21 is 5:1:1: 1; in the step S22, the polyether polyol is polypropylene glycol 3000, the catalyst is MDI elastomer catalyst CUCAT-HSF, and the dosage ratio of the polyether polyol, 1, 4-butanediol, the catalyst, liquefied MDI, benzoyl peroxide, N-dihydroxyethylaniline and the monomer mixture is 5 mL: 10mL of: 0.1 g: 10mL of: 0.1 g: 0.1 g: 8 mL.

Wherein the lubricant is paraffin.

Example 2

The binder for preparing the zirconia grinding beads comprises the following raw materials in parts by weight: 25 parts of skeleton resin, 10 parts of elastomer resin liquid, 2 parts of polyethylene glycol, 2 parts of hydroxypropyl methyl cellulose, 3 parts of triethanolamine, 90 parts of deionized water, 1 part of heat-conducting filler, 0.2 part of lubricant and 0.2 part of antioxidant;

the binder for preparing the zirconia grinding beads is prepared by the following steps:

firstly, adding skeleton resin, elastomer resin liquid, polyethylene glycol, triethanolamine and deionized water into a reaction kettle, stirring and mixing at the rotating speed of 250r/min for 30min at room temperature, adding a heat-conducting filler, hydroxypropyl methyl cellulose, a lubricant and an antioxidant into the reaction kettle, heating to 58 ℃, and continuously reacting for 45min under the condition that the rotating speed is not changed to obtain a mixture;

and secondly, transferring the mixture into a storage container, aging and standing for 20 hours to obtain the binder for preparing the zirconia grinding beads.

Wherein the heat conductive filler is prepared by the following steps:

step S11, mixing sodium sulfate, potassium sulfate, aluminum sulfate and deionized water according to the ratio of 1 g: 1 g: 1 g: adding 8mL of the solution into a four-neck flask, stirring for 7min at the rotating speed of 60r/min under the condition of room temperature to obtain a solution A, preparing saturated sodium carbonate solution from sodium carbonate and deionized water, adding the saturated sodium carbonate solution into the four-neck flask to adjust the pH value to 7 under the water bath heating condition of 60 ℃, then adding deionized water into the four-neck flask to dilute the volume of the solution to 3 times of the original volume, ultrasonically dispersing the solution for 30min under the frequency of 40kHz, standing the solution for 7h, filtering, drying a filter cake in a 100 ℃ constant temperature drying oven for 8h, putting the dried product into a crucible, calcining the product in a muffle furnace at the temperature of 1200 ℃ for 5h, cooling the product, washing the product with deionized water for 4 times, filtering, and finally drying the product in a 95 ℃ oven to constant weight to obtain nano-dried aluminum;

step S12, mixing the nano-alumina, the deionized water, the anhydrous ethanol and the zirconate coupling agent according to the proportion of 2 g: 30mL of: 8mL of: adding 0.2g of the mixture into a reaction kettle, controlling the temperature to be 50 ℃, stirring and reacting for 40min under the condition of the rotating speed of 150r/min, carrying out suction filtration, washing a filter cake for 4 times by using distilled water, and finally drying in an oven at the temperature of 85 ℃ to constant weight to obtain the heat-conducting filler.

Wherein the skeleton resin is prepared from polyvinylpyrrolidone, polyacrylamide and polymaleic anhydride according to a mass ratio of 0.5: 2: 1 are mixed.

Wherein the antioxidant is phenothiazine, the molecular weight of the polyethylene glycol is 2000, and the molecular weight of the hydroxypropyl methyl fiber is 200000.

Wherein the elastomer resin liquid is prepared by the following steps:

step S21, adding aqueous epoxy resin into a three-neck flask, heating to 88 ℃, adding methoxyphenol into the three-neck flask, stirring for 30min at the rotation speed of 120r/min, and mixing methacrylic acid and N, N-dimethylbenzylamine according to the volume ratio of 1:1, after mixing, dropwise adding the mixture into a three-neck flask by using a constant-pressure dropping funnel at the dropping speed of 2 drops/second, controlling the reaction temperature to be 105 ℃, after the dropwise adding is finished, reacting for 30min at the rotating speed of 200r/min, cooling to 80 ℃, adding styrene into the three-neck flask, and continuously stirring for 30min at the constant rotating speed to obtain a monomer mixture;

and S22, adding polyether glycol, 1, 4-butanediol and a catalyst into a reaction kettle, stirring for 10min at the rotation speed of 50r/min, adding liquefied MDI, increasing the rotation speed to 130r/min, stirring for 40min to obtain a polyurethane component, adding benzoyl peroxide and N, N-dihydroxyethyl aniline into the polyurethane component, stirring for 5min at the constant rotation speed, adding the monomer mixture obtained in the step S21 into the reaction kettle, and stirring for reaction for 3h to obtain the elastomer resin liquid.

Wherein the mass ratio of the waterborne epoxy resin, the methoxyphenol, the methacrylic acid and the styrene in the step S21 is 7:1:1: 1; in the step S22, the polyether polyol is polypropylene glycol 3000, the catalyst is MDI elastomer catalyst CUCAT-HSF, and the dosage ratio of the polyether polyol, 1, 4-butanediol, the catalyst, liquefied MDI, benzoyl peroxide, N-dihydroxyethylaniline and the monomer mixture is 5 mL: 10mL of: 0.1 g: 10mL of: 0.1 g: 0.1 g: 10 mL.

Wherein the lubricant is paraffin.

Example 3

The binder for preparing the zirconia grinding beads comprises the following raw materials in parts by weight: 30 parts of skeleton resin, 15 parts of elastomer resin liquid, 10 parts of polyethylene glycol, 5 parts of hydroxypropyl methyl cellulose, 5 parts of triethanolamine, 99 parts of deionized water, 2 parts of heat-conducting filler, 0.5 part of lubricant and 0.3 part of antioxidant;

the binder for preparing the zirconia grinding beads is prepared by the following steps:

firstly, adding skeleton resin, elastomer resin liquid, polyethylene glycol, triethanolamine and deionized water into a reaction kettle, stirring and mixing at the rotating speed of 300r/min for 30min at room temperature, adding a heat-conducting filler, hydroxypropyl methyl cellulose, a lubricant and an antioxidant into the reaction kettle, heating to 60 ℃, and continuously reacting for 60min under the condition that the rotating speed is not changed to obtain a mixture;

and secondly, transferring the mixture into a storage container, aging and standing for 20 hours to obtain the binder for preparing the zirconia grinding beads.

Wherein the heat conductive filler is prepared by the following steps:

step S11, mixing sodium sulfate, potassium sulfate, aluminum sulfate and deionized water according to the ratio of 1 g: 1 g: 1 g: adding 10mL of the solution into a four-mouth flask, stirring for 8min at the rotating speed of 60r/min under the condition of room temperature to obtain a solution A, preparing saturated sodium carbonate solution from sodium carbonate and deionized water, adding the saturated sodium carbonate solution into the four-mouth flask to adjust the pH value to 7 under the water bath heating condition of 60 ℃, then adding deionized water into the four-mouth flask to dilute the volume of the solution to 3 times of the original volume, ultrasonically dispersing the solution for 40min under the frequency of 50kHz, standing the solution for 8h, filtering, drying a filter cake in a 100 ℃ constant temperature drying oven for 10h, putting the dried product into a crucible, calcining the product in a muffle furnace at the temperature of 1200 ℃ for 5h, cooling the product, washing the product with deionized water for 5 times, filtering, and finally drying the product in a 100 ℃ oven to constant weight to obtain nano-alumina;

step S12, mixing the nano-alumina, the deionized water, the anhydrous ethanol and the zirconate coupling agent according to the proportion of 3 g: 40mL of: 10mL of: adding 0.2g of the mixture into a reaction kettle, controlling the temperature to be 50 ℃, stirring and reacting for 50min under the condition of the rotating speed of 200r/min, carrying out suction filtration, washing a filter cake for 5 times by using distilled water, and finally drying in a 90 ℃ oven to constant weight to obtain the heat-conducting filler.

Wherein the skeleton resin is prepared from polyvinylpyrrolidone, polyacrylamide and polymaleic anhydride according to a mass ratio of 0.5: 3: 1 are mixed.

Wherein the antioxidant is phenothiazine, the molecular weight of the polyethylene glycol is 2000, and the molecular weight of the hydroxypropyl methyl fiber is 200000.

Wherein the elastomer resin liquid is prepared by the following steps:

step S21, adding aqueous epoxy resin into a three-neck flask, heating to 90 ℃, adding methoxyphenol into the three-neck flask, stirring for 40min at the rotation speed of 120r/min, and mixing methacrylic acid and N, N-dimethylbenzylamine according to the volume ratio of 1:1, after mixing, dropwise adding the mixture into a three-neck flask by using a constant-pressure dropping funnel at the dropping speed of 3 drops/second, controlling the reaction temperature to be 110 ℃, after the dropwise adding is finished, reacting for 45min at the rotating speed of 200r/min, cooling to 80 ℃, adding styrene into the three-neck flask, and continuously stirring for 30min at the constant rotating speed to obtain a monomer mixture;

and S22, adding polyether glycol, 1, 4-butanediol and a catalyst into a reaction kettle, stirring for 10min at the rotation speed of 50r/min, adding liquefied MDI, increasing the rotation speed to 130r/min, stirring for 50min to obtain a polyurethane component, adding benzoyl peroxide and N, N-dihydroxyethyl aniline into the polyurethane component, stirring for 5min at the constant rotation speed, adding the monomer mixture obtained in the step S21 into the reaction kettle, and stirring for reaction for 4h to obtain the elastomer resin liquid.

Wherein the mass ratio of the waterborne epoxy resin, the methoxyphenol, the methacrylic acid and the styrene in the step S21 is 8:1:1: 1; in the step S22, the polyether polyol is polypropylene glycol 3000, the catalyst is MDI elastomer catalyst CUCAT-HSF, and the dosage ratio of the polyether polyol, 1, 4-butanediol, the catalyst, liquefied MDI, benzoyl peroxide, N-dihydroxyethylaniline and the monomer mixture is 5 mL: 10mL of: 0.1 g: 10mL of: 0.1 g: 0.1 g: 12 mL.

Wherein the lubricant is paraffin.

Comparative example 1

The heat conductive filler in example 1 was removed, and the remaining raw materials and the preparation process were unchanged.

Comparative example 2

The elastomer resin liquid in example 2 was removed, and the remaining raw materials and preparation process were unchanged.

Comparative example 3

The comparative example is a common binder for producing zirconia grinding beads on the market.

The binders of examples 1 to 3 and comparative examples 1 to 3 and the same zirconia powder body were mixed at a mass ratio of 90; 10 mixing, preparing zirconia grinding beads with the same size by the same rolling forming method, and performing performance test on the zirconia grinding beads prepared from the raw materials of each group, wherein the test results are shown in the following table:

remarking: wherein the defective rate is a result of multiplying 100% by the ratio of the number of cracks, delamination, and chipping of the produced grinding beads to the total number of grinding beads.

As can be seen from the above table, the test results of the grinding beads prepared in examples 1 to 3 are superior to those of comparative examples 1 to 3 in the processes of testing density, strength, toughness, hardness and defective percentage, which shows that the binder for zirconia grinding beads prepared by the present invention has the advantages of heat conduction, uniform dispersion of the components, no delamination during the process of forming the grinding beads, reduced wall adhesion of powder in the forming equipment, improved compactness and sphericity of the zirconia bead forming blank, and ensured crushing resistance and toughness of the zirconia beads after sintering, so that the zirconia beads have excellent wear resistance.

The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.