A multiphase particle, a method of making the same and uses thereof

Abstract

The present invention relates to a multiphase particle, its manufacturing method and use. The multiphase particle has a multiphase structure comprising a first phase and a second phase, and an average particle size of 0.1-100 mm. The multiphase particle has high bulk strength and good interfacial adhesion with cement stone, and is particularly suitable for cement stone toughening applications.

Description

Technical Field

[0001] This invention relates to multiphase particles, and more particularly to multiphase particles for toughening cement paste. The invention also relates to a method for manufacturing the multiphase particles and their uses. Background Technology

[0002] Cementing is a crucial step in drilling operations. During the drilling cycle of an oil well, cementing is typically required multiple times. Cementing mainly involves injecting cement slurry downhole, which solidifies between the cementing casing and the wellbore to form a "cement sheath." Typically, the cement sheath formed by cement slurry must withstand the impact of high-energy jet perforation, large-scale fracturing and staged fracturing, as well as the collisions and impacts from the casing and drill bit during casing installation and continued drilling. Furthermore, due to crustal forces, the cement sheath is also subject to significant internal stresses caused by changes in the crustal structure. If the strength and toughness of the cement stone are insufficient, deformation and cracks will occur, compromising its overall integrity and leading to failure of interlayer sealing performance. This poses a potential safety hazard, especially for oil and gas wells with high acid gas content, particularly in later-stage production enhancement measures and development. In severe cases, it can affect the normal operation of the oil well, even causing permanent damage and significant economic losses. Therefore, cement sheaths typically require the addition of components that improve their toughness and strength to reduce their brittleness and the likelihood of them breaking.

[0003] To improve the toughness of cement paste, existing technologies mainly modify it by adding elastic particles such as rubber elastomers. Elastic particles are elastic materials, and cement composed of elastic particles has a lower Young's modulus and a higher Poisson's ratio compared to ordinary cement. This allows it to better absorb the cement deformation energy caused by casing expansion during fracturing, reducing the risk of "cement ring" seal failure.

[0004] Chinese patent CN201310066429 (An Elastic Cement Slurry and Its Manufacturing Method) discloses a cement slurry, in which the elastic material is a material designated WF-1. Chinese patent 201210029069 (An Elastic-Plastic Cement Slurry and Its Manufacturing Method) also discloses a cement slurry, in which the elastic material is natural rubber powder or industrial synthetic rubber powder. Summary of the Invention

[0005] The inventors of this invention discovered that traditional cementing elastic particles are generally elastic rubber powders. Due to the poor hydrophobicity or hydrophilicity of rubber powder surfaces, their adhesion to cement is poor. Adhesion refers to the intermolecular force at the interface between the cement and the bonded object. For a long time, the influence of oil well cement on the interfacial adhesion of the bonded object has been a focus of engineering attention, primarily concerning changes in adhesion and load-bearing capacity. Currently, due to insufficient interfacial adhesion between cementing elastic particles and cement stone, under the influence of fracturing or crustal movement stress, the elastic particles easily delaminate from the cement stone, causing internal "voids" within the cement stone, a serious defect. Therefore, in such cases, the elastic particles not only fail to provide toughening but also become a detrimental factor to the cement stone.

[0006] Through diligent research, the inventors of this invention discovered a multiphase particle. This multiphase particle can overcome the deficiency of insufficient bonding strength between elastic particles and cement paste in existing technologies, and this invention was completed based on this.

[0007] Specifically, the present invention relates to the following aspects.

[0008] 1. A multiphase particle having a multiphase structure comprising a first phase and a second phase (preferably composed of a first phase and a second phase), wherein the multiphase structure at least partially has a morphology (1): the first phase is a continuous phase having at least partially a porous structure, the second phase is a dispersed phase, wherein at least one (preferably more than 50%, 60%, 80%, 90%, or substantially all) of the second phase has a substantially spherical shape (referred to as a spherical second phase), and at least one (preferably more than 50%, 60%, 80%, 90%, or substantially all) of the spherical second phase is located within the pores (particularly substantially circular pores) of the porous structure of the first phase, or, the multiphase structure at least partially has a morphology (2): the second phase is a continuous phase (e.g., having a loose structure). The first phase is a dispersed phase, wherein at least one (preferably more than 50%, 60%, 80%, 90%, or substantially all of the total) of the first phase has a substantially columnar shape (e.g., at least one columnar shape selected from cylinders and prisms) (referred to as columnar first phase), or the multiphase structure has at least part of a morphology (3): a combination of the morphology (1) and the morphology (2), and the average particle size of the multiphase particles is at least 0.1 mm (preferably at least 0.2 mm, at least 0.35 mm, at least 0.5 mm, at least 0.75 mm, or at least 0.8 mm), and at most 100 mm (preferably at most 50 mm, at most 20 mm, at most 10 mm, at most 5 mm, at most 2 mm, at most 1.2 mm, or at most 1.0 mm).

[0009] 2. The multiphase particles described above or below, wherein the ratio of the Si element content (in wt%) in the second phase to the Si element content (in wt%) in the first phase is 5-20, 8-12, or 9-11.

[0010] 3. The multiphase particles described above or below have surface silanol groups and / or surface -NCO groups.

[0011] 4. The multiphase particles described above or below have a BET specific surface area of ​​1-200 m². 2 / g, 5-50m 2 / g or 10-30m 2 / g, and / or, with a water contact angle of 20-60°, 25-50°, 30-45° or 35-40°, and / or, with a pH of 7-10, 7.5-9 or 8-9, and / or, with an apparent density of 1.1-1.6 g / cm³. 3 Or 1.2-1.3 g / cm³ 3 .

[0012] 5. The multiphase particles described above or below, wherein the diameter of the spherical second phase is 0.1-50 micrometers (preferably 0.2-25 micrometers, 0.5-20 micrometers, 1-10 micrometers, or 2-8 micrometers), and / or the pore size is 0.05-100 micrometers (preferably 0.2-50 micrometers, 0.5-25 micrometers, or 1-15 micrometers), and / or the length of the columnar first phase is 0.1-50 micrometers (preferably 0.2-20 micrometers, 0.5-10 micrometers, or 1-5 micrometers), and the diameter is 0.1-10 micrometers (preferably 2-5 micrometers), and / or the Si content (based on Si) of the multiphase particles is 0.5-5 wt% (preferably 1-3.5 wt%), based on a total mass of 100 wt% of the multiphase particles.

[0013] 6. The multiphase particles described above or below, wherein the spherical second phase is located within the pore, and the ratio of the pore opening size to the diameter of the spherical second phase is at least 1, greater than 1, 1.05, 1.1, 1.15 or 1.2, and at most 10, 5, 2 or 1.5.

[0014] 7. The multiphase particles described above or below, comprising at least an organic compound (particularly an organic polymer, preferably a polyurethane, particularly an aromatic polyurethane) and silicon (particularly silicon in oxide form, particularly at least one silicon-containing substance selected from silicates and silicon dioxide), and optionally containing inorganic compounds other than said silicon (e.g., at least one inorganic compound selected from carbonates, phosphates, sulfates, aluminates, refractory oxides (other than silicon dioxide) and hydroxides, particularly at least one inorganic compound selected from carbonates and hydroxides).

[0015] 8. The multiphase particles described above or below, wherein the Si element (based on Si) content of the second phase is 15-25 wt% (preferably 18-21 wt%), and the Si element (based on Si) content of the first phase is 1-8 wt% (preferably 1.5-5 wt%).

[0016] 9. A method for manufacturing multiphase particles, comprising at least the following steps:

[0017] Reaction Step: At least one multifunctional organic monomer (e.g., an organic compound having two or more isocyanate groups (-NCO) in one molecule, particularly selected from at least one of polyisocyanates, polyurethane prepolymers, and polyurea prepolymers, especially selected from at least one of C4+ aliphatic polyisocyanates, C4+ alicyclic polyisocyanates, aromatic polyisocyanates, polyurethane prepolymers derived from at least one of these polyisocyanates, and polyurea prepolymers derived from at least one of these polyisocyanates, particularly selected from at least one of C4+ aliphatic diisocyanates, C4+ alicyclic diisocyanates, aromatic diisocyanates, and polyurethane prepolymers derived from at least one of these diisocyanates) is used to... And at least one of the polyurea prepolymers derived from at least one of these diisocyanates, particularly selected from toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, naphthalene diisocyanate, polyurethane prepolymers derived from at least one of these diisocyanates, and at least one of the polyurea prepolymers derived from at least one of these diisocyanates, particularly selected from 4,4'-diphenylmethane diisocyanate, polyurethane prepolymers derived from the diisocyanate, and at least one of the polyurea prepolymers derived from the diisocyanate, particularly selected from 4,4'-diphenylmethane diisocyanate, polyurethane prepolymers derived from the diisocyanate, and polyurea prepolymers derived from the diisocyanate, particularly selected from 4,4'-dicyclohexane ... polyurethane prepolymers derived from the diisocyanate, and polyurea prepolymers derived from the diisocyanate, particularly selected from 4,44'-Diphenylmethane diisocyanate-derived polyurethane prepolymers) and at least one polyfunctional inorganic monomer (e.g., an inorganic compound having two or more -OH groups in one molecule and / or its precursor, particularly selected from at least one of silica sol, alumina sol, zirconium sol, titanium sol, silicates, aqueous silicate solutions, silicates, aqueous silicate solutions, aluminates, aqueous aluminate solutions, titanates, zirconates, aqueous zirconate solutions, and water, particularly selected from at least one of silica sol and aqueous silicate solutions, particularly aqueous silicate solutions, such as water glass) exhibiting chemical reactivity with the polyfunctional organic monomers, in optional At least one inorganic nanoparticle (e.g., nanoparticles composed essentially of inorganic substances, such as at least one selected from calcium carbonate nanoparticles, silica nanoparticles, and hydrotalcite nanoparticles, particularly calcium carbonate nanoparticles, and more particularly heavy calcium carbonate nanoparticles) and optionally at least one polyfunctional active hydrogen organic compound (e.g., an organic compound having two or more active hydrogen atoms in one molecule, particularly at least one selected from polyamines, polycarboxylic acids, polyphenols, polythiols, and polyols, particularly at least one selected from polyether polyols and polyester polyols, particularly polyether polyols, preferably polyether polyols) The average molecular weight is 500-8000, preferably 1000-6000, and the hydroxyl functionality is 2-3. Particularly preferred is that the polyether polyol is selected from at least one of polytetrahydrofuran diol and polypropylene oxide polyol, particularly preferably polypropylene oxide polyol or polypropylene oxide diol, especially selected from at least one of polypropylene oxide diol 1000, polypropylene oxide diol 2000, polypropylene oxide diol 3000, polypropylene oxide diol 5000, and polypropylene oxide diol 6000, in the presence of a catalyst (e.g., selected from carboxylates, metal alkyl compounds, quaternary ammonium salts, and tertiary amines, especially selected from stannous octoate). The organic-inorganic composite material is reacted in the presence of at least one of potassium carboxylate and dibutyltin dilaurate, or in the absence of a catalyst, to obtain a solid form of organic-inorganic composite material, and a pulverization step: pulverizing the organic-inorganic composite material to obtain the multiphase particles, wherein the average particle size of the multiphase particles is at least 0.1 mm (preferably at least 0.2 mm, at least 0.35 mm, at least 0.5 mm, at least 0.75 mm, or at least 0.8 mm) and at most 100 mm (preferably at most 50 mm, at most 20 mm, at most 10 mm, at most 5 mm, at most 2 mm, at most 1.2 mm, or at most 1.0 mm).

[0018] 10. A method for manufacturing multiphase particles according to any of the foregoing or subsequent aspects, wherein the ratio of the sum of the mass of the at least one multifunctional organic monomer and the optional at least one multifunctional active hydrogen organic compound to the sum of the mass of the at least one multifunctional inorganic monomer and the optional at least one inorganic nanoparticle is 1:1-5:1, preferably 1.5:1-3.5:1, and / or, the ratio of the at least one multifunctional inorganic monomer (particularly the aqueous solution or the sol, particularly silicate aqueous solution or silica sol, more particularly water glass) to the mass of the at least one The mass ratio of the inorganic nanoparticles is 100:90-100:30, 100:80-100:40, 100:75-100:45, or 100:65-100:55, and / or the molar ratio of the at least one polyfunctional organic monomer (based on functional groups, especially isocyanate groups) to the molar ratio of the at least one polyfunctional active hydrogen organic compound (based on active hydrogen, especially hydroxyl groups) is 1.1:1-2:1, 1.1:1-1.5:1, or 1.1:1-1.2:1.

[0019] 11. The method for manufacturing multiphase particles according to any of the foregoing or the following aspects, wherein the solid content of the aqueous solution or the sol (especially silicate aqueous solution or silica sol, more particularly water glass) is 20-70 wt%, 35-55 wt%, or 40-50 wt%, and / or the average particle size of the at least one inorganic nanoparticle is 150-500 nm, 200-350 nm, or 270-300 nm.

[0020] 12. A method for manufacturing multiphase particles according to any of the foregoing or subsequent aspects, wherein the polyurethane prepolymer is produced by reacting the polyisocyanate (particularly selected from at least one of toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate and naphthalene diisocyanate, particularly 4,4'-diphenylmethane diisocyanate) with a polyol (particularly selected from at least one of polyether polyols and polyester polyols, particularly polyether polyols, preferably with a number average molecular weight of 500-8000, preferably 1000-6000, and a hydroxyl functionality of 2-3, particularly...) Preferably, the polyether polyol is selected from at least one of polytetrahydrofuran diol and polypropylene oxide polyol, particularly preferably polypropylene oxide polyol or polypropylene oxide diol, especially at least one of polypropylene oxide diol 1000, polypropylene oxide diol 2000, polypropylene oxide diol 3000, polypropylene oxide diol 5000 and polypropylene oxide diol 6000, in the presence of a catalyst (such as at least one selected from carboxylates, metal alkyl compounds, quaternary ammonium salts and tertiary amines, especially at least one selected from stannous octoate, potassium carboxylate and dibutyltin dilaurate) or in the absence of a catalyst, and its NCO content is 1-7 wt%, 2-5 wt% or 3-4 wt%.

[0021] 13. A method for manufacturing multiphase particles as described above or below, comprising the following steps:

[0022] (1) The at least one multifunctional organic monomer and the at least one multifunctional active hydrogen organic compound are reacted in a predetermined ratio in the presence of the catalyst or in the absence of the catalyst to obtain component A (especially a polyurethane prepolymer with an NCO content of 1-7 wt%, 2-5 wt%, or 3-4 wt%).

[0023] (2) Mix the at least one multifunctional inorganic monomer with the at least one inorganic nanoparticle in a predetermined ratio to obtain component B;

[0024] (3) Mix and cure component B with component A; and

[0025] (4) The solid obtained in step (3) is crushed and optionally sieved to obtain the multiphase particles.

[0026] 14. A method for manufacturing multiphase particles according to any of the foregoing or subsequent aspects, wherein in step (1), the molar ratio of the at least one multifunctional organic monomer (based on functional groups, particularly isocyanate groups) to the molar ratio of the at least one multifunctional active hydrogen organic compound (based on active hydrogen, particularly hydroxyl groups) is 1.1:1-2:1, 1.1:1-1.5:1, or 1.1:1-1.2:1, and / or, in step (2), the mass ratio of the at least one multifunctional inorganic monomer to the at least one inorganic nanoparticle is 100: 90-100:30, 100:80-100:40, 100:75-100:45 or 100:65-100:55, and / or, in step (3), the mixing conditions of component A and component B are: the mass ratio of component A to component B is 1:1-5:1 (preferably 1.5:1-3.5:1), the stirring speed is 1500-2000 rpm (preferably 1600-1800 rpm), the mixing time is 15-90s (preferably 20-40s), and the mixing temperature is 30-90℃ (preferably 50-70℃).

[0027] 15. The use of the multiphase particles described above or below, or the multiphase particles manufactured by the manufacturing methods described above or below, as toughening agents.

[0028] 16. An inorganic cementitious composition comprising at least an inorganic cementitious material (such as a hydraulic inorganic cementitious material, particularly cement) and multiphase particles as described above or below, or multiphase particles manufactured by the manufacturing method described above or below, wherein the multiphase particles are 0.5-50 parts by weight (preferably 5-30 parts by weight, particularly 10-20 parts by weight) relative to 100 parts by weight of the inorganic cementitious material.

[0029] 17. A method for manufacturing an inorganic cementitious composition, comprising at least the step of mixing an inorganic cementitious material (such as a hydraulic inorganic cementitious material, particularly cement) with multiphase particles as described above or below, or multiphase particles manufactured by the manufacturing method described above or below, wherein the multiphase particles are 0.5-50 parts by weight (preferably 5-30 parts by weight, particularly 10-20 parts by weight) relative to 100 parts by weight of the inorganic cementitious material.

[0030] 18. A method for toughening an inorganic cementitious material, comprising at least the step of introducing the multiphase particles described above or below, or multiphase particles manufactured by the manufacturing method described above or below, into the inorganic cementitious material (e.g., a hydraulic inorganic cementitious material, particularly cement). The multiphase particles are 0.5-50 parts by weight (preferably 5-30 parts by weight, particularly 10-20 parts by weight) relative to 100 parts by weight of the inorganic cementitious material.

[0031] Alternatively, the present invention relates to the following aspects.

[0032] 1. A multiphase particle, characterized in that the multiphase particle comprises an organic component and an inorganic component, wherein the mass ratio of the organic component to the inorganic component is 1:1-5:1, and the particle size of the multiphase particle is 0.5-1.2 mm;

[0033] The organic component is a polyurethane prepolymer, and the inorganic component includes a silicate aqueous solution and nanofillers. The mass ratio of the silicate aqueous solution to the nanofillers is 100:90-100:30, and the concentration of the silicate aqueous solution is 20-70 wt%.

[0034] 2. The multiphase particles according to any of the foregoing or hereinafter described, characterized in that:

[0035] The nanofiller is selected from at least one of nano-calcium carbonate, nano-silica, or nano-hydrotalcite, and the particle size of the nanofiller is 150-500 nm.

[0036] 3. The multiphase particles according to any of the foregoing or hereinafter described, characterized in that:

[0037] The particle size of the nanofiller is 200-350 nm, preferably 270-300 nm.

[0038] 4. The multiphase particles according to any of the foregoing or hereinafter described, characterized in that:

[0039] The multiphase particles have a particle size of 0.75-1.0 mm, the mass ratio of the organic component to the inorganic component is 1.5:1-3.5:1, the mass ratio of the silicate aqueous solution to the nanofiller is 100:80-100:40, and the concentration of the silicate aqueous solution is 35-55 wt%.

[0040] 5. The multiphase particles according to any of the foregoing or hereinafter described, characterized in that:

[0041] The mass ratio of the silicate aqueous solution to the nanofiller is 100:75-100:45, and the concentration of the silicate aqueous solution is 40%-50%.

[0042] 6. The multiphase particles according to any of the foregoing or hereinafter described, characterized in that:

[0043] The polyurethane prepolymer is generated by reacting polyisocyanate with polyether polyol.

[0044] 7. The multiphase particles according to any of the foregoing or hereinafter described, characterized in that:

[0045] The polyisocyanate is selected from one or more of toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, naphthalene diisocyanate and their modified, isomer or polymer.

[0046] The polyether polyol has a number average molecular weight of 500-8000 and a functionality of 2-3. The polyether polyol is selected from one or more of polytetrahydrofuran diol and propylene oxide polyether polyol.

[0047] 8. A method for preparing multiphase particles according to any of the foregoing or hereinafter described aspects, characterized by comprising the following steps:

[0048] (1) React polyisocyanate with polyether polyol to form polyurethane prepolymer to obtain component A;

[0049] (2) Mix raw materials including silicate aqueous solution and nanofiller to obtain component B, then mix with component A and cure to form sheet elastic product;

[0050] (3) The sheet-like elastic product is crushed and sieved to obtain the multiphase particles.

[0051] 9. The method for preparing multiphase particles according to any of the foregoing or hereinafter described aspects, characterized in that:

[0052] In step (1), the ratio of the number of moles of isocyanate in the polyisocyanate to the number of moles of hydroxyl groups in the polyether polyol is 1.1:1-2:1; in step (2), the mixing conditions for components A and B are: stirring speed 1500-2000 rpm, mixing time 15-90s, and mixing temperature 50-70℃.

[0053] 10. The method for preparing multiphase particles according to any of the foregoing or hereinafter described aspects, characterized in that:

[0054] In step (1), the ratio of the number of moles of isocyanate in the polyisocyanate to the number of moles of hydroxyl groups in the polyether polyol is 1.1:1-1.5:1, preferably 1.1:1-1.2:1.

[0055] Technical effect

[0056] According to the present invention, at least one of the following technical effects can be achieved:

[0057] (1) The multiphase particles of the present invention can improve the cementing effect when applied to cementing applications, reduce the number of cementing operations during the service life of the oil well, increase the economic value of a single well, and save operating costs.

[0058] (2) The multiphase particles according to the present invention have high bulk strength and good interfacial adhesion with cement stone.

[0059] (3) The multiphase particles of the present invention have good compatibility with cement, can significantly reduce the elastic modulus of cement stone, and have a significant toughening effect.

[0060] (4) The multiphase particles of the present invention can be dry-mixed into cement or drilling mud in any proportion as needed, without affecting the mixing and injection of mud or changing the original cementing process, and have strong applicability.

[0061] (5) According to a preferred embodiment of the multiphase particles of the present invention, the elastic modulus of cement stone can be reduced while maintaining the strength of cement stone with almost no reduction (and in some cases even increasing the strength of cement stone). Attached Figure Description

[0062] Figure 1a These are SEM images (at different magnifications) of the multiphase particles in Example 4. Figure 1b This is the EDS energy spectrum of the multiphase particles.

[0063] Figure 2a These are SEM images (at different magnifications) of the multiphase particles in Example 5. Figure 2b This is the EDS energy spectrum of the multiphase particles.

[0064] Figure 3 This is the infrared spectrum of the multiphase particles in Example 3. Detailed Implementation

[0065] The specific embodiments of the present invention will be described in detail below. However, it should be noted that the scope of protection of the present invention is not limited to these specific embodiments, but is determined by the claims in the appendix.

[0066] All publications, patent applications, patents, and other references mentioned in this specification are incorporated herein by reference. Unless otherwise defined, all technical and scientific terms used in this specification have the meanings commonly understood by those skilled in the art. In case of conflict, the definitions in this specification shall prevail.

[0067] When this specification uses the prefixes “known to those skilled in the art,” “prior art,” or similar terms to derive materials, substances, methods, steps, apparatus, or components, the objects derived from such prefixes cover those commonly used in the art at the time of this application, but also include those that are not currently commonly used but will become generally recognized in the art as suitable for similar purposes.

[0068] Unless otherwise specified, all percentages, parts, ratios, etc. mentioned in this instruction manual are based on weight, and the pressure is gauge pressure.

[0069] In the context of this specification, any two or more embodiments of the present invention can be arbitrarily combined, and the resulting technical solutions are part of the original disclosure of this specification and also fall within the protection scope of the present invention.

[0070] In the context of this specification, the term "substantially" means that deviations that are acceptable or reasonable to a person skilled in the art are permitted, such as deviations within ±20%, ±15%, ±10%, ±5%, or ±2%.

[0071] According to one embodiment of the present invention, a multiphase particle is disclosed. The multiphase particle has a multiphase structure comprising a first phase and a second phase. Preferably, the multiphase structure is composed of the first phase and the second phase. Here, the multiphase structure can be confirmed by SEM images of the multiphase particle.

[0072] Without being limited by any theoretical constraints, the inventors of this invention believe that the first phase is mainly composed of organic matter, and the second phase is mainly composed of inorganic matter. This can be confirmed by the significantly different Si and C element contents of the two phases in the EDS energy spectrum of the multiphase particles. For this reason, the multiphase particles are sometimes also referred to as organic-inorganic composite particles.

[0073] In the context of this instruction manual, the measurement conditions for SEM images and EDS spectra include: field emission scanning electron microscope (JEOL, Japan, model JSM-7200F), 10.0 kV, magnification 5000x, using the built-in energy dispersive spectroscopy scanner of the electron microscope to test the sample surface, automatically calculating and outputting the mass percentage measurement results. The sample is thoroughly dried before measurement. Before measurement, a conductive layer is sprayed onto the sample in a vacuum coating apparatus, and then the sample is adhered to the sample stage with conductive double-sided tape before being sent into the electron microscope for measurement.

[0074] According to one embodiment of the present invention, the multiphase structure at least partially has a morphology (1). According to the morphology (1), the first phase is a continuous phase at least partially having a porous structure, and the second phase is a dispersed phase. Here, the morphology (1) can be confirmed by SEM images of the multiphase particles.

[0075] According to one embodiment of the invention, in the configuration (1), at least one of the second phases has a substantially spherical shape (referred to as a spherical second phase). Preferably, more than 50%, 60%, 80%, 90%, or substantially all of the total number of the second phases have a substantially spherical shape.

[0076] According to one embodiment of the invention, in the configuration (1), at least one of the spherical second phases is located within a pore of the porous structure of the first phase. Here, a substantially circular pore is particularly exemplified as the pore. Preferably, more than 50%, 60%, 80%, 90%, or substantially all of the spherical second phases are located within the pore. Generally, the number of pores is greater than the number of spherical second phases, but there is no particular limitation. Here, multiple pores can exist independently of each other, or multiple pores can overlap to form a composite pore. In the context of this specification, composite pores and single pores are sometimes simply referred to as pores without distinction.

[0077] For example, Figure 1a These are SEM images (at different magnifications) of the multiphase particles in Example 4. Figure 1a As shown, the first phase is a porous continuous phase, and the second phase is substantially spherical and is embedded in some of the pores of the first phase.

[0078] According to one embodiment of the present invention, the multiphase structure at least partially has a morphology (2). According to the morphology (2), the second phase is a continuous phase, and the first phase is a dispersed phase. Here, the morphology (2) can be confirmed by SEM images of the multiphase particles.

[0079] According to one embodiment of the invention, in the configuration (2), at least one of the first phases has a substantially columnar shape (referred to as a columnar first phase). Here, the columnar shape can be exemplified by, for example, a cylinder or a prism. Preferably, more than 50%, more than 60%, more than 80%, more than 90%, or substantially all of the first phases have a substantially columnar shape.

[0080] According to one embodiment of the present invention, in the form (2), the continuous phase is, for example, having a loose structure or an amorphous structure.

[0081] For example, Figure 2a These are SEM images (at different magnifications) of the multiphase particles in Example 5. Figure 2a As shown, the second phase is a continuous phase with a soil-like loose structure, while the first phase is substantially prismatic.

[0082] According to one embodiment of the present invention, the multiphase structure at least partially has a morphology (3): a combination of morphology (1) and morphology (2). In other words, morphology (3) is a mixture of morphology (1) and morphology (2). Here, morphology (3) can be confirmed by SEM images of the multiphase particles.

[0083] According to one embodiment of the present invention, the average particle size of the multiphase particles is at least 0.1 mm, at least 0.2 mm, at least 0.35 mm, at least 0.5 mm, at least 0.75 mm, or at least 0.8 mm. Alternatively, the average particle size of the multiphase particles is at most 100 mm, at most 50 mm, at most 20 mm, at most 10 mm, at most 5 mm, at most 2 mm, at most 1.2 mm, or at most 1.0 mm. Here, the average particle size is determined by sieving using a vibrating screen (FRITSCH analyzette3, Germany) with screens of different aperture sizes.

[0084] According to one embodiment of the present invention, in the multiphase particles, the Si element content (calculated as Si) of the first phase is generally 1-8 wt%, preferably 1.5-5 wt%. Here, the measurement conditions for the Si element content of the first phase include: measuring the Si element content by EDS energy dispersive spectroscopy.

[0085] According to one embodiment of the present invention, in the multiphase particles, the Si element content (calculated as Si) of the second phase is generally 15-25 wt%, preferably 18-21 wt%. Here, the measurement conditions for the Si element content of the second phase include: measuring the Si element content by EDS energy dispersive spectroscopy.

[0086] According to one embodiment of the present invention, in the multiphase particles, the ratio of the Si element content (in wt%) in the second phase to the Si element content (in wt%) in the first phase is 5-20, 8-12, or 9-11. Here, the measurement conditions for the Si element content ratio include: measuring the Si element content of the second phase and the Si element content of the first phase by EDS energy dispersive spectroscopy, and then performing calculations.

[0087] For example, Figure 1b This is the EDS energy spectrum of the multiphase particles in Example 4. Figure 2bThe above are EDS energy spectra of the multiphase particles in Example 5, showing the content (in wt%) of each constituent element in the first and second phases, including the content of Si and C elements.

[0088] According to one embodiment of the present invention, the multiphase particles have surface silanol groups. According to another embodiment of the present invention, the multiphase particles have surface -NCO groups. Alternatively, according to a preferred embodiment of the present invention, the multiphase particles have surface silanol groups and surface -NCO groups. Here, these surface groups can be identified by infrared analysis. For example, Figure 3 The infrared spectrum of the multiphase particles in Example 3 clearly shows the presence of Si-OH and -NCO.

[0089] According to one embodiment of the present invention, the BET specific surface area of ​​the multiphase particles is 1-200 m². 2 / g, 5-50m 2 / g or 10-30m 2 / g. The measurement conditions for specific surface area include: a specific surface area and pore size analyzer (China Jin'epu Technology, model V-Sorb 2800P), and the BET method for testing specific surface area (nitrogen adsorption specific surface area testing method). The measurement process is as follows: ① Weigh the empty sample tube, m0; ② Add a certain amount of sample to the sample tube; ③ Place the sample tube in the degassing station and degas at 200℃ for 12 hours; ④ Remove the sample tube and weigh it, m1; ⑤ Place the sample tube in the specific surface area analyzer, add liquid nitrogen, and input m = m1 - m0 on the computer to start the test.

[0090] According to one embodiment of the present invention, the water contact angle of the multiphase particles is 20-60°, 25-50°, 30-45°, or 35-40°. Here, the contact angle measurement conditions include: using a contact angle surface performance meter (Dataphysics, Germany, model OCA50), employing droplet capture technology, using deionized water, using the contact angle meter to droplets onto the surface of the sample to be tested, at room temperature of 25°C, and magnifying and observing the contact angle between the droplets and the sample.

[0091] According to one embodiment of the present invention, the pH value of the multiphase particles is 7-10, 7.5-9, or 8-9. Here, the pH measurement conditions include: taking 10 grams of sample and immersing it in 100 grams of deionized water, stirring for 24 hours, and then measuring the pH value of the supernatant.

[0092] According to one embodiment of the present invention, the apparent density of the multiphase particles is 1.1-1.6 g / cm³. 3 Or 1.2-1.3 g / cm³ 3Here, the measurement conditions for apparent density are as follows: after weighing a standard material module with a length, width, and height of 2.54 cm, the apparent density is obtained by dividing the mass by the volume.

[0093] According to one embodiment of the present invention, in the multiphase particles, the diameter of the spherical second phase is 0.1-50 micrometers, preferably 0.2-25 micrometers, 0.5-20 micrometers, 1-10 micrometers, or 2-8 micrometers. Here, the diameter of the spherical second phase refers to the maximum size of the spherical second phase measured in an SEM image.

[0094] According to one embodiment of the present invention, in the multiphase particles, the pore size is 0.05-100 micrometers, preferably 0.2-50 micrometers, 0.5-25 micrometers, or 1-15 micrometers. Here, the term "pore" refers to the opening of the pore to the outside. Furthermore, the term "pore size" refers to the maximum value of the distance between any two points on the pore in a SEM image.

[0095] According to one embodiment of the present invention, in the multiphase particles, the length of the columnar first phase is 0.1-50 micrometers, preferably 0.2-20 micrometers, 0.5-10 micrometers, or 1-5 micrometers. Here, "length" refers to the maximum dimension in the longitudinal direction in the SEM image.

[0096] According to one embodiment of the present invention, in the multiphase particles, the diameter of the columnar first phase is 0.1-10 micrometers, preferably 2-5 micrometers. Here, the term "diameter" refers to the maximum dimension in a cross-section perpendicular to the length direction in an SEM image.

[0097] According to one embodiment of the present invention, the Si element content (based on Si) of the multiphase particles is 0.5-5 wt%, preferably 1-3.5 wt%, based on a total mass of 100 wt% of the multiphase particles. Here, the Si element content is measured by elemental analysis.

[0098] According to one embodiment of the present invention, in the multiphase particles, the spherical second phase is located within the pores, for example, exhibiting the following characteristics: Figure 1a The shown fitting state. Preferably, the ratio of the aperture size to the diameter of the spherical second phase is at least 1, greater than 1, 1.05, 1.1, 1.15 or 1.2, and at most 10, 5, 2 or 1.5.

[0099] According to one embodiment of the invention, the multiphase particles contain at least an organic compound and silicon in their composition. Here, silicon in oxide form is particularly suitable, and silicates and silicon dioxide are even more particularly suitable. The organic compound can be, for example, an organic polymer, preferably a polyurethane, and particularly aromatic polyurethanes. For example, Figure 3 The infrared spectrum of the multiphase particles in Example 3 clearly shows the presence of Si-OH (corresponding to silicon) and benzene rings (corresponding to aromatic polyurethanes).

[0100] According to one embodiment of the invention, the multiphase particles optionally contain inorganic substances other than silicon in their composition. Examples of such inorganic substances include carbonates, phosphates, sulfates, aluminates, refractory oxides (other than silicon dioxide), and hydroxides, with carbonates and hydroxides being particularly noteworthy.

[0101] According to one embodiment of the present invention, the compressive strength of the multiphase particles is generally 25-60 MPa, and the tensile strength of the multiphase particles is generally 12-18 MPa. The cement-stone interfacial bond strength of the multiphase particles is generally 1-3 MPa. Here, the compressive strength of the multiphase particles is measured according to GB / T 19139-2012 (Test Method for Oil Well Cement), the tensile strength is measured according to GB / T1040-2006 (Determination of Tensile Properties of Plastics), and the cement-stone interfacial bond strength is measured according to GB / T 16777-2008 (Test Method for Waterproof Coatings for Buildings).

[0102] According to one embodiment of the present invention, the multiphase particles can be manufactured according to the following manufacturing method. The manufacturing method includes at least a reaction step and a pulverization step.

[0103] According to one embodiment of the present invention, in the reaction step, at least one polyfunctional organic monomer and at least one polyfunctional inorganic monomer (hereinafter referred to as polyfunctional inorganic monomer) exhibiting chemical reactivity to the polyfunctional organic monomer are reacted in the presence of at least one inorganic nanoparticle and at least one polyfunctional active hydrogen organic compound, in the presence of a catalyst or in the absence of a catalyst, to obtain an organic-inorganic composite material in solid form. Preferably, the reaction is carried out in the absence of a catalyst.

[0104] According to one embodiment of the invention, in the reaction step, the polyfunctional organic monomer can be, for example, an organic compound having two or more isocyanate groups (-NCO) in one molecule, particularly polyisocyanates, polyurethane prepolymers, and polyurea prepolymers, especially C4+ aliphatic polyisocyanates, C4+ alicyclic polyisocyanates, aromatic polyisocyanates, polyurethane prepolymers derived from at least one of these polyisocyanates, and polyurea prepolymers derived from at least one of these polyisocyanates, particularly C4+ aliphatic diisocyanates, C4+ alicyclic diisocyanates, aromatic diisocyanates, polyurethane prepolymers derived from at least one of these diisocyanates, and so on. Polyurea prepolymers derived from at least one of these diisocyanates, particularly toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, naphthalene diisocyanate, polyurethane prepolymers derived from at least one of these diisocyanates, and polyurea prepolymers derived from at least one of these diisocyanates, particularly 4,4'-diphenylmethane diisocyanate, polyurethane prepolymers derived from the diisocyanate, and polyurea prepolymers derived from the diisocyanate, particularly polyurethane prepolymers derived from 4,4'-diphenylmethane diisocyanate.

[0105] According to one embodiment of the invention, in the reaction step, the multifunctional inorganic monomer can be, for example, an inorganic compound having two or more -OH groups in one molecule and / or its precursor, particularly silica sol, alumina sol, zirconium sol, titanium sol, silicate esters, aqueous silicate ester solutions, silicates, aqueous silicate solutions, aluminates, aqueous aluminate ester solutions, titanates, aqueous titanates, zirconates, aqueous zirconate ester solutions, and water. More particularly, silica sol and aqueous silicate solutions are examples, and even more particularly, aqueous silicate solutions, such as water glass, are examples. Here, "solution" includes both true solutions and colloidal solutions, without distinction.

[0106] According to one embodiment of the present invention, in the reaction step, the inorganic nanoparticles can be, for example, nanoparticles composed of essentially inorganic substances, such as calcium carbonate nanoparticles, silica nanoparticles and hydrotalcite nanoparticles, especially calcium carbonate nanoparticles, and even more particularly heavy calcium carbonate nanoparticles.

[0107] According to one embodiment of the present invention, in the reaction step, the polyfunctional active hydrogen organic compound can be, for example, an organic compound having two or more active hydrogen atoms in one molecule, particularly polyamines, polycarboxylic acids, polyphenols, polythiols and polyols, particularly polyether polyols and polyester polyols, particularly polyether polyols.

[0108] According to one embodiment of the present invention, in the reaction step, the number average molecular weight of the polyether polyol is generally 500-8000, preferably 1000-6000. Furthermore, the hydroxyl functionality of the polyether polyol is generally 2-3.

[0109] According to one embodiment of the present invention, in the reaction step, the polyether polyol can be, for example, polytetrahydrofuran glycol and polypropylene oxide polyol, preferably polypropylene oxide polyol or polypropylene oxide diol. Polypropylene oxide diol 1000, polypropylene oxide diol 2000, polypropylene oxide diol 3000, polypropylene oxide diol 5000 and polypropylene oxide diol 6000 are particularly exemplified here.

[0110] According to one embodiment of the present invention, in the reaction step, the catalyst may be, for example, a carboxylate, a metal alkyl compound, a quaternary ammonium salt and a tertiary amine, particularly stannous octoate, potassium carboxylate and dibutyltin dilaurate.

[0111] According to one embodiment of the present invention, in the pulverization step, the organic-inorganic composite material is pulverized to obtain the multiphase particles.

[0112] According to one embodiment of the invention, in the pulverizing step, the average particle size of the multiphase particles is at least 0.1 mm, preferably at least 0.2 mm, at least 0.35 mm, at least 0.5 mm, at least 0.75 mm, or at least 0.8 mm. Furthermore, the average particle size of the multiphase particles is at most 100 mm, preferably at most 50 mm, at most 20 mm, at most 10 mm, at most 5 mm, at most 2 mm, at most 1.2 mm, or at most 1.0 mm. Sieving is performed using a vibrating screen (FRITSCH analyzette3, Germany) with screens of different aperture sizes.

[0113] According to one embodiment of the present invention, in the manufacturing method, the ratio of the sum of the masses of the at least one polyfunctional organic monomer and the optional at least one polyfunctional active hydrogen organic compound (referred to as the organic component mass) to the sum of the masses of the at least one polyfunctional inorganic monomer and the optional at least one inorganic nanoparticle (referred to as the inorganic component mass) is 1:1-5:1, preferably 1.5:1-3.5:1.

[0114] According to one embodiment of the present invention, when the mass ratio of the organic component to the inorganic component is 1-10:99-90, the multiphase particles generally exhibit a multiphase structure as shown in morphology (1). Alternatively, when the mass ratio of the organic component to the inorganic component is 20-60:80-40, the multiphase particles generally exhibit a multiphase structure as shown in morphology (2). Alternatively, when the mass ratio of the organic component to the inorganic component is 10-20:90-80, the multiphase particles generally exhibit a multiphase structure as shown in morphology (3).

[0115] According to one embodiment of the present invention, in the manufacturing method, the mass ratio of the at least one multifunctional inorganic monomer to the at least one inorganic nanoparticle is 100:90-100:30, 100:80-100:40, 100:75-100:45, or 100:65-100:55. Here, various aqueous solutions or sols as described above are particularly suitable examples of the multifunctional inorganic monomer, especially silicate aqueous solutions or silica sols, and even more particularly, water glass.

[0116] According to one embodiment of the present invention, in the manufacturing method, the molar ratio of the at least one polyfunctional organic monomer (based on functional groups, particularly isocyanate groups) to the molar ratio of the at least one polyfunctional active hydrogen organic compound (based on active hydrogen, particularly hydroxyl groups) is 1.1:1-2:1, 1.1:1-1.5:1, or 1.1:1-1.2:1.

[0117] According to one embodiment of the present invention, in the manufacturing method, the solid content of the various aqueous solutions or sols described above is generally 20-70 wt%, 35-55 wt%, or 40-50 wt%. Here, silicate aqueous solutions or silica sols are particularly exemplified as the aqueous solutions or sols, and water glass is even more particularly exemplified.

[0118] According to one embodiment of the present invention, in the manufacturing method, the average particle size of the at least one inorganic nanoparticle is generally 150-500 nm, 200-350 nm, or 270-300 nm. Here, the average particle size is measured using a laser particle size analyzer (FRITSCH analyzette22, Germany) in dry powder measurement mode. The powder is added to the dry powder tank, and the measurement is performed automatically.

[0119] According to one embodiment of the present invention, in the manufacturing method, the polyurethane prepolymer is formed by polymerizing the aforementioned polyisocyanate with a polyol in the presence of a catalyst or in the absence of a catalyst. Preferably, the polymerization reaction occurs in the absence of the catalyst. Here, examples of the polyisocyanate include toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, and naphthalene diisocyanate, with 4,4'-diphenylmethane diisocyanate being particularly noteworthy. Examples of the polyol include polyether polyols and polyester polyols, with polyether polyols being particularly noteworthy. Preferably, the polyether polyol has a number-average molecular weight generally of 500-8000, preferably 1000-6000, and a hydroxyl functionality of 2-3. Examples of polyether polyols include, in particular, polytetrahydrofuran glycol and polypropylene oxide polyols, preferably polypropylene oxide polyols or polypropylene oxide diols, and more particularly, polypropylene oxide diol 1000, polypropylene oxide diol 2000, polypropylene oxide diol 3000, polypropylene oxide diol 5000 and polypropylene oxide diol 6000. Examples of catalysts include, for example, carboxylates, metal alkyl compounds, quaternary ammonium salts and tertiary amines, particularly stannous octoate, potassium carboxylate and dibutyltin dilaurate.

[0120] According to one embodiment of the present invention, in the manufacturing method, the NCO content of the polyurethane prepolymer is generally 1-7 wt%, 2-5 wt%, or 3-4 wt%. Here, the NCO content is calculated by the proportion of excess NCO in the prepolymer.

[0121] According to one embodiment of the present invention, the manufacturing method includes the following steps:

[0122] (1) React the at least one multifunctional organic monomer with the at least one multifunctional active hydrogen organic compound in a predetermined ratio in the presence of the catalyst or in the absence of the catalyst to obtain component A;

[0123] (2) Mix the at least one multifunctional inorganic monomer with the at least one inorganic nanoparticle in a predetermined ratio to obtain component B;

[0124] (3) Mix and cure component B with component A; and

[0125] (4) The solid obtained in step (3) is crushed and optionally sieved to obtain the multiphase particles.

[0126] According to one embodiment of the present invention, in step (1), the reaction is preferably carried out in the absence of the catalyst.

[0127] According to one embodiment of the present invention, in step (1), the at least one polyfunctional organic monomer (in particular the polyisocyanate) and the at least one polyfunctional active hydrogen organic compound (in particular the polyether polyol) can be carried out by addition polymerization reaction conventionally known in the art, without any particular limitation.

[0128] According to one embodiment of the present invention, in step (1), the reaction temperature is generally 80-95°C and the reaction time is generally 2-5 hours, without any particular limitation. Stirring may also be used as needed.

[0129] According to one embodiment of the present invention, in step (1), a polyurethane prepolymer is particularly suitable as the component A obtained. Preferably, the NCO content of the polyurethane prepolymer is generally 1-7 wt%, 2-5 wt%, or 3-4 wt%. Here, the NCO content is calculated by the percentage of excess NCO in the prepolymer.

[0130] According to one embodiment of the present invention, in step (1), the molar ratio of the at least one polyfunctional organic monomer (based on functional groups, particularly isocyanate groups) to the molar ratio of the at least one polyfunctional active hydrogen organic compound (based on active hydrogen, particularly hydroxyl groups) is 1.1:1-2:1, 1.1:1-1.5:1, or 1.1:1-1.2:1.

[0131] According to one embodiment of the present invention, in step (2), the mass ratio of the at least one multifunctional inorganic monomer to the at least one inorganic nanoparticle is 100:90-100:30, 100:80-100:40, 100:75-100:45 or 100:65-100:55.

[0132] According to one embodiment of the present invention, in step (2), the mixing can be carried out in a manner conventionally known in the art, and is not particularly limited. For example, room temperature can be used as the mixing temperature, and 2-3 hours can be used as the mixing time.

[0133] According to one embodiment of the present invention, in step (3), the mixing can be carried out in a manner conventionally known in the art, without any particular limitation. Through this mixing, a mixture to be cured is obtained.

[0134] According to one embodiment of the present invention, in step (3), the mass ratio of component A to component B is generally 1:1-5:1, preferably 1.5:1-3.5:1.

[0135] According to one embodiment of the present invention, in step (3), the mixing is carried out under stirring. Here, the stirring speed is generally 1500-2000 rpm, preferably 1600-1800 rpm.

[0136] According to one embodiment of the present invention, in step (3), the mixing time is generally 15-90s, preferably 20-40s.

[0137] According to one embodiment of the present invention, in step (3), the mixing temperature is generally 30-90°C, preferably 50-70°C.

[0138] According to one embodiment of the present invention, in step (3), the curing can be carried out in a manner conventionally known in the art, without particular limitation. For example, the mixture to be cured can be poured into a mold and cured for 5-10 hours, thereby forming a sheet with a thickness of 1-1.2 mm.

[0139] According to one embodiment of the present invention, in step (4), the crushing and sieving can be performed in a manner conventionally known in the art, without particular limitation. Specifically, for example, the multiphase particles can be obtained by crushing and sieving the sheet obtained in step (3).

[0140] According to one embodiment of the present invention, in step (4), the average particle size of the multiphase particles is at least 0.1 mm, preferably at least 0.2 mm, at least 0.35 mm, at least 0.5 mm, at least 0.75 mm, or at least 0.8 mm. Furthermore, the average particle size of the multiphase particles is at most 100 mm, preferably at most 50 mm, at most 20 mm, at most 10 mm, at most 5 mm, at most 2 mm, at most 1.2 mm, or at most 1.0 mm. Here, the average particle size is determined by sieving using a vibrating screen (FRITSCH analyzette3, Germany) with screens of different aperture sizes.

[0141] According to one embodiment of the present invention, the application of the multiphase particles described in any of the foregoing embodiments as toughening agents is also involved, particularly as toughening agents for cement stone.

[0142] According to one embodiment of the present invention, an inorganic cementing composition is also disclosed. The inorganic cementing composition comprises at least an inorganic cementing material and the multiphase particles described in any of the foregoing embodiments. Preferably, the inorganic cementing composition further comprises water.

[0143] According to one embodiment of the invention, in the inorganic cementitious composition, the multiphase particles are generally 0.5-50 parts by weight, preferably 5-30 parts by weight, and particularly 10-20 parts by weight, compared to 100 parts by weight of the inorganic cementitious material.

[0144] According to one embodiment of the present invention, a method for manufacturing an inorganic cementitious composition is also provided. The manufacturing method includes at least the step of mixing the inorganic cementitious material with the multiphase particles described in any of the foregoing embodiments (hereinafter referred to as the mixing step). Depending on the circumstances, water may also be added before, during, or after mixing.

[0145] According to one embodiment of the invention, in the mixing step, the multiphase particles are generally 0.5-50 parts by weight, preferably 5-30 parts by weight, and particularly 10-20 parts by weight, compared to 100 parts by weight of the inorganic cementitious material.

[0146] According to one embodiment of the present invention, a method for toughening an inorganic cementitious material is also provided. This toughening method includes at least the step of introducing the multiphase particles described in any of the foregoing embodiments into the inorganic cementitious material (hereinafter referred to as the introduction step).

[0147] According to one embodiment of the present invention, in the introduction step, the multiphase particles are generally 0.5-50 parts by weight, preferably 5-30 parts by weight, and particularly 10-20 parts by weight, compared to 100 parts by weight of the inorganic cementitious material.

[0148] According to one embodiment of the present invention, the aforementioned inorganic cementitious material can be, for example, a hydraulic inorganic cementitious material, particularly cement. Furthermore, various additives conventionally known in the art can be added to the inorganic cementitious material as needed, without particular limitation. Specific examples of such additives include water, aggregates, inorganic fillers (e.g., fly ash), organic fillers, plasticizers, colorants, foaming agents, leveling agents, water-reducing agents, reinforcing agents, waterproofing agents, binders, and rust inhibitors. The amount of these additives used can be any amount conventionally known in the art, without particular limitation.

[0149] Example

[0150] The present invention will be further described in detail below through embodiments and comparative examples, but the present invention is not limited to the following embodiments.

[0151] Example 1

[0152] 70g of diphenylmethane diisocyanate (MDI) (Yantai Wanhua Chemical Group, MDI100) and 186.7g of polypropylene oxide glycol (Lanxing Group Shandong Dongda Chemical Co., Ltd., DL1000, number average molecular weight 1000, functionality 2) (100g ppg 1000) were mixed and reacted at 95℃ for 3h to prepare a polyurethane prepolymer formed by polyisocyanate and polyether polyol (molar ratio of isocyanate to polyether polyol is 1.5:1). The NCO content of the polyurethane prepolymer was 3.05%, which was used as component A. 100g of silicate aqueous solution (Zhangjiakou Tonglida Sodium Silicate Co., Ltd., TLD-38) (38% solid content) and 30g of heavy calcium carbonate (Hebei Yixian Shenglan Mineral Powder Factory, 280nm) were mixed for 3h to obtain component B. Mix 100g of component A and 100g of component B at 1500rpm, 60℃, for 30s. Pour the mixture into a plate mold and cure for 10 hours to obtain a 1mm thick sheet measuring 30mm x 30mm. The sheet properties are: compressive strength 30MPa, tensile strength 3.5MPa, and cement-stone interfacial bond strength 2.2MPa. The sheet is then pulverized to produce multiphase particles with an average particle size of 0.7mm-1.2mm. The BET specific surface area of ​​the multiphase particles is 8.8m². 2 / g; water contact angle is 42°; pH value is 8.5; apparent density is 1.45g / cm³ 3 The Si element content (calculated as Si) is 3.3 wt%.

[0153] Example 2

[0154] 100g of diphenylmethane diisocyanate (MDI) (Yantai Wanhua Chemical Group, MDI100) and 200g of polypropylene oxide glycol (Lanxing Group Shandong Dongda Chemical Co., Ltd., DL1000, number average molecular weight 1000, functionality 2) (100g ppg 1000) were mixed and reacted at 95℃ for 3h to obtain a polyurethane prepolymer formed by polyisocyanate and polyether polyol (molar ratio of isocyanate to polyether polyol is 2:1). The NCO content of the polyurethane prepolymer was 5.6%, which was designated as component A. 100g of silicate aqueous solution (Zhangjiakou Tonglida Sodium Silicate Co., Ltd., TLD-38) (38% solid content) and 50g of heavy calcium carbonate (Hebei Yixian Shenglan Mineral Powder Factory, 280nm) were mixed for 3h to obtain component B. 100g of component A and 80g of component B were mixed at 1500rpm, 60℃, and for 30s. The mixture was then poured into a plate mold and cured for 10 hours to obtain a 1mm thick sheet measuring 30mm x 30mm. The sheet properties were: compressive strength 45MPa, tensile strength 6.5MPa, and cement-stone interfacial bond strength 2MPa. The sheet was then pulverized to produce multiphase particles with an average particle size of 0.7mm-1.2mm. The BET specific surface area of ​​the multiphase particles was 18m². 2 / g; water contact angle is 38.5°; pH value is 8; apparent density is 1.35g / cm³. 3 The Si element content (calculated as Si) is 2.4 wt%.

[0155] Example 3

[0156] 100g of diphenylmethane diisocyanate (MDI) (Yantai Wanhua Chemical Group, MDI100) and 222.2g of polypropylene oxide glycol (Lanxing Group Shandong Dongda Chemical Co., Ltd., DL1000, number average molecular weight 1000, functionality 2) (100Gppg1000) were mixed and reacted at 95℃ for 3h to obtain a polyurethane prepolymer formed by polyisocyanate and polyether polyol (molar ratio of isocyanate to polyether polyol is 1.8:1). The NCO content of the polyurethane prepolymer was 4.64%, which was designated as component A. 100g of silicate aqueous solution (Zhangjiakou Tonglida Sodium Silicate Co., Ltd., TLD-38) (38% solid content) and 40g of heavy calcium carbonate (Hebei Yixian Shenglan Mineral Powder Factory, 280nm) were mixed for 3h to obtain component B. 100g of component A and 80g of component B were mixed at 2000rpm, 65℃, and for 35s. The mixture was then poured into a plate mold and cured for 10 hours to obtain a 1mm thick sheet measuring 30mm x 30mm. The sheet properties were: compressive strength 55MPa, tensile strength 8MPa, and cement-stone interfacial bond strength 2.7MPa. The sheet was then pulverized to produce multiphase particles with an average particle size of 0.5mm-1.1mm. The BET specific surface area of ​​the multiphase particles was 8.8m².2 / g; water contact angle is 37.5°; pH value is 9; apparent density is 1.35g / cm³. 3 The Si element content (calculated as Si) is 2.6 wt%.

[0157] Figure 3 This is the infrared spectrum of the multiphase particles in Example 3, 3350 cm⁻¹. -1 The presence of Si-OH (silanol) was observed at 1450 cm⁻¹. -1 The presence of a benzene ring (corresponding to an aromatic polyurethane) was observed at 2265 cm⁻¹. -1 The presence of the -NCO group is shown at this location.

[0158] Example 4

[0159] 100g of diphenylmethane diisocyanate (MDI) (Yantai Wanhua Chemical Group, MDI100) and 222.2g of polypropylene oxide glycol (Lanxing Group Shandong Dongda Chemical Co., Ltd., DL1000, number average molecular weight 1000, functionality 2) (100Gppg1000) were mixed and reacted at 95℃ for 3h to obtain a polyurethane prepolymer formed by polyisocyanate and polyether polyol (molar ratio of isocyanate to polyether polyol is 1.8:1). The NCO content of the polyurethane prepolymer was 4.64%, which was designated as component A. 100g of silicate aqueous solution (Zhangjiakou Tonglida Sodium Silicate Co., Ltd., TLD-38) (38% solid content) and 35g of heavy calcium carbonate (Hebei Yixian Shenglan Mineral Powder Factory, 280nm) were mixed for 3h to obtain component B. Mix 100g of component A and 100g of component B at 2000rpm, 70℃, for 20s. Pour the mixture into a plate mold and cure for 10h to obtain a 1mm thick sheet measuring 30mm x 30mm. The sheet properties are: compressive strength 65MPa, tensile strength 3.5MPa, and cement-stone interfacial bond strength 4.5MPa. The sheet is then pulverized to produce multiphase particles with an average particle size of 0.6mm-1.1mm. The BET specific surface area of ​​the multiphase particles is 26m². 2 / g; water contact angle is 37.5°; pH value is 9.5; apparent density is 1.45g / cm³. 3 The Si element content (calculated as Si) is 3.1 wt%.

[0160] Figure 1a These are SEM images (at different magnifications) of the multiphase particles in Example 4. Figure 1a As shown, the first phase is a porous continuous phase, and the second phase is substantially spherical. The pore size of the first phase is 5-10 micrometers, and the diameter of the spherical second phase is 2-8 micrometers. The second phase is embedded within the pores. Figure 1bThis is the EDS energy spectrum of the multiphase particles in Example 4, showing the content (in wt%) of each constituent element in the first and second phases, including the Si and C content. The porous continuous first phase has a Si content of 1.9 wt% and a C content of 76.5 wt%. The spherical second phase has a Si content of 19.6 wt% and a C content of 34.5 wt%. The ratio of the Si content (in wt%) in the second phase to the Si content (in wt%) in the first phase is 10.3.

[0161] Example 5

[0162] 100g of diphenylmethane diisocyanate (MDI) (Yantai Wanhua Chemical Group, MDI100) and 307.7g of polypropylene oxide glycol (Lanxing Group Shandong Dongda Chemical Co., Ltd., DL1000, number average molecular weight 1000, functionality 2) (100Gppg1000) were mixed and reacted at 95℃ for 3h to obtain a polyurethane prepolymer formed by polyisocyanate and polyether polyol (molar ratio of isocyanate to polyether polyol is 1.3:1). The NCO content of the polyurethane prepolymer was 1.9%, which was designated as component A. 100g of silicate aqueous solution (Zhangjiakou Tonglida Sodium Silicate Co., Ltd., TLD-38) (38% solid content) and 40g of heavy calcium carbonate (Hebei Yixian Shenglan Mineral Powder Factory, 280nm) were mixed for 3h to obtain component B. 400g of component A and 80g of component B were mixed at 2000rpm, 60℃, and for 35s. The mixture was then poured into a plate mold and cured for 10 hours to obtain a 1mm thick sheet measuring 30mm x 30mm. The sheet properties were: compressive strength 55MPa, tensile strength 10MPa, and cement-stone interfacial bond strength 3.0MPa. The sheet was then pulverized to produce multiphase particles with an average particle size of 0.5mm-1.1mm. The BET specific surface area of ​​the multiphase particles was 28m². 2 / g; water contact angle is 40°; pH value is 8; apparent density is 1.25g / cm³ 3 The content of Si (calculated as Si) is 0.99 wt%.

[0163] Figure 2a These are SEM images (at different magnifications) of the multiphase particles in Example 5. Figure 2a As shown, the second phase is a continuous phase with a soil-like loose structure, while the first phase is essentially prismatic. The prismatic first phase has a length of 4-8 micrometers and a diameter of 0.5-4 micrometers. Figure 2bThis is the EDS energy spectrum of the multiphase particles in Example 5, showing the elemental content (in wt%) of the first and second phases, including the Si and C content. The second phase has a soil-like loose structure with a Si content of 18.4 wt% and a C content of 20.9 wt%. The first phase is substantially prismatic with a Si content of 1.9 wt% and a C content of 65.2%. The ratio of the Si content (in wt%) in the second phase to that in the first phase is 9.7.

[0164] Example 6

[0165] 100g of diphenylmethane diisocyanate (MDI) (Yantai Wanhua Chemical Group, MDI100) and 266.7g of polypropylene oxide glycol (Lanxing Group Shandong Dongda Chemical Co., Ltd., DL1000, number average molecular weight 1000, functionality 2) (100Gppg1000) were mixed and reacted at 95℃ for 3h to obtain a polyurethane prepolymer formed by polyisocyanate and polyether polyol (molar ratio of isocyanate to polyether polyol is 1.5:1). The NCO content of the polyurethane prepolymer was 3.05%, which was designated as component A. 100g of silicate aqueous solution (Zhangjiakou Tonglida Sodium Silicate Co., Ltd., TLD-38) (38% solid content) and 55g of heavy calcium carbonate (Hebei Yixian Shenglan Mineral Powder Factory, 280nm) were mixed for 3h to obtain component B. 280g of component A and 80g of component B were mixed at 2000rpm, 65℃, and for 35s. The mixture was then poured into a plate mold and cured for 10 hours to obtain a 1mm thick sheet measuring 30mm x 30mm. The sheet properties were: compressive strength 62MPa, tensile strength 12MPa, and cement-stone interfacial bond strength 2.5MPa. The sheet was then pulverized to produce multiphase particles with an average particle size of 0.5mm-1.1mm. The BET specific surface area of ​​the multiphase particles was 25m². 2 / g; water contact angle is 36°; pH value is 7.5; apparent density is 1.2g / cm³ 3 The Si element content (calculated as Si) is 1.2 wt%.

[0166] Multiphase particulate materials were added to cement to prepare cement paste, and its mechanical properties were measured. The cement paste was cured at 90℃ for 24 hours. The specific results are as follows:

[0167] Example 7

[0168] (1) Weigh 500g of oil well cement, 50g of the multiphase particulate material prepared in Example 4, and 242g of deionized water. (Water-cement ratio 0.44)

[0169] (2) Mix cement and multiphase particulate materials evenly to obtain a mixed powder; add deionized water to a mixing container, and rotate the agitator at a low speed (4000±200 rpm) for 15 seconds to obtain a uniformly mixed powder. Cover the agitator and continue stirring at a high speed (12000±500 rpm) for 35 seconds until the mixture is uniformly mixed to obtain a cement paste system with a density of 1.86 g / cm³. 3 .

[0170] (3) Pour the above cement slurry into curing modules of 4cm×4cm×16cm (for measuring flexural strength and modulus of elasticity) and 5.08cm×5.08cm×5.08cm (for measuring compressive strength), respectively, and place them in a water bath at 90℃ for 24 hours. Take out the cement that has solidified to obtain cement stone modules.

[0171] (4) The compressive strength, flexural strength, and modulus of elasticity (modulus of elasticity of cement stone under one-third compressive strength) of the cement stone module were tested using a German Toni compressive and flexural strength tester (model: ToniPRAXFmax.300KN) at room temperature of 25℃. Test results: The compressive strength of the cement stone module was 35.7MPa, the flexural strength was 7.5MPa, and the modulus of elasticity was 7.5GPa.

[0172] Example 8

[0173] Weigh out 500g of oil well cement, 50g of the multiphase particulate material prepared in Example 3, and 242g of deionized water. (Water-cement ratio 0.44)

[0174] According to the operation method in Example 7(2), a cement slurry with a density of 1.86 g / cm³ was obtained. 3 According to the operation method in Example 7 (3), the cement stone module was obtained. According to the operation method in Example 7 (4), the test results were as follows: the compressive strength of the cement stone module was 27.6 MPa, the flexural strength was 7.2 MPa, and the elastic modulus was 7.1 GPa.

[0175] Example 9

[0176] Weigh out 500g of oil well cement, 50g of the multiphase particulate material prepared in Example 5, and 242g of deionized water. (Water-cement ratio 0.44)

[0177] According to the operation method in Example 7(2), a cement slurry with a density of 1.86 g / cm³ was obtained. 3 According to the operation method in Example 7 (3), the cement stone module was obtained. According to the operation method in Example 7 (4), the test results were as follows: the compressive strength of the cement stone module was 27.2 MPa, the flexural strength was 6.0 MPa, and the elastic modulus was 6.7 GPa.

[0178] Example 10

[0179] Weigh out 500g of oil well cement, 50g of the multiphase particulate material prepared in Example 1, and 242g of deionized water. (Water-cement ratio 0.44)

[0180] According to the operation method in Example 7(2), a cement slurry with a density of 1.86 g / cm³ was obtained. 3 According to the operation method in Example 7 (3), the cement stone module was obtained. According to the operation method in Example 7 (4), the test results were as follows: the compressive strength of the cement stone module was 24.5 MPa, the flexural strength was 6.1 MPa, and the elastic modulus was 6.9 GPa.

[0181] Example 11

[0182] Weigh out 500g of oil well cement, 25g of the multiphase particulate material prepared in Example 1, and 231g of deionized water. (Water-cement ratio 0.44)

[0183] Following the procedure in Example 7(2), a cement slurry with a density of 1.87 g / cm³ was obtained. 3 According to the operation method in Example 7 (3), the cement stone module was obtained. According to the operation method in Example 7 (4), the test results were as follows: the compressive strength of the cement stone module was 29.1 MPa, the flexural strength was 7.0 MPa, and the elastic modulus was 7.7 GPa.

[0184] Comparative Example 12

[0185] Preparation of blank cement paste (clean paste)

[0186] Weigh out 500g of oil well cement and 220g of deionized water. (Water-cement ratio 0.44)

[0187] Following the procedure in Example 7(2), a cement slurry with a density of 1.90 g / cm³ was obtained. 3 According to the operation method in Example 7 (3), the cement stone module was obtained. According to the operation method in Example 7 (4), the test results were as follows: the compressive strength of the cement stone module was 23.4 MPa, the flexural strength was 6.2 MPa, and the elastic modulus was 8.7 GPa.

[0188] The results show that the cement stone with added multiphase particulate material in Examples 7-11 has a lower elastic modulus than the cement stone of Comparative Example 12, but no decrease in strength.

Claims

1. A multiphase particle having a multiphase structure comprising a first phase and a second phase, wherein the multiphase structure has at least partially a morphology (1): the first phase is a continuous phase having at least partially a porous structure, the second phase is a dispersed phase, wherein at least one of the second phases has a spherical shape, and at least one spherical second phase is located within the pores of the porous structure of the first phase; or, the multiphase structure has at least partially a morphology (2): the second phase is a continuous phase, the first phase is a dispersed phase, wherein at least one of the first phases has a columnar shape; or, the multiphase structure has at least partially a morphology (3): a combination of the morphology (1) and the morphology (2), and the average particle size of the multiphase particle is at least 0.1 mm and at most 100 mm; The ratio of the Si element content in the second phase to the Si element content in the first phase is 5-20, wherein... The Si element content is expressed in wt%; The multiphase particles have surface silanol groups and surface -NCO groups; The Si element content of the multiphase particles is 0.5-5 wt% based on Si, and is calculated based on the total mass of the multiphase particles being 100 wt%. The composition includes at least an organic substance and a silicon-containing substance, and includes inorganic substances other than the silicon-containing substance, wherein the organic substance is polyurethane, the silicon-containing substance is selected from at least one of silicates and silicon dioxide, and the inorganic substances other than the silicon-containing substance are selected from at least one of carbonates, phosphates, sulfates and aluminates. The Si content of the second phase is 15-25 wt% based on Si, and the Si content of the first phase is 1-8 wt% based on Si.

2. The multiphase particles according to claim 1, characterized in that, The multiphase particles are composed of a first phase and a second phase.

3. The multiphase particles according to claim 1, characterized in that, In morphology (1), more than 50% of the second phase has a spherical shape.

4. The multiphase particles according to claim 1, characterized in that, In morphology (1), more than 60% of the second phase has a spherical shape.

5. The multiphase particles according to claim 1, characterized in that, In morphology (1), more than 80% of the second phase has a spherical shape.

6. The multiphase particles according to claim 1, characterized in that, In morphology (1), more than 90% of the second phase has a spherical shape.

7. The multiphase particles according to claim 1, characterized in that, In morphology (1), all of the second phases have a spherical shape.

8. The multiphase particles according to claim 1, characterized in that, In morphology (1), more than 50% of the total number of the spherical second phases are located within the pores of the porous structure of the first phase.

9. The multiphase particles according to claim 1, characterized in that, In morphology (1), more than 50% of the total number of the spherical second phases are located within the circular pores of the porous structure of the first phase.

10. The multiphase particles according to claim 1, characterized in that, In morphology (1), more than 60% of the total number of the spherical second phases are located within the pores of the porous structure of the first phase.

11. The multiphase particles according to claim 1, characterized in that, In morphology (1), more than 60% of the total number of the spherical second phases are located within the circular pores of the porous structure of the first phase.

12. The multiphase particles according to claim 1, characterized in that, In morphology (1), more than 80% of the total number of the spherical second phases are located within the pores of the porous structure of the first phase.

13. The multiphase particles according to claim 1, characterized in that, In morphology (1), more than 80% of the total number of the spherical second phases are located within the circular pores of the porous structure of the first phase.

14. The multiphase particles according to claim 1, characterized in that, In morphology (1), more than 90% of the total number of the spherical second phases are located within the pores of the porous structure of the first phase.

15. The multiphase particles according to claim 1, characterized in that, In morphology (1), more than 90% of the total number of the spherical second phases are located within the circular pores of the porous structure of the first phase.

16. The multiphase particles according to claim 1, characterized in that, In morphology (1), all of the spherical second phases are located within the pores of the porous structure of the first phase.

17. The multiphase particles according to claim 1, characterized in that, In morphology (1), all of the spherical second phases are located within the circular pores of the porous structure of the first phase.

18. The multiphase particles according to claim 1, characterized in that, In morphology (2), the second phase has a loose structure or an amorphous structure.

19. The multiphase particles according to claim 1, characterized in that, In morphology (2), more than 50% of the first phase has a columnar shape.

20. The multiphase particles according to claim 1, characterized in that, In morphology (2), more than 50% of the first phases have a columnar shape selected from cylinders and prisms.

21. The multiphase particles according to claim 1, characterized in that, In morphology (2), more than 60% of the first phase has a columnar shape.

22. The multiphase particles according to claim 1, characterized in that, In morphology (2), more than 60% of the first phases have a columnar shape selected from at least one of cylinders and prisms.

23. The multiphase particles according to claim 1, characterized in that, In morphology (2), more than 80% of the first phase has a columnar shape.

24. The multiphase particles according to claim 1, characterized in that, In morphology (2), more than 80% of the first phases have a columnar shape selected from cylinders and prisms.

25. The multiphase particles according to claim 1, characterized in that, In morphology (2), more than 90% of the first phase has a columnar shape.

26. The multiphase particles according to claim 1, characterized in that, In morphology (2), more than 90% of the first phases have a columnar shape selected from cylinders and prisms.

27. The multiphase particles according to claim 1, characterized in that, In morphology (2), all of the first phases have a columnar shape.

28. The multiphase particles according to claim 1, characterized in that, In morphology (2), all of the first phases have a columnar shape selected from at least one of cylinders and prisms.

29. The multiphase particles according to claim 1, characterized in that, The average particle size of the multiphase particles is at least 0.2 mm.

30. The multiphase particles according to claim 1, characterized in that, The average particle size of the multiphase particles is at least 0.35 mm.

31. The multiphase particles according to claim 1, characterized in that, The average particle size of the multiphase particles is at least 0.5 mm.

32. The multiphase particles according to claim 1, characterized in that, The average particle size of the multiphase particles is at least 0.75 mm.

33. The multiphase particles according to claim 1, characterized in that, The average particle size of the multiphase particles is at least 0.8 mm.

34. The multiphase particles according to claim 1, characterized in that, The average particle size of the multiphase particles is at most 50 mm.

35. The multiphase particles according to claim 1, characterized in that, The average particle size of the multiphase particles is at most 20 mm.

36. The multiphase particles according to claim 1, characterized in that, The average particle size of the multiphase particles is at most 10 mm.

37. The multiphase particles according to claim 1, characterized in that, The average particle size of the multiphase particles is at most 5 mm.

38. The multiphase particles according to claim 1, characterized in that, The average particle size of the multiphase particles is at most 2 mm.

39. The multiphase particles according to claim 1, characterized in that, The average particle size of the multiphase particles is at most 1.2 mm.

40. The multiphase particles according to claim 1, characterized in that, The average particle size of the multiphase particles is at most 1.0 mm.

41. The multiphase particles according to claim 1, characterized in that, The ratio of the Si content in the second phase to the Si content in the first phase is 8-12.

42. The multiphase particles according to claim 41, characterized in that, The ratio of the Si content in the second phase to the Si content in the first phase is 9-11.

43. The multiphase particles according to claim 1, characterized in that, The specific surface area of ​​the multiphase particles obtained by the BET method is 1-200 m². 2 / g, and / or, the water contact angle of the multiphase particles is 20-60°, and / or, the pH value of the multiphase particles is 7-10, and / or, the apparent density of the multiphase particles is 1.1-1.6 g / cm³. 3 .

44. The multiphase particles according to claim 43, characterized in that, The specific surface area of ​​the multiphase particles obtained by the BET method is 5-50 m². 2 / g.

45. The multiphase particles according to claim 44, characterized in that, The specific surface area of ​​the multiphase particles obtained by the BET method is 10-30 m². 2 / g.

46. ​​The multiphase particles according to claim 43, characterized in that, The contact angle of the multiphase particles with water is 25-50°.

47. The multiphase particles according to claim 46, characterized in that, The contact angle of the multiphase particles with water is 30-45°.

48. The multiphase particles according to claim 47, characterized in that, The contact angle of the multiphase particles with water is 35-40°.

49. The multiphase particles according to claim 43, characterized in that, The multiphase particles have a pH value of 7.5-9.

50. The multiphase particles according to claim 49, characterized in that, The pH value of the multiphase particles is 8-9.

51. The multiphase particles according to claim 43, characterized in that, The apparent density of the multiphase particles is 1.2-1.3 g / cm³. 3 .

52. The multiphase particles according to claim 1, characterized in that, In morphology (1), the diameter of the spherical second phase is 0.1-50 micrometers.

53. The multiphase particles according to claim 52, characterized in that, In morphology (1), the aperture size of the hole is 0.05-100 micrometers.

54. The multiphase particles according to claim 52, characterized in that, In morphology (2), the length of the columnar first phase is 0.1-50 micrometers and the diameter is 0.1-10 micrometers.

55. The multiphase particles according to claim 52, characterized in that, The Si element content of the multiphase particles is 0.5-5 wt% based on Si, and is calculated based on the total mass of the multiphase particles being 100 wt%.

56. The multiphase particles according to claim 52, characterized in that, In morphology (1), the spherical second phase is located within the hole, and the ratio of the orifice size of the hole to the diameter of the spherical second phase is at least 1 and at most 10.

57. The multiphase particles according to claim 52, characterized in that, In morphology (1), the diameter of the spherical second phase is 0.2-25 micrometers.

58. The multiphase particles according to claim 57, characterized in that, In morphology (1), the diameter of the spherical second phase is 0.5-20 micrometers.

59. The multiphase particles according to claim 58, characterized in that, In morphology (1), the diameter of the spherical second phase is 1-10 micrometers.

60. The multiphase particles according to claim 59, characterized in that, In morphology (1), the diameter of the spherical second phase is 2-8 micrometers.

61. The multiphase particles according to claim 53, characterized in that, In morphology (1), the aperture size of the hole is 0.2-50 micrometers.

62. The multiphase particles according to claim 61, characterized in that, In morphology (1), the aperture size of the hole is 0.5-25 micrometers.

63. The multiphase particles according to claim 62, characterized in that, In morphology (1), the aperture size of the hole is 1-15 micrometers.

64. The multiphase particles according to claim 54, characterized in that, In morphology (2), the length of the columnar first phase is 0.2-20 micrometers.

65. The multiphase particles according to claim 64, characterized in that, In morphology (2), the length of the columnar first phase is 0.5-10 micrometers.

66. The multiphase particles according to claim 65, characterized in that, In morphology (2), the length of the columnar first phase is 1-5 micrometers.

67. The multiphase particles according to claim 52, characterized in that, In morphology (2), the diameter of the columnar first phase is 2-5 micrometers.

68. The multiphase particles according to claim 55, characterized in that, The Si element content of the multiphase particles is 1-3.5 wt% (based on Si).

69. The multiphase particles according to claim 56, characterized in that, In morphology (1), the spherical second phase is located inside the hole, and the ratio of the hole opening size to the diameter of the spherical second phase is greater than 1.

70. The multiphase particles according to claim 69, characterized in that, In morphology (1), the spherical second phase is located within the hole, and the ratio of the orifice size of the hole to the diameter of the spherical second phase is at least 1.

05.

71. The multiphase particles according to claim 70, characterized in that, In morphology (1), the spherical second phase is located within the hole, and the ratio of the orifice size of the hole to the diameter of the spherical second phase is at least 1.

1.

72. The multiphase particles according to claim 71, characterized in that, In morphology (1), the spherical second phase is located within the hole, and the ratio of the orifice size of the hole to the diameter of the spherical second phase is at least 1.

15.

73. The multiphase particles according to claim 72, characterized in that, In morphology (1), the spherical second phase is located within the hole, and the ratio of the orifice size of the hole to the diameter of the spherical second phase is at least 1.

2.

74. The multiphase particles according to claim 56, characterized in that, In morphology (1), the spherical second phase is located within the hole, and the ratio of the orifice size of the hole to the diameter of the spherical second phase is at most 5.

75. The multiphase particles according to claim 74, characterized in that, In morphology (1), the spherical second phase is located within the hole, and the ratio of the orifice size of the hole to the diameter of the spherical second phase is at most 2.

76. The multiphase particles according to claim 75, characterized in that, In morphology (1), the spherical second phase is located within the hole, and the ratio of the orifice size of the hole to the diameter of the spherical second phase is at most 1.

5.

77. The multiphase particles according to claim 1, characterized in that, The organic material is an aromatic polyurethane, and / or the inorganic material other than the silicon-containing material is selected from at least one inorganic material in the carbonate group.

78. The multiphase particles according to claim 1, characterized in that, The Si content of the second phase is 18-21 wt% based on Si, and the Si content of the first phase is 1.5-5 wt% based on Si.

79. The use of the multiphase particles according to any one of claims 1-78 as a toughening agent.

80. An inorganic cementitious composition comprising at least an inorganic cementitious material and multiphase particles according to any one of claims 1-78, wherein the multiphase particles are 0.5-50 parts by weight relative to 100 parts by weight of the inorganic cementitious material.

81. The inorganic gelling composition according to claim 80, characterized in that, The inorganic cementing material is a hydraulic inorganic cementing material.

82. The inorganic gelling composition according to claim 81, characterized in that, The inorganic cementitious material is cement.

83. The inorganic cementitious composition according to claim 80, characterized in that, Compared to 100 parts by weight of the inorganic cementitious material, the multiphase particles are 5-30 parts by weight.

84. The inorganic cementitious composition according to claim 83, characterized in that, Compared to 100 parts by weight of the inorganic cementitious material, the multiphase particles are 10-20 parts by weight.

85. A method for manufacturing an inorganic cementitious composition, comprising at least the step of mixing an inorganic cementitious material with multiphase particles according to any one of claims 1-78, wherein the multiphase particles are 0.5-50 parts by weight relative to 100 parts by weight of the inorganic cementitious material.

86. The manufacturing method according to claim 85, characterized in that, The inorganic cementing material is a hydraulic inorganic cementing material.

87. The manufacturing method according to claim 86, characterized in that, The inorganic cementitious material is cement.

88. The manufacturing method according to claim 85, characterized in that, Compared to 100 parts by weight of the inorganic cementitious material, the multiphase particles are 5-30 parts by weight.

89. The manufacturing method according to claim 86, characterized in that, Compared to 100 parts by weight of the inorganic cementitious material, the multiphase particles are 10-20 parts by weight.

90. A method for toughening an inorganic cementitious material, comprising at least the step of introducing multiphase particles according to any one of claims 1-78 into the inorganic cementitious material, wherein the multiphase particles are 0.5-50 parts by weight relative to 100 parts by weight of the inorganic cementitious material.

91. The toughening method according to claim 90, characterized in that, The inorganic cementing material is a hydraulic inorganic cementing material.

92. The toughening method according to claim 91, characterized in that, The inorganic cementitious material is cement.

93. The toughening method according to claim 90, characterized in that, Compared to 100 parts by weight of the inorganic cementitious material, the multiphase particles are 5-30 parts by weight.

94. The toughening method according to claim 93, characterized in that, Compared to 100 parts by weight of the inorganic cementitious material, the multiphase particles are 10-20 parts by weight.

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